US3857870A - Ferrocene containing monomers and copolymers - Google Patents
Ferrocene containing monomers and copolymers Download PDFInfo
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- US3857870A US3857870A US00849254A US84925469A US3857870A US 3857870 A US3857870 A US 3857870A US 00849254 A US00849254 A US 00849254A US 84925469 A US84925469 A US 84925469A US 3857870 A US3857870 A US 3857870A
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- United States
- Prior art keywords
- ferrocenoate
- pentaerythritol
- tris
- butadiene
- copolymer
- 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.)
- Expired - Lifetime
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 32
- 239000000178 monomer Substances 0.000 title claims abstract description 32
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 title abstract description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000007983 Tris buffer Substances 0.000 claims abstract description 10
- NWOBPRNWFOYMDO-UHFFFAOYSA-N [C-]1(C=CC=C1)C(=O)OCC(COC(C(=C)C)=O)(COC(=O)[C-]1C=CC=C1)COC(=O)[C-]1C=CC=C1.[CH-]1C=CC=C1.[Fe+2].[CH-]1C=CC=C1.[Fe+2].[CH-]1C=CC=C1.[Fe+2] Chemical compound [C-]1(C=CC=C1)C(=O)OCC(COC(C(=C)C)=O)(COC(=O)[C-]1C=CC=C1)COC(=O)[C-]1C=CC=C1.[CH-]1C=CC=C1.[Fe+2].[CH-]1C=CC=C1.[Fe+2].[CH-]1C=CC=C1.[Fe+2] NWOBPRNWFOYMDO-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZCZFEIZSYJAXKS-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COC(=O)C=C ZCZFEIZSYJAXKS-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 PENTAERYTHRITOL ACRYLATE TRIS (FERROCENOATE) Chemical compound 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 8
- APZPSKFMSWZPKL-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCC(CO)(CO)CO APZPSKFMSWZPKL-UHFFFAOYSA-N 0.000 claims description 5
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000003380 propellant Substances 0.000 abstract description 33
- 239000000203 mixture Substances 0.000 abstract description 20
- 239000011230 binding agent Substances 0.000 abstract description 16
- 239000003054 catalyst Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000004014 plasticizer Substances 0.000 abstract description 4
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000446 fuel Substances 0.000 abstract description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000007858 starting material Substances 0.000 description 4
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 2
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-M nonanoate Chemical compound CCCCCCCCC([O-])=O FBUKVWPVBMHYJY-UHFFFAOYSA-M 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- FJSNTQXNQNSZJS-UHFFFAOYSA-N 2-(2-nonanoyloxypropoxy)propyl nonanoate Chemical compound CCCCCCCCC(=O)OCC(C)OCC(C)OC(=O)CCCCCCCC FJSNTQXNQNSZJS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NUCFNMOPTGEHQA-UHFFFAOYSA-N 3-bromo-2h-pyrazolo[4,3-c]pyridine Chemical compound C1=NC=C2C(Br)=NNC2=C1 NUCFNMOPTGEHQA-UHFFFAOYSA-N 0.000 description 1
- BJJVDFADUDDTQK-UHFFFAOYSA-N 5-hydroxy-2-methylpentanenitrile Chemical compound N#CC(C)CCCO BJJVDFADUDDTQK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ZDWGXBPVPXVXMQ-UHFFFAOYSA-N bis(2-ethylhexyl) nonanedioate Chemical compound CCCCC(CC)COC(=O)CCCCCCCC(=O)OCC(CC)CCCC ZDWGXBPVPXVXMQ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- VTDVIWPHJXANHZ-UHFFFAOYSA-M chloro(cyclopenta-2,4-dien-1-ylidene)methanolate;cyclopenta-1,3-diene;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.[O-]C(Cl)=C1C=CC=C1 VTDVIWPHJXANHZ-UHFFFAOYSA-M 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- pentaerythritol methacrylate tris (ferrocenoate') and pentaerythritol acrylate tris (ferrocenoate), are disclosed along with the pertinent preparative procedures therefor.
- the specified ferrocene-containing monomers when copolymerized with butadiene serve as the propellant binder and catalyst for fastburning composite propellants.
- the copolymers perform the functions of binder and catalyst in a propellant composition containing ammonium perchlorate, a plasticizer, and aluminum metal fuel.
- pentaerythritol which serve as the starting compounds for. the preparation of the ferrocene containing monomers of this invention are pentaerythritol arsenite methacrylate and pentaerythritol arsenite acrylate.
- polymerizable monomer is well known.
- the term when applied to the propellant art generally means a compound useful in propellants because. it is capable of forming an elastic tough rubbery polymer by condensation or polymerization reactions in the propellant mix.
