DK154948B - FURTHER BINDING AGENT, FUEL INCLUDING SUCH A BINDING AGENT AND PROCEDURE FOR MANUFACTURING THE FUEL - Google Patents
FURTHER BINDING AGENT, FUEL INCLUDING SUCH A BINDING AGENT AND PROCEDURE FOR MANUFACTURING THE FUEL Download PDFInfo
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- DK154948B DK154948B DK015577AA DK15577A DK154948B DK 154948 B DK154948 B DK 154948B DK 015577A A DK015577A A DK 015577AA DK 15577 A DK15577 A DK 15577A DK 154948 B DK154948 B DK 154948B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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Description
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Den foreliggende opfindelse angår et hærdeligt bindemiddel til anvendelse ved fremstilling af et støbeligt, sammensat drivmiddel. Opfindelsen angår endvidere drivmidlet omfattende et sådant bindemiddel samt en fremgangsmåde til fremstilling af drivmidlet.The present invention relates to a curable binder for use in the manufacture of a castable composite propellant. The invention further relates to the propellant comprising such a binder as well as to a process for preparing the propellant.
Støbelige drivmidler, der er baseret på polybutadien-holdige bindemidler i forbindelse med f.eks. ammonium-perchlorat-oxidations-midler er kendt. De mekaniske og ballistiske egenskaber af sådanne sammensatte, faste drivmidler afhænger meget af kvaliteten af den klæbende binding mellem bindemidlet og oxidationsmidlet, som diskuteret i beskrivelsen til USA patent nr. 3 745 074. Man kender systemer, der udviser rimelig god adhæsion mellem brændstof-Castable propellants based on polybutadiene-containing binders in connection with e.g. ammonium perchlorate oxidants are known. The mechanical and ballistic properties of such composite solid propellants greatly depend on the quality of the adhesive bond between the binder and the oxidizing agent, as discussed in U.S. Patent No. 3,745,074, which discloses systems which exhibit reasonably good adhesion between
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bindemidlet og oxidationsmidlet, men sådanne systemer har andre ulemper.the binder and the oxidant, but such systems have other disadvantages.
Ved et sådant kendt system anvendes bindemidler med carboxyl-termi-neret polybutadien (CTPB), hærdet med aziridiner eller epoxider eller blandinger deraf. Sådanne drivmidler udviser stor forlængelse over et bredt temperaturinterval og en relativt stor evne til at bære faste partikler, udtrykt som belastning af tørstoffer. Adhæsionen mellem bindemiddel og oxidationsmiddel er ret god, da det foretrukne aziridinhærdemiddel, tris(2-methyl-aziridinyl-1)phosphin-oxid kendt som MAPO, polymeriserer omkring partiklerne af ammoniumperchlorat-oxidationsmidlet til frembringelse af et stærkt lag, der er bundet til hovedportionen af bindemidlet ved kemiske bindinger. Dette system har dog de ulemper, at der kræves et kompliceret hærdeystem, at drivmidlerne har ringe ældningsegenskaber, når de udsættes for høj temperatur, og at egenskaberne af det polymere bindemiddel varierer fra en portion til en anden.In such a known system, binders are used with carboxyl-terminated polybutadiene (CTPB), cured with aziridines or epoxides or mixtures thereof. Such propellants exhibit great elongation over a wide range of temperatures and a relatively high ability to support solid particles, expressed as a load of solids. The adhesion between binder and oxidant is quite good as the preferred aziridine curing agent, tris (2-methyl-aziridinyl-1) phosphine oxide known as MAPO, polymerizes around the particles of the ammonium perchlorate oxidant to produce a strong layer bound to the major portion. of the binder by chemical bonds. However, this system has the disadvantages that a complicated curing system is required, that the propellants have poor aging properties when exposed to high temperature, and that the properties of the polymeric binder vary from one portion to another.
Et andet system, der blev udviklet i et forsøg på at overvinde ulemperne ved de foregående systemer, omfatter sammensatte drivmidler på basis af HTPB, baseret på hydroxyterminerede poly-butadien-præpolymere. Disse systemer hærdes med diisocyanater. Disse drivmidler krævede anvendelse af et bindemiddel til opnåelse af god adhæsion af bindemidlet til partiklerne af oxidationsmiddel. Aziridin-polyestere er effektive bindemidler til disse drivmidler, hvorved en foretrukken aziridin-polyester er et reaktionsprodukt af MåPO med disyrer. Imidlertid må dette foretrukne bindemiddel syntetiseres in situ i relativt små mængder, fordi det har en kort lager-holdbarhed ved stuetemperatur og må opbevares ved lav temperatur for at forlænge anvendeligheden deraf, og der kræves en relativt høj koncentration, ca, 2 til 3 % aziridin-polyester i bindemidlet, til at opnå en effektiv adhæsion mellem oxidationsmidlet og bindemidlet, især når belastningen med tørstoffet er høj.Another system developed in an attempt to overcome the disadvantages of the preceding systems comprises compound propellants based on HTPB based on hydroxy terminated polybutadiene prepolymers. These systems are cured with diisocyanates. These propellants required the use of a binder to achieve good adhesion of the binder to the particles of oxidizing agent. Aziridine polyesters are effective binders for these propellants, wherein a preferred aziridine polyester is a reaction product of MåPO with diacids. However, this preferred binder must be synthesized in situ in relatively small quantities because it has a short shelf life at room temperature and must be stored at low temperature to extend its usefulness and a relatively high concentration, about 2 to 3% aziridine, is required. polyester in the binder, to achieve an effective adhesion between the oxidizing agent and the binder, especially when the dry matter load is high.
Den foreliggende opfindelse er baseret på den erkendelse, at en kombination af to bindemidler, aziridin-polyester og en amin-polyester, med drivmidler af HTPB-typen tilvejebringer en passende adhæsion til opretholdelse af drivmidlets spændingsegenskaber og muliggør en redukThe present invention is based on the recognition that a combination of two binders, aziridine polyester and an amine polyester, with HTPB type propellants provides an appropriate adhesion to maintain the tension properties of the propellant and allows for a reduction.
