EP0983285A1 - Diesters d'acides dicarboxyliques de ferrocenes et combustibles solides composites les contenant - Google Patents

Diesters d'acides dicarboxyliques de ferrocenes et combustibles solides composites les contenant

Info

Publication number
EP0983285A1
EP0983285A1 EP98925522A EP98925522A EP0983285A1 EP 0983285 A1 EP0983285 A1 EP 0983285A1 EP 98925522 A EP98925522 A EP 98925522A EP 98925522 A EP98925522 A EP 98925522A EP 0983285 A1 EP0983285 A1 EP 0983285A1
Authority
EP
European Patent Office
Prior art keywords
solid composite
solid
ferrocendicarboxylic
composite fuel
fuel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98925522A
Other languages
German (de)
English (en)
Inventor
Hans-Peter Mackowiak
Klaus Gottlieb
Hubert Jungbluth
Horst Neitsch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hebekreuzer Hans-Peter
Dynamit Nobel AG
Chemische Betriebe Pluto GmbH
Dynamit Nobel GmbH Explosivstoff und Systemtechnik
Original Assignee
Hebekreuzer Hans-Peter
Dynamit Nobel AG
Chemische Betriebe Pluto GmbH
Dynamit Nobel GmbH Explosivstoff und Systemtechnik
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hebekreuzer Hans-Peter, Dynamit Nobel AG, Chemische Betriebe Pluto GmbH, Dynamit Nobel GmbH Explosivstoff und Systemtechnik filed Critical Hebekreuzer Hans-Peter
Publication of EP0983285A1 publication Critical patent/EP0983285A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin