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tion med en faktor på 3 til 4 i mængden af aziridin-polyester, som kræves i sammenligning med de kendte systemer. Drivmiddelsystemer ifølge opfindelsen har f.eks. forbedrede mekaniske egenskaber, herunder- forbedret forlængelse under maximal belastning og ved brud med sammenlignelig brudstyrke og initiale moduler under henvisning til ΗΊΤΒ drivmiddelsystemer, som kun gør brug af som bindemiddel tjenende aziridin-polyester.by a factor of 3 to 4 in the amount of aziridine polyester required in comparison with the known systems. Fuel systems according to the invention have e.g. improved mechanical properties, including- improved elongation under maximum load and at breakage with comparable breaking strength and initial modules with reference to ΗΊΤΒ propellant systems which use only aziridine-polyester binder.
Opfindelsen tilvejebringer således et hærdeligt bindemiddel til anvendelse ved dannelse af et støbeligt drivmiddel, der omfatter: 1. en hydroxy-termineret butadien-rpolymer, 2. et diisocyanat-hærdemiddel, og 3. et bindemiddelsystem af en aziridin-polyester, som er reaktionsproduktet af et aziridin-phosphin-oxid og i det mindste en polycarbox-ylsyre, og en amin-polyester, der er reaktionsproduktet af en alkanol-amin og en mættet alifatisk polycarboxylsyre. Yderligere kan der være inkorporeret en antioxidant, såsom phenyl-beta-naphthyl-amin, sammen med isodecyl-pelargonat, som blødgøringsmiddel.Thus, the invention provides a curable binder for use in forming a moldable propellant comprising: 1. a hydroxy-terminated butadiene polymer, 2. a diisocyanate curing agent, and 3. an aziridine polyester binder system which is the reaction product of an aziridine phosphine oxide and at least one polycarboxylic acid, and an amine polyester which is the reaction product of an alkanol amine and a saturated aliphatic polycarboxylic acid. Further, an antioxidant such as phenyl-beta-naphthylamine may be incorporated together with isodecyl pelargonate as a plasticizer.
Opfindelsen angår yderligere et støbeligt drivmiddel, der omfatter det før angivne bindemiddel, og hvori der homogent er dis-pergeret et findelt perchlorat-oxidationsmiddel i di- eller tri-modale fordelinger, og andre fakultative bestanddele, såsom et metaladditiv. Opfindelsen tilvejebringer tillige en fremgangsmåde til fremstilling af det sammensatte drivmiddel under opnåelse af god dispergering af bestanddelene og reproducerbarhed af mekaniske og ballistiske egenskaber.The invention further relates to a moldable propellant comprising the aforementioned binder and wherein a finely divided perchlorate oxidant is dispersed in di- or tri-modal distributions and other optional constituents such as a metal additive. The invention also provides a process for preparing the composite propellant while obtaining good dispersion of the constituents and reproducibility of mechanical and ballistic properties.
De HTPB-præpolymere, der er velegnet i bindemiddel- og drivmiddelsystemerne ifølge opfindelsen, er for eksempel af den type, der er genstand for canadisk patent 891.562 eller USA patent 3.792.003.For example, the HTPB prepolymers suitable in the binder and propellant systems of the invention are of the type subject to Canadian Patent 891,562 or U.S. Patent 3,792,003.
De præpolymere, der er beskrevet deri, er hydroxy-telecheliske polybutadiener, især hydroxy-terminerede polybutadiener, der fortrinsvis er rige på cis-isomer. De fremkommer ved reaktion mellem en mono-epoxy-forbindelse og de tilsvarende carboxy-polymere. Produktet er en polymer med hydroxylgrupper, herunder primære og sekundære grupper af den art, som sidder i umiddelbar nærhed af enderne afThe prepolymers described therein are hydroxy-telechelic polybutadiene, especially hydroxy-terminated polybutadiene, which are preferably rich in cis isomers. They occur by reaction between a mono-epoxy compound and the corresponding carboxy polymers. The product is a polymer with hydroxyl groups, including primary and secondary groups of the kind that are in close proximity to the ends of the
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det polymere molekyle, og fortrinsvis ved enderne af molekylet. Monoepoxy- forbindelsen er en organisk forbindelse, der indeholder en enkelt epoxy-gruppe, herunder mono-epoxy-harpikser; især foretrækkes epoxy-forbindelser med formlen: Λ R - C - C - R' hvor hvert af radikalerne R og R' er hydrogen, aryl, eller et alkyl, fortrinsvis en lavere alkylgruppe, og især 1,2-alkylenoxider, såsom propylenoxid og 1,2-butylenoxid, som frembringer sekundære hydroxyl-grupper ved reaktion med den carboxyl-telecheliske polymer.the polymeric molecule, and preferably at the ends of the molecule. The monoepoxy compound is an organic compound containing a single epoxy group including mono-epoxy resins; especially epoxy compounds of the formula are preferred: Λ R - C - C - R 'wherein each of the radicals R and R' is hydrogen, aryl, or an alkyl, preferably a lower alkyl group, and especially 1,2-alkylene oxides such as propylene oxide and 1,2-butylene oxide which produces secondary hydroxyl groups by reaction with the carboxyl-telechelic polymer.
De hydroxy-terminerede polybutadiener er fortrinsvis dem, der sælges under varemærket HC 434 af Thiokol Chemical Corporation og under varemærket HYCÅR-CTB af B.F., Goodrich and Company. Således har en typisk hydroxy-termineret polybutadien en molekylvægt på ca. 3800, og det antages, at den har følgende formelThe hydroxy-terminated polybutadienes are preferably those sold under the trademark HC 434 by Thiokol Chemical Corporation and under the trademark HYCÅR-CTB by B.F., Goodrich and Company. Thus, a typical hydroxy-terminated polybutadiene has a molecular weight of approx. 3800, and is assumed to have the following formula
0 . O0. ISLAND
II ) IIII) II
ho-ch-ch2-o-c-(ch2-ch=chch2)x - ch2-ch -c-och2-choh CH3 jl· ^h3 l N y hvor x og y hver for sig kan variere mellem 1 og 67.ho-ch-ch2-o-c- (ch2-ch = chch2) x - ch2-ch -c-och2-choh CH3 jl · ^ h3 l N y where x and y can individually vary between 1 and 67.
En foretrukken HTPB-præpolymer er en, der salges under varemærket Poly bd R-45M af Arco Chemicals Co., og den har følgende formelA preferred HTPB prepolymer is one sold under the trademark Poly bd R-45M by Arco Chemicals Co. and it has the following formula
H0-|(CH2-CH=CH-CH2)0 ^ 2 -—(CH2-CH) 2 -(CH2-CH=CH-CH2 )^- —OHH 2 - (CH 2 -CH = CH-CH 2) O 2 - (CH 2 -CH) 2 - (CH 2 -CH = CH-CH 2)
ch=ch2 hvor n=44-60 og hvor polybutadien-strukturen er 60 % trans-1,4, 20 % cis-1,4, og 20 % vinyl-1,2. Index1ene 0,2 og 0,6 angiver de relative mængder.ch = ch 2 where n = 44-60 and where the polybutadiene structure is 60% trans-1.4, 20% cis-1.4, and 20% vinyl-1,2. The indexes 0.2 and 0.6 indicate the relative amounts.
En særlig foretrukken HTPB præpolymer er den, der sælges under varemærket R-45HT af Arco Chemicals, hvilken har den samme formel som R-45M, hvorved forskellen ligger i værdien af "n”, der i tilfælde af R-45HT er 57-65.A particularly preferred HTPB prepolymer is that sold under the trademark R-45HT by Arco Chemicals, which has the same formula as R-45M, whereby the difference lies in the value of "n" which in the case of R-45HT is 57-65 .
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Den præpolymere anvendes som den hovedsagelige bestanddel i drivmid-del-bindemiddelsystemet, passende i en mængde på ca. 50-85 vægt-%, fortrinsvis i en mængde på ca. 60-65 vægt-% af bindemiddelkomposi-tionen. Passende anvendes der en antioxidant sammen med den præpolymere, og denne kan f.eks. være phenyl-beta-naphthylaminen (PBNA), bisphenol AO-2246 (American Cyanamid) eller forskellige forbindelser, der indeholder den kemiske gruppe p-phenylendiamin. Den foretrukne antioxidant i forbindelse med opfindelsen er phenyl-beta-naphthyl-amin i en koncentration på ca. 1 vægt-% af den præpolymere.The prepolymer is used as the major constituent of the propellant-binder system, suitably in an amount of approx. 50-85% by weight, preferably in an amount of approx. 60-65% by weight of the binder composition. Suitably, an antioxidant is used with the prepolymer, and this can e.g. be the phenyl-beta-naphthylamine (PBNA), bisphenol AO-2246 (American Cyanamid) or various compounds containing the chemical group p-phenylenediamine. The preferred antioxidant of the invention is phenyl-beta-naphthylamine at a concentration of about 1% by weight of the prepolymer.
Når man anvender R-45HT som den HTPB-præpolymere, kan man anvende en antioxidant bestående af en eller flere af de følgende stoffer:When using R-45HT as the HTPB prepolymer, one can use an antioxidant consisting of one or more of the following substances:
Varemærke Leveringsfirma Kemisk navn PBNA Uniroyal Phenyl-beta-naphthylamin A02246 Cyanamid Hindret bis-phenol NAUGARDQ Uniroyal Polymeriseret trimethyl- dihydroquinolin ACTAMINE Uniroyal Diphenylamin-diisobu£ylen reaktionsprodukt FLEXZONE 7L Uniroyal N-phenyl, N*-(l,3-dimethyl- butyl) p-phenelen-diamin UOP-36 Universal Oil N-phenyl-N-cyclohexyl-Trademark Delivery company Chemical name PBNA Uniroyal Phenyl-beta-naphthylamine A02246 Cyanamide Inhibited bis-phenol NAUGARDQ Uniroyal Polymerized trimethyl-dihydroquinoline ACTAMINE Uniroyal Diphenylamine-diisobuylene reaction product FLEXZONE 7L Uniroyal - N-Nyl-N-3-Nyl p-phenylene diamine UOP-36 Universal Oil N-phenyl-N-cyclohexyl
Oil Products parafin-diamin DTBHQ Eastman Di-tert.-butylhydroquinonOil Products paraffin-diamine DTBHQ Eastman Di-tert.-butylhydroquinone
En synergistisk effekt fremkom, når man tilsatte en kombination af DTBHQ med UOP-36 eller FLEXZONE 7L til drivmiddelblandingen i en udstrækning af 1 procent af den præpolymere.A synergistic effect emerged when a combination of DTBHQ with UOP-36 or FLEXZONE 7L was added to the propellant mixture to an extent of 1 percent of the prepolymer.