Definitions

  • Ferrocendicarboxylic acid diesters and composite solid fuels containing them
  • the invention relates to ferrocendicarboxylic acid diesters of the general formula
  • Ferrocenyl esters are known in principle from the prior art, for. B. the 2- (2-n-butoxyethoxy) ethyl ferrocene from US 3,558,680, which can be prepared from ferrocene carboxylic acid and 2- (2-n-butoxyethoxy) ethanol.
  • Ferrocene derivatives are used in a wide range of areas, including as combustion moderators for solid fuels. Most of the known ferrocene-based combustion moderators, however, show the undesirable property of migration, i.e. they migrate from the rubber-elastic binder matrix of the solid fuel into the surrounding insulation material, which leads to irregular erosion and a deterioration in the aging resistance of the solid fuel.
  • the object of the present invention is to provide ferrocendicarboxylic acid diesters which have no tendency to migrate in solid fuels and nevertheless have good to excellent combustion behavior. They are said to be particularly suitable as combustion moderators for solid fuels. Furthermore, they should have a low viscosity and a low vapor pressure.
  • X is an oligoethylene glycol residue with 2 to 20 ethoxy units and / or an ⁇ , ⁇ -alkyldiol residue with 2 to 8 C atoms.
  • This compound has particularly favorable properties, in particular with regard to the viscosity and the vapor pressure.
  • the compounds in which the alkyldiol radical has 2 to 8 C atoms are particularly suitable for the same reasons.
  • the aliphatic chain of the alkyldiol radicals having 3 to 8 carbon atoms can also be branched. However, compounds with a linear carbon chain are preferred.
  • a suitable way of producing the ferrocendicarboxylic acid diesters according to the invention is synthesis via ferrocendi (carboxylic acid chloride).
  • ferrocendi carboxylic acid chloride
  • an excess of the corresponding diol or glycol compound is used.
  • a method based on the corresponding ferrocene dicarboxylic acid is preferred.
  • a stoichiometric excess of the diol or glycol compound is generally used.
  • carboxylic acids generally react slowly with alcohols due to the low carbonyl activity.
  • the esterification can be considerably accelerated by adding catalysts, usually typical esterification catalysts, in particular anhydrous hydrogen chloride.
  • the reaction mixture can be saturated with dry hydrogen chloride gas at the beginning of the reaction or dry hydrogen chloride gas can be passed through the reaction mixture during the entire reaction.
  • the ferrocendicarboxylic acid diesters according to the invention can be used, inter alia. in composite solid fuels.
  • Another object was therefore to provide solid composite fuels which do not have the disadvantages of the composite solid fuels known from the prior art, but which are distinguished by improved combustion behavior. According to the invention, this object was achieved by a composite solid propellant with the features of claim 9. Preferred embodiments are characterized in claims 10 to 28.
  • the ferrocendicarboxylic acid diesters according to the invention have a liquid, not too viscous consistency and miscibility with the binder polymers of the composite solid fuels and, because of their terminal OH groups, they have a clearly reproducible binding functionality with constant equivalence values, they ensure a constant pouring viscosity of the ready-mixed fuel slurries Negative influence hardening reaction or pot life. In addition, they show no significant impairment of the rubber-elastic properties of the binder polymer z. B. by increasing the crosslink density. They are stable to oxidation in the composite solid propellant matrix, so that the stability of the composite solid propellant is not impaired. The safety properties of the solid composite fuel are not adversely affected by the incorporation of the substances according to the invention.
  • the ferrocendicarboxylic acid diester derivatives according to the invention serve as combustion moderators in the solid composite fuel.
  • the binder used in the solid composite fuel fixes the ferrocendicarboxylic acid diester derivatives according to the invention via their terminal hydroxyl groups.
  • Suitable polymer binders for the composite solid propellants according to the invention consist of prepolymers with terminal hydroxyl groups, which are reacted with suitable linking reagents to form the actual binder.
  • prepolymers are polyurethane binders such as polybutadiene (HTPB), polyester polyols or polyether polyols.
  • Linking reagents to be used are, for example, bifunctional or trifunctional isocyanates, preferably isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI) or mixtures thereof. Toluene diisocyanate (TDI) is particularly preferably used.
  • triols of bifunctional isocyanates for example trimethylolpropane, trimethylolethane or 1,2,4-butanetriol, trifunctional polyethers or polyesters in a molar concentration corresponding approximately to the ferrocendicarboxylic acid diester derivative.
  • Preferred polyurethane prepolymers are polybutadienes (HTPB) with terminal hydroxyl groups with an average molecular weight of 400 to 4000, preferably 1000 to 3000.
  • polymer binders made from a crosslinkable mixture of hydroxyl-containing polymers and a polymer based on a 1,3-butadiene with pendant succinic anhydride groups have been found to be particularly suitable. These polymer binders harden in the heat. The use of such polymers as binders for blowing agent bodies is described in DE-PS 38 09 297.
  • the hydroxyl-containing polymer generally has an average molecular weight between 1,000 and 10,000 and a hydroxyl number between 5 and 200 [mg KOH / g]. A hydroxyl-containing polybutadiene is particularly preferred.
  • hydroxyl-containing polymers that are liquid at room temperature can also be used. These include the polyester polyols or polyether polyols already mentioned above, the polyethylene polyols or the polypropylene polyols.
  • the reaction partner based on 1,3-butadiene with pendant succinic anhydride groups is generally also referred to as a maleated butadiene polymer.
  • the composite solid propellant according to the invention comprises, as high-energy fuels, crystalline explosives, for example the nitramines hexogen or octogen, aromatic or aliphatic nitro compounds or amino-nitro compounds, the use of which in fuels is known per se. Mixtures of the explosives can also be used.
  • a crystalline inorganic oxidizing agent from the group of alkali metal, alkaline earth metal and ammonium chlorates, perchlorates or nitrates, preferably ammonium perchlorate, can be used as the oxidizing agent (AP) or ammonium nitrate (AN), or mixtures of these oxidizing agents can be used.
  • a preferred composition of the solid composite fuel consists of 40 to 85% by mass of the high-energy fuel, 1 to 40% by mass of the oxidizing agent, 10 to 45% by mass of binder and 0.1 to 10% by mass of the ferrocendicarboxylic acid diester derivative according to the invention .
  • Conventional additives such as antioxidants, stabilizers, plasticizers and / or adhesion promoters can optionally be added.
  • the substances to be used are known to the person skilled in the art.
  • Additives known per se for example metal powder such as aluminum, magnesium, titanium, boron and / or iron, can optionally be added to increase the performance.
  • the type and amount of additives to be used depends on the fuel or oxidizing agent selected.
  • the amount of additives is between 0.1 and 2.0% by mass; the amount of additives can make up to 15% by mass, based in each case on the solid composite fuel.
  • the combustion moderators according to the invention it is also possible to use other combustion moderators known per se, as well as emulsifiers and lubricants. Mixtures of the components mentioned can also be used.
  • the composite solid propellants according to the invention with a binder composed of a prepolymer having terminal hydroxyl groups and isocyanates as the linking reagents can be prepared by mixing the liquid prepolymer with the ferrocendicarboxylic acid diester derivative according to the invention, the fuel and the linking reagent to form a slurry and the ferrocendicarboxylic acid diester derivative in the binder is involved.
  • the linking reagent can also be added after the other constituents have been mixed.
  • the composite fuels according to the invention are produced in a manner known per se using a polymer binder from a crosslinkable mixture of hydroxyl-containing polymers and a polymer based on 1,3-butadiene with pendant succinic anhydride groups. All compo- nents can be mixed together. It is particularly advantageous when using this polymer binding system that the mixture obtained can be stored in the non-crosslinked state for a long time without negative changes occurring.
  • the mixture is then thoroughly kneaded at room temperature and then processed into composite solid propellant moldings of the desired dimension, for example pressed into strands. After this shaping, the polymer binder is cured by heat treatment.
  • the curing temperature depends on the binder system chosen. Generally it is above 35 ° C. The upper limit of the curing temperature should be significantly below the deflagration or decomposition temperature of the fuel used.
  • the ferrocendicarboxylic acid diesters according to the invention can also be used as non-halogenated reactive flame retardants and as surfactants.
  • the starting materials are introduced into a reflux reaction apparatus, heated to 60 ° C. with stirring and kept at this temperature for 6 hours.
  • the reaction product is then mixed with 500 ml of methylene chloride, with saturated
  • the yield is 88.5% based on ferrocendi (carboxylic acid chloride).
  • the experimental apparatus consisted of a multi-necked flask with stirrer, thermometer, reflux condenser and gas inlet pipe.
  • the components to be used are mixed in the desired mixing ratio, the mixture is kneaded for about 30 minutes at room temperature and then pressed into the desired shape, for example into strands.
  • the composite solid propellants obtained are elastic even at temperatures down to -40 ° C and show no brittle fracture.
  • samples were tempered at 105 ° C for 78 hours. Then the weight loss is determined in the so-called Holland test. No significant weight loss could be observed with any of the composite solid propellants according to the invention.
  • the following table shows some formulations of composite solid propellants according to the invention, as well as the burning rates and the pressure exponents determined at 20 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Ces diesters d'acides dicarboxyliques de ferrocènes répondent à la formule (I), dans laquelle X désigne un radical oligoéthylène glycol avec 2 à 20 unités éthoxy et/ou un radical alpha , omega -alkyldiol avec 2 à 18 atomes de C. L'invention concerne également leurs procédés de préparation, leur utilisation, des combustibles solides composites qui contiennent ces diesters d'acides dicarboxyliques de ferrocènes et leurs procédés de préparation.
EP98925522A 1997-05-07 1998-05-02 Diesters d'acides dicarboxyliques de ferrocenes et combustibles solides composites les contenant Withdrawn EP0983285A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19719126 1997-05-07
DE19719126 1997-05-07
PCT/EP1998/002600 WO1998050396A1 (fr) 1997-05-07 1998-05-02 Diesters d'acides dicarboxyliques de ferrocenes et combustibles solides composites les contenant