Det i det omhandlede bindemiddel indeholdte diisocyanat-hærdemiddel kan f.eks. være 2,4-tolylen-diisocyanat (TDI), 1,6-hexamethylen-di-isocyanat (HMDI) eller DDI, som er en blanding af isomere af diiso-cyanat indeholdende 36 carbonatomer fremstillet ved dimerisering af fedtsyrer med 18 carbonatomer. Det foretrukne diisocyanat er DDI i forbindelse med de foreliggende drivmiddel-bindemiddelsystemer. Forholdet isocyanat/hydroxyl (NCO/OH) er indstillet, så man optimerer de mekaniske egenskaber af det resulterende drivmiddel i overensstemmelse med erfaringer fra tidligere systemer. I forbindelse med opfindelsen ligger et typisk ækvivalent forhold NCO/OH i intervallet 0,75-0,95.The diisocyanate curing agent contained in the binder of the present invention can, e.g. be 2,4-tolylene diisocyanate (TDI), 1,6-hexamethylene di-isocyanate (HMDI) or DDI which is a mixture of isomers of diisocyanate containing 36 carbon atoms prepared by the dimerization of fatty acids with 18 carbon atoms. The preferred diisocyanate is DDI in connection with the present propellant binder systems. The ratio of isocyanate / hydroxyl (NCO / OH) is adjusted to optimize the mechanical properties of the resulting propellant in accordance with the experience of previous systems. In the context of the invention, a typical equivalent ratio of NCO / OH is in the range of 0.75-0.95.
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For at lette blandingen af bindemiddelkompositionen med det faste oxidationsmiddel ved fremstillingen af de støbelige drivmidler ifølge opfindelsen, inkorporerer man passende et blødgøringsmiddel i bindemiddelkompositionen i en andel på ca. 15 til 30 % på basis af den totale vægt af bindemiddelkompositionen. Forbindelser, der er velegnet som blødgøringsmidler, er kendt på polymerområdet, og i de foreliggende kompositioner kan de f.eks. være dioctyladipat (DOA), diethylhexylazelat (DEHA), eller isodecylpelargonat (IDP). Det foretrukne blødgøringsmiddel er dog IDP.In order to facilitate the mixing of the binder composition with the solid oxidant in the manufacture of the moldable propellants according to the invention, a plasticizer is suitably incorporated into the binder composition in a proportion of approx. 15 to 30% based on the total weight of the binder composition. Compounds suitable as plasticizers are known in the polymer field, and in the present compositions, be dioctyl adipate (DOA), diethylhexylazelate (DEHA), or isodecyl pelargonate (IDP). However, the preferred plasticizer is IDP.
Aziridin-polyester-bestanddelen af bindemiddelsystemet er som angivet reaktionsproduktet af et aziridinyl-phosphinoxid med en polycarboxyl-syre. Disse materialer er beskrevet i for eksempel USA patent nr.The aziridine-polyester component of the binder system is, as indicated, the reaction product of an aziridinyl phosphine oxide with a polycarboxylic acid. These materials are described in, for example, U.S. Patent
3.745.074 og 3.762.972. Mere specifikt udtrykt er reaktionsproduk-teme af di- eller tri-funktionelt aziridin-phosphin-oxid eller derivater deraf med organiske molekyler, som er polyfunktionelle hvad angår carboxylgrupper, og som i sine strukturer kan indeholde en eller flere hydroxylgrupper. Reaktanterne er / \ ° Ϊ X1- -X2 (I) og R- C - OH (II) 1 n X \ hvor X1 repræsenterer en aziridingruppe med strukturen H^^Q13,745,074 and 3,762,972. More specifically, the reaction products are di- or tri-functional aziridine phosphine oxide or derivatives thereof with organic molecules which are polyfunctional in carboxyl groups and which may contain in one of their structures one or more hydroxyl groups. The reactants are / \ ° Ϊ X1- -X2 (I) and R- C - OH (II) 1n X \ where X1 represents an aziride group of structure H ^^ Q1
CC
—-
CC
l\ 2 H Cr 1 2 hvor Q og Q enten er hydrogen eller alkylgrupper med 1 til 4 car- /12 o bonatomer (Q og Q kan være ens eller forskellige), hvor X kan være det samme som X^ eller kan være et organisk radikal såsom phenyl, benzyl, methyl, ethyl, o.s.v., hvor R er et alkyl, der indeholder mindst et aktivt hydrogenatom eller en organisk del af molekyler, som indeholder en eller flere hydroxylgrupper, og hvor n er 2, 3, eller 4. Reaktionsproduktet er en blanding af forbindelser, hvis nominelle struktur kan repræsenteres ved formlen: 71 \ 2 H Cr 1 2 where Q and Q are either hydrogen or alkyl groups having 1 to 4 car- / 12 o bon atoms (Q and Q may be the same or different) where X may be the same as X organic radical such as phenyl, benzyl, methyl, ethyl, etc., wherein R is an alkyl containing at least one active hydrogen atom or organic portion of molecules containing one or more hydroxyl groups and wherein n is 2, 3, or 4. The reaction product is a mixture of compounds whose nominal structure can be represented by the formula: 7
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/ o h or or o ./ o h or or o.
X1- P - N - C - C - O - C — R (III) V X2 HH Jn 12 12 hvor X , X , Q , Q , R og n er som allerede defineret.X1-P - N - C - C - O - C - R (III) V X2 HH Jn 12 12 where X, X, Q, Q, R and n are as already defined.
De optimale forhold er af en sådan art, at i det væsentlige carboxyl-grupper i (II) omsættes, og at nominelt en aziridingruppe i (i) omsættes, dvs. et mol af (I) for hvert carboxyl-ækvivalent af (II).The optimum conditions are such that essentially carboxyl groups in (II) are reacted and that nominally an aziride group in (i) is reacted, i.e. one mole of (I) for each carboxyl equivalent of (II).
De foretrukne aziridin-polyester-materialer til anvendelse ifølge opfindelsen fremstilles ud fra tri's-1-(2-methyl-aziridinyl)-phosphin-oxid, der er almindelig kendt som MAPO, og disyrer, såsom adipinsyre, æblesyre, sebacinsyre, ravsyre og vinsyre.The preferred aziridine polyester materials for use in the invention are prepared from tri's 1- (2-methyl-aziridinyl) phosphine oxide, commonly known as MAPO, and diacids such as adipic acid, malic acid, sebacic acid, succinic acid and tartaric acid. .