Publications (1)

Publication Number Publication Date
EP0983285A1 true EP0983285A1 (fr) 2000-03-08

Family

ID=7828786

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98925522A Withdrawn EP0983285A1 (fr) 1997-05-07 1998-05-02 Diesters d'acides dicarboxyliques de ferrocenes et combustibles solides composites les contenant

Country Status (5)

Country Link
US (1) US6313334B1 (fr)
EP (1) EP0983285A1 (fr)
DE (1) DE19819587A1 (fr)
NO (1) NO995374D0 (fr)
WO (1) WO1998050396A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITBO20010308A1 (it) * 2001-05-17 2002-11-17 Univ Bologna Procedimento per la preparazione di complessi metallici contenenti unlegante idrossialcossicarbonil - ciclopentadienilico
WO2004016160A2 (fr) * 2002-08-19 2004-02-26 Iowa State University Research Foundation, Inc. Nanoparticules polymeres redox
US8114229B1 (en) * 2008-03-27 2012-02-14 University Of Central Florida Research Foundation, Inc. Self-extinguishable solid propellant
CN103288886B (zh) * 2013-06-17 2015-05-20 陕西师范大学 双核二茂铁高氮含能离子化合物及其制备方法
CN110305174B (zh) * 2019-05-28 2023-03-24 黎明化工研究设计院有限责任公司 一种制备二茂铁二羧酸二羟烷基酯的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3558680A (en) * 1962-09-27 1971-01-26 Thiokol Chemical Corp Ferrocene derivative
US3932240A (en) * 1973-06-04 1976-01-13 The United States Of America As Represented By The Secretary Of The Navy Burning rate modifying binder for propellant and method
DE19516517C1 (de) * 1995-05-05 1997-02-06 Pluto Chem Betriebe Ferrocenverbindungen, Verfahren zu deren Herstellung sowie der Zwischenprodukte

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9850396A1 *

Also Published As

Publication number Publication date
US6313334B1 (en) 2001-11-06
NO995374L (no) 1999-11-03
WO1998050396A1 (fr) 1998-11-12
NO995374D0 (no) 1999-11-03
DE19819587A1 (de) 1998-11-12

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