PAZ er et kondensationsprodukt af MAPO, tris-(2-methyl-aziridimyl-l)-phosphin-oxid, med en ligekædet disyre med den almene formel HOOC (0¾^ COOH (x er 2 til 8 og fortrinsvis 4, 5 eller 6) og en sekundær substitueret disyre med den almene formel HOOC CH(R) (CHgiy CH(R^) COOH, hvor R og R1 kan være ens eller forskellige, idet de er H eller OH, og hvor y = 0 til 6, fortrinsvis 0, 1 eller 2. Ved en typisk syntese kondenseres 3 til 8 mol MAPO, fortrinsvis 5 til 6 mol, med 0,5 til 1,0 mol af den substituerede disyre og 1,75 til 2,5 mol af den ligekædede disyre ved 50 til 65° C i 4 timer under n2.PAZ is a condensation product of MAPO, tris- (2-methyl-aziridimyl-1) -phosphine oxide, with a straight-chain diacid of the general formula HOOC (0¾COOH (x is 2 to 8 and preferably 4, 5 or 6)) and a secondary substituted diacid of the general formula HOOC CH (R) (CHgiyCH (R ^) COOH where R and R kan may be the same or different, being H or OH and where y = 0 to 6, preferably 0 , 1 or 2. In a typical synthesis, 3 to 8 moles of MAPO, preferably 5 to 6 moles, are condensed with 0.5 to 1.0 moles of the substituted diacid and 1.75 to 2.5 moles of the straight chain diacid at 50 to 65 ° C for 4 hours under n2.
Andelen af aziridin-polyester-bindemidlet i bindemiddelsystemet ifølge opfindelsen ligger mellem ca.0,1 og 1 vægt-% af den totale bindemiddel-komposition.The proportion of the aziridine-polyester binder in the binder system of the invention is between about 0.1 and 1% by weight of the total binder composition.
Den anden komponent i den bindemiddelkombination, som anvendes i bindemidlet ifølge opfindelsen, er aminpolyester-materialet, der som angivet er reaktionsproduktet af en alkanolamin og en mættet alifatisk polycarboxylsyre. Den foretrukne aminpolyester til det foreliggende formål er en polymer afledt af N-methyldiethanolamin og sebacinsyre, hvilken er kendt som polymer N-8. Passende N-8 Polymere har følgende speci fikationer:The second component of the binder combination used in the binder of the invention is the amine polyester material which is, as stated, the reaction product of an alkanolamine and a saturated aliphatic polycarboxylic acid. The preferred amine polyester for the present purpose is a polymer derived from N-methyldiethanolamine and sebacic acid, which is known as polymer N-8. Suitable N-8 polymers have the following specifications:
8 DK 15 4 9 4 8 B8 DK 15 4 9 4 8 B
Μη (gennemsnitlig molekylvægt efter antal) : 1200-2000; fortrinsvis 1500-1800 aciditet : ¢0,02 ækv,/100 g ækvivalent OH : 1-1,5 mæk./g; fortrinsvis 1,1-1,3 fugtighed : < 0,15 vægt-%Μη (average molecular weight by number): 1200-2000; preferably 1500-1800 acidity: ¢ 0.02 eq, / 100 g equivalent OH: 1-1.5 meq / g; preferably 1.1-1.3 humidity: <0.15% by weight
Andre passende midler ftar følgende formlerOther suitable means include the following formulas
HO-CH-CR-,-N- CH0-CHO-ΓCO(0Ho) OOOCH-CH9-N-CHP-CHo1 HHO-CH-CR -, - N- CH0-CHO-ΓCO (0Ho) OOOCH-CH9-N-CHP-CHo1 H
| J |L ^n|‘^| jJ0'| J | L ^ n | '^ | jJ0 '
Ril RI I I R|V R, , R, || R|VRil RI I I R | V R,, R, || R | V
hvor R’1 og R,v kan være ens eller forskellige og kan være hydrogen eller en mættet alkylkæde med 1 eller 2 carbonatomer; R*’1 kan være en mættet alkylkæde med 1 til 18 carbonatomer; n er et helt tal fra 2 til 16, fortrinsvis 8; og or er et helt tal på 3 - 10, fortrinsvis 5-7. Dette bindemiddel anvendes i en mængde på ca. 0,1 til 0,5 vægt-% af den totale bindemiddelkomposition.wherein R'1 and R, v may be the same or different and may be hydrogen or a saturated alkyl chain having 1 or 2 carbon atoms; R 1 can be a saturated alkyl chain having 1 to 18 carbon atoms; n is an integer from 2 to 16, preferably 8; and or is an integer of 3 - 10, preferably 5-7. This binder is used in an amount of approx. 0.1 to 0.5% by weight of the total binder composition.
Til dannelse af det støbelige drivmiddel ifølge opfindelsen tilblander man til bindemidlet før hærdning i henhold til en foretrukken fremgangsmåde, der i detaljer vil blive beskrevet i det følgende, findelt ammoniumperchlorat som oxidationsmiddel i dimodale eller trimodale fordelinger af fine pulvere med gennemsnitlige partikelstørrelser på l-400^um. En foretrukken partikelstørrelsesfordeling af ammoniumperchloratet er 1,7/2,7/1,0 dele med partikelstørrelse 400yum, 200yum og 17/um. Til anvendelse ved høj temperatur kan ammoniumperchloratet erstattes med kaliumperchlorat. Fortrinsvis inkorporeres et antisammenbagningsmiddel, f.eks. tricalciumphosphat, i en mængde på ca. 1 vægt-% af det 17/um perchlorat. Et metallisk additiv kan inkorporeres i drivmiddelkompositionen, om ønsket i en koncentration på 0 til 20 vægt-% af det totale drivmiddel. Dette additiv kan være findelt aluminium-eller magnesiumpulver, fortrinsvis med en gennemsnitlig partikeldiameter på 5-50yum. Et andet fast materiale, der passende er inkorporeret i den totale komposition, er et brændehastighedsadditiv eller en katalysator, der f.eks. kan være jernoxid, kobberchromit eller en organometallisk forbindelse. Det foretrukne additiv eller katalysator til det foreliggende formål er ferrioxid i en mængde på 0,1-1 vægt-% af drivmiddelkompositionen.To form the moldable propellant of the invention, the binder is admixed prior to curing according to a preferred process, which will be described in detail below, finely divided ammonium perchlorate as oxidizing agent in dimodal or trimodal distributions of fine powders having average particle sizes of 1-400. ^ um. A preferred particle size distribution of the ammonium perchlorate is 1.7 / 2.7 / 1.0 parts of particle size 400 µm, 200 µm and 17 µm. For high temperature use, the ammonium perchlorate can be replaced with potassium perchlorate. Preferably, an anti-caking agent, e.g. tricalcium phosphate, in an amount of approx. 1% by weight of the 17 µm perchlorate. A metallic additive can be incorporated into the propellant composition, if desired, at a concentration of 0 to 20% by weight of the total propellant. This additive may be comminuted aluminum or magnesium powder, preferably having an average particle diameter of 5-50 µm. Another solid which is suitably incorporated into the total composition is a burn rate additive or a catalyst, e.g. may be iron oxide, copper chromite or an organometallic compound. The preferred additive or catalyst for the present purpose is ferric oxide in an amount of 0.1-1% by weight of the propellant composition.
9 DK 154948 B9 DK 154948 B
I sammensatte drivmiddelkompositioner er det naturligvis ønskværdigt at opnå en så høj belastning af tørstoffer som muligt, og med drivmiddelkompositionerne ifølge opfindelsen kan det totale indhold· af tørstoffer variere mellem 85 og 90 vægt-% af den totale komposition, hvoraf naturligvis ammoniumperchloratet vil udgøre størstedelen og kan være mellem 68 og 88 vægt-% af den totale drivmiddelkomposition. De andre faste bestanddele indpasses deri i overensstemmelse dermed. Det polymere bindemiddel vil således udgøre ca. 10 til 15 vægt-% af den totale drivmiddelkomposition.Of course, in compound propellant compositions it is desirable to obtain as high a load of solids as possible, and with the propellant compositions of the invention, the total content of solids may vary between 85 and 90% by weight of the total composition, of which of course the ammonium perchlorate will constitute the majority and may be between 68 and 88% by weight of the total propellant composition. The other solid components are adapted therein accordingly. Thus, the polymeric binder will constitute approx. 10 to 15% by weight of the total propellant composition.
For at opnå en god dispersion af alle bestanddelene under fremstillingen af drivmiddelkompositionen og desuden reproducerbarhed af egenskaberne fra en portion til.en anden, er den foretrukne metode, at man først til en blander tilfører de flydende bestanddele, som er den præpolymere, blødgøringsmidlet og de to bindemidler. Pulveret af aluminium eller andet metal, når et sådant anvendes, og brændehastighedsadditivet for ferrioxid bliver derpå tilsat, og indholdet bliver blandet i 15 minutter under atmosfæretryk. Derpå tilsættes ca. 3/4 af den totale mængde af am-moniumperchlorat til blandingen, og blandeprocessen fortsættes i yderligere 10 minutter. Man gør brug af et vacuum, og blanderens indhold opvarmes til 60°C i ca. 60 minutter. Vacuummet frigøres derpå, og den resterende mængde ammonium-perchlorat tilsættes, og blandingen fortsættes i yderligere 5 minutter under atmosfæretryk. Diisocyanat-hærdemidlet tilsættes derpå til de andre bestanddele i blandingen, og blandeprocessen fortsættes i 5 minutter under atmosfæretryk. Herefter gør man igen brug af dette vacuum, og blandeprocessen fortsættes i 45 minutter ved en temperatur på 60°C. Drivmidlet bliver derpå støbt i forme under vacuum.In order to obtain a good dispersion of all the constituents during the preparation of the propellant composition and, in addition, reproducibility of the properties from one portion to another, the preferred method is to first add to the mixer the liquid constituents which are the prepolymer, the plasticizer and the two binders. The powder of aluminum or other metal when used and the burning rate additive of ferric oxide are then added and the contents are mixed for 15 minutes under atmospheric pressure. Then approx. 3/4 of the total amount of ammonium perchlorate to the mixture and the mixing process is continued for a further 10 minutes. A vacuum is used and the contents of the mixer are heated to 60 ° C for approx. 60 minutes. The vacuum is then released and the remaining amount of ammonium perchlorate is added and the mixture is continued for an additional 5 minutes under atmospheric pressure. The diisocyanate curing agent is then added to the other ingredients in the mixture and the mixing process is continued for 5 minutes under atmospheric pressure. This vacuum is then re-used and the mixing process is continued for 45 minutes at a temperature of 60 ° C. The propellant is then molded into molds under vacuum.
Det følgende eksempel illustrerer anvendelsen af bindemiddelsy-stemet i henhold til den foreliggende opfindelse ved fremstilling af sammensatte faste drivmidler. Det er tilsigtet, at dette eksempel skal illustrere opfindelsen. De drivmiddelkompositioner, der er angivet i eksemplet, var alle fremstillet i henhold til den metode, der er angivet i det foregående afsnit.The following example illustrates the use of the binder system of the present invention in the preparation of composite solid propellants. It is intended that this example should illustrate the invention. The propellant compositions listed in the example were all prepared according to the method set forth in the previous section.
10 DK 154948 BDK 154948 B
De mekaniske egenskaber, der er undersøgt i forbindelse med drivmiddelkompositionerne ifølge opfindelsen, var brudstyrke (c^), forlængelse under maximal belastning (8m), forlængelse ved brud (£^u) og initiale moduler (E). Disse forsøg blev gennemført med et Instron-apparat med en hastighed af tværhovedet på 5,1 cm/minut svarende til en spændehastighed på 0,741 min.""'*' for ICRPG “hårdvægt"-prøvestykket.The mechanical properties investigated in connection with the propellant compositions of the invention were fracture strength (c ^), elongation under maximum load (8m), elongation at break (£ ^) and initial modules (E). These tests were performed with an Instron apparatus at a speed of 5.1 cm / min, corresponding to a clamping speed of 0.741 min. "" * * For the ICRPG "heavyweight" test piece.
EKSEMPELEXAMPLE
Man fremstillede drivmiddelkompositioner med følgende forhold mellem egenskaberne udtrykt i vægt-%:Propellant compositions having the following proportions, expressed in% by weight, were prepared:
Ammoniumperchlorat (400^um) )Ammonium Perchlorate (400 µm))
Ammoniumper chlorat (200yUm) ) 69,4Ammonium per chlorate (200 µm)) 69.4
Ammoniumperchlorat (17 ^-) )Ammonium Perchlorate (17
Aluminium (sfæroidal kvalitet 22 yUm ) 18,0Aluminum (spheroidal grade 22 µm) 18.0
Ferrioxid katalysator 0,6 HTPB bindemiddel 12,0Ferric oxide catalyst 0.6 HTPB binder 12.0
Med henblik på undersøgelse anvendtes tre bindemiddelkompositioner i den i det foregående angivne drivmiddelkomposition. Den præ-polymere, der anvendtes i hvert bindemiddel, var af typen R45-M (varemærke) af HTPB bindemiddel solgt af Arco Chemical Co., som før beskrevet. Phenyl-beta-naphthylamin blev inkorporeret som antioxidant, isodecyl-pelargonat som blødgøringsmiddel, og DDI diisocyanat som hærdemiddel. I en bindemiddelkomposition blev de to bindemidler ifølge opfindelsen ikke udnyttet, men derimod aziridin-polyesteren af sammenligningsgrunde. I de andre to kompositioner var begge bindemidler inkorporeret.For the purpose of examination, three binder compositions were used in the aforementioned propellant composition. The prepolymer used in each binder was of type R45-M (trademark) of HTPB binder sold by Arco Chemical Co., as previously described. Phenyl-beta-naphthylamine was incorporated as antioxidant, isodecyl pelargonate as plasticizer, and DDI diisocyanate as curing agent. In a binder composition, the two binders of the invention were not utilized, but the aziridine polyester for comparative reasons. In the other two compositions, both binders were incorporated.
Bindemiddelkompositioneme var som følger:The binder compositions were as follows:
I II IIII II III
R45-M polymer (herunder 1% PBNA) 62,91 62,91 62,91 DDI 12,09 12,09 12,09R45-M polymer (including 1% PBNA) 62.91 62.91 62.91 DDI 12.09 12.09 12.09
Aziridin-polyester 2,40 0,9 0,6Aziridine polyester 2.40 0.9 0.6
Amin-polyester (N-8) - 0,2 0,2 IDP blødgøringsmiddel 22,60 23,9 24,2Amine polyester (N-8) - 0.2 0.2 IDP plasticizer 22.60 23.9 24.2
11 DK 154948 B11 DK 154948 B
Aziridin-polyesteren i dette eksempel blev fremstillet ved at omsætte 0,15 mol d-vinsyre og 0,3 mol adipinsyre med 1 mol MAPO (aziridin) i den proces, som tidligere er beskrevet i denne beskrivelse. Amin-polyesteren (N-8) i dette eksempel havde følgende egenskaber: (i) OH ækvivalent 1,19 M ækviv./g (ii) Aciditet 0,016 ækviv./lOO g (iii) Molekylvægt (Mh) 1430 bestemt ved V80.The aziridine polyester in this example was prepared by reacting 0.15 mole of d-tartaric acid and 0.3 mole of adipic acid with 1 mole of MAPO (aziridine) in the process previously described in this specification. The amine polyester (N-8) in this example had the following properties: (i) OH equivalent 1.19 M equiv / g (ii) Acidity 0.016 equiv / 100 g (iii) Molecular weight (Mh) 1430 determined at V80.
Fremstillingsegenskåberne og de mekaniske egenskaber, der opnåedes for drivmiddelkompositionerne under anvendelse af de før angivne bindemidler, var:The manufacturing properties and mechanical properties obtained for the propellant compositions using the aforementioned binders were:
I XI IIIIn XI III
Aziridin/amin-polyester (% i bindemiddel) 2,4/- 0,9/0,2 0,6/0,iAziridine / Amine Polyester (% in Binder) 2.4 / 0.9 / 0.2 0.6 / 0
Viskositet ved slutningen af blandingen (kP/60°C) 2,5 2,7 2,7Viscosity at the end of the mixture (kP / 60 ° C) 2.5 2.7 2.7
Beholderliv til 10 kP (h) 4,2 4,2 4,5Container life for 10 kP (h) 4.2 4.2 4.5
Mekaniske egenskaber (initiale) ved 22,8°C (MN/m2) 0,58 0,79 0,63 ved " {%) 30,6 36,9 41,6 E ved " (MN/m2) 3,41 4,04 3,24 fm ved -45,6°c (%) 48,2 58,8 65,6 ved " (%) 54,5 59,8 68,5Mechanical properties (initial) at 22.8 ° C (MN / m2) 0.58 0.79 0.63 at "(%) 30.6 36.9 41.6 E at" (MN / m2) 3.41 4.04 3.24 fm at -45.6 ° C (%) 48.2 58.8 65.6 at "(%) 54.5 59.8 68.5
Mekaniske egenskaber (56 dage ved 60°C) o-m ved 22,8°C (MN/m2) 0,58 0,79 0,73 ved " (%) 35,2 35,9 39,1 E ved " (MN/m2) 3,37 4,82 3,85 f m ved -45,s°c (%) 49,4 48,9 59,5 fr ved " (%) 50,7 50,4 60,9Mechanical properties (56 days at 60 ° C) at 22.8 ° C (MN / m2) 0.58 0.79 0.73 at "(%) 35.2 35.9 39.1 E at" (MN / m2) 3.37 4.82 3.85 sc at -45, ° C (%) 49.4 48.9 59.5 fr at "(%) 50.7 50.4 60.9
Det fremgår af de i det foregående angivne resultater, at fremstillingsegenskaberne, d.v.s. viskositeten ved slutningen af blandingen og beholderlivet, for drivmidlerne ifølge opfindelsen (II og III) i det væsentlige var de samme som disse egenskaber af reference-drivmidlet. Imidlertid er den mængde af aziridinpolyester, der anvendes ifølge opfindelsen, betydeligt mindre end den, derIt is clear from the results set forth above that the manufacturing properties, i.e. the viscosity at the end of the mixture and the container life, for the propellants of the invention (II and III) were essentially the same as these properties of the reference propellant. However, the amount of aziridine polyester used in the invention is significantly less than that of
12 DK 154948 B12 DK 154948 B
kræves for referencekompositionen. Drivmidlerne ifølge opfindelsen udviser også forbedrede forlængelser under maximal belastning og ved brud, mens brudstyrken og de initiale moduler er komparable med referencekompositionen.required for the reference composition. The propellants of the invention also exhibit improved extensions under maximum load and at break, while the break strength and the initial modules are comparable to the reference composition.
Claims (14)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA243,659A CA1056984A (en) | 1976-01-16 | 1976-01-16 | Curable binding systems |
| CA243659 | 1976-01-16 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK15577A DK15577A (en) | 1977-07-17 |
| DK154948B true DK154948B (en) | 1989-01-09 |
| DK154948C DK154948C (en) | 1989-05-29 |
Family
ID=4104991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK015577A DK154948C (en) | 1976-01-16 | 1977-01-14 | FURTHER BINDING AGENT, FUEL INCLUDING SUCH A BINDING AGENT AND PROCEDURE FOR MANUFACTURING THE FUEL |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5941957B2 (en) |
| BE (1) | BE850420A (en) |
| CA (1) | CA1056984A (en) |
| DE (1) | DE2701494A1 (en) |
| DK (1) | DK154948C (en) |
| FR (1) | FR2352030A1 (en) |
| GB (1) | GB1513706A (en) |
| IT (1) | IT1076219B (en) |
| NL (1) | NL180428C (en) |
| NO (1) | NO144486C (en) |
| SE (2) | SE437271B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL53672A (en) * | 1977-01-06 | 1982-03-31 | Thiokol Corp | Method for bonding solid propellant grain to rocket motor casing and polymeric composition therefor |
| GB1604197A (en) * | 1977-12-13 | 1981-12-02 | Ca Minister Nat Defence | Polyester bonding agents for htpb propellants |
| NO831850L (en) * | 1982-05-28 | 1997-02-26 | Royal Ordnance Plc | Process for producing a shaped rubbery propellant charge for rockets and the like |
| DE19917672A1 (en) * | 1999-04-19 | 2000-10-26 | Fraunhofer Ges Forschung | Rocket propellant |
| US8821859B2 (en) * | 2004-05-19 | 2014-09-02 | Agency For Science, Technology And Research | Methods and articles for the delivery of therapeutic agents |
| JP2016011624A (en) * | 2014-06-27 | 2016-01-21 | カーリットホールディングス株式会社 | Composite propellant |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3745074A (en) * | 1969-07-30 | 1973-07-10 | Us Army | Composite solid propellant with additive to improve the mechanical properties thereof |
| CA975494A (en) * | 1970-09-29 | 1975-09-30 | Gonzague L. Duchesne | Propellants |
-
1976
- 1976-01-16 CA CA243,659A patent/CA1056984A/en not_active Expired
-
1977
- 1977-01-04 NO NO770011A patent/NO144486C/en unknown
- 1977-01-13 SE SE7700279A patent/SE437271B/en not_active IP Right Cessation
- 1977-01-14 BE BE174117A patent/BE850420A/en not_active IP Right Cessation
- 1977-01-14 IT IT19330/77A patent/IT1076219B/en active
- 1977-01-14 DK DK015577A patent/DK154948C/en not_active IP Right Cessation
- 1977-01-14 GB GB1443/77A patent/GB1513706A/en not_active Expired
- 1977-01-14 DE DE19772701494 patent/DE2701494A1/en active Granted
- 1977-01-14 FR FR7701093A patent/FR2352030A1/en active Granted
- 1977-01-14 NL NLAANVRAGE7700352,A patent/NL180428C/en not_active IP Right Cessation
- 1977-01-17 JP JP52003005A patent/JPS5941957B2/en not_active Expired
-
1982
- 1982-12-13 SE SE8207110A patent/SE460476B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| SE437271B (en) | 1985-02-18 |
| BE850420A (en) | 1977-05-02 |
| JPS52110752A (en) | 1977-09-17 |
| NO144486C (en) | 1981-09-09 |
| NL7700352A (en) | 1977-07-19 |
| NO770011L (en) | 1977-07-19 |
| JPS5941957B2 (en) | 1984-10-11 |
| GB1513706A (en) | 1978-06-07 |
| SE460476B (en) | 1989-10-16 |
| SE7700279L (en) | 1977-07-17 |
| NL180428B (en) | 1986-09-16 |
| DK15577A (en) | 1977-07-17 |
| NL180428C (en) | 1987-02-16 |
| FR2352030A1 (en) | 1977-12-16 |
| NO144486B (en) | 1981-06-01 |
| CA1056984A (en) | 1979-06-19 |
| SE8207110D0 (en) | 1982-12-13 |
| DE2701494A1 (en) | 1977-07-21 |
| DK154948C (en) | 1989-05-29 |
| SE8207110L (en) | 1982-12-13 |
| IT1076219B (en) | 1985-04-27 |
| DE2701494C2 (en) | 1987-01-15 |
| FR2352030B1 (en) | 1981-02-27 |
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