- the resulting rubbery polymer functions as a binder forthe propellant charge.
- the binder provides strength for the propellant charge or grain.
- Many of the prior art compounds have been concerned with binder materials.
- the present trend has been to increase the performance of propellants by employing an energetic binder material, improved oxidizer, and'burning rate catalyst. I
- the prior art esters of polymerizable compounds have been employed as energetic binder materials having oxidizing and plasticizing capabilities.
- the term enprocess is 'a complex process requiring a proper bal-' ance of fuel, oxidizer, and catalysts.
- The'oxygen'content of a number of energetic binders of the prior art enables those binders to contribute to the oxidizing capability of the propellant composition in addition to the binder and catalyst which does not evaporate during propellant processing or migrate in the finished propellant.
- ferrocene-containing monomers pentaerythritol methacrylate tris (ferrocenoate) and pentaerythritol acrylate tris (ferrocenoate) are produced from pentaerythritol arsenite methacrylate and pentaerythritol arsenite acrylate respectively as the starting compounds.
- the “monomers become constituents of copolymers of DESCRIPTION OF THE PREFERRED EMBODIMENTS
- the starting compound, pentaerythritol arsenitemethacrylate, formsone ofthe monomers of this invention and may be produceda's follows.
- a burning rateadditive' has been required for use in the prior art propellant compositions to obtainincreased burning rates.
- These additives or catalysts have included metallic oxides and organo-metallic compounds.
- .Ferrocene and n-butyl ferrocene have been utilized as burning rate catalysts.
- the liquid ferrocene compounds have been effective in promoting
- the present invention has as its principal object to provide ferrocene-containing monomers which can be polymerized to form an energetic binder having a burning rate catalyst as an integral part thereof.
- Another object is to provide copolymerization prodnets of ferrocene containing monomers and butadiene which serves as energetic binder and burning rate catalyst for propellant compositions.
- A'further object of this invention is to provide a propellant composition having a combination energetic moved at reduced pressure, and the residue is dried at ambient temperature and l millimeter of pressure for 3-0 minutes.
- the residue- is extracted with three 100 ml. portions of hot ligroin (each containing 5 mg. of hydroquinone).
- the extracts are concentrated and chilled and the product removed by filtration.
- the solid obtained is recrystallized from ligroin to g'ive 5.40 grams of the monomer, pertaerythritol arsenite methacrylate, m.p. 83C to 845C.
- pentaerythritol arsenite acrylate forms anothermonomer-and may be produced as follows.
- acetonitrile is added over a 15 minute period.
- the reaction mixture is cooled to keep the temperature below 30C during the addition; after the benzenesulfonyl chloride addition, the mixture is stirred'at30C for l hour, .
- the solvent is then removed at reduced pressure and the residue dried at ambient temperature and 'l millimeter of pressure for 30 minutes.
- the residue is extracted three times with 200 ml. of'hot ligroin con- Pentaerythritol methacrylate tris (ferrocenoate) .and pentaerythritol acrylate'tris (ferrocenoate) are monomers which are prepared as set forth hereinbelow under Example 1 and 11.
- Example 111 and Example IV are illustrative of the procedures for preparation of the copolymers of this invention.
- Table 1 sets forth burning rates of uncured composite propellants using the hydroxy-terminated copolymer of butadiene and pentaerythritol methacrylate tris (ferrocenoate) as compared with a propellant using unmodified hydroxy-terminated polybutadiene, and a propellant using n-butyl ferrocene, a standard burningrate-promoter.
- the copolymer of pentaerythritol acrylate tris (ferrocenoate) and butadiene may be used as the binder and catalyst for a propellant composition.
- EXAMPLE 11 Preparation of Pentaerythritol Acrylate tris (ferrocenoate) 1
- pentaerythritol monoacrylate prepared by hydrolysis of pentaerythritol arsenite acrylate
- ferrocenoyl chloride 10 g.
- the organic residue obtained upon evaporation of the organic solvents is re-crystallized from methanol.
- the yield is pens ljst i qttfi-(tetressaeetelt 1. .255 F I-P- l07-109C.
- EXAMPLE 111 Copolymerization With Butadiene Introduce to a glass-high-pressure reactor (Aerosol tube): 30 ml. of toluene. 2.1 12g (0.0084 mole) azo-bis- (2-methyl-5-hydroxy-valeronitrile) as initiator. and 2.1g (0.0025 mole) pentaerythritol methacrylate tris- (ferrocenoate). The reactor is attached to a vacuum line and deaerated by three alternate freeze-thaw cycles. Butadiene (10.8g.. 0.2 mole) is condensed into the reactor, and the reactor transferred to an oil bath at 6667C. Heating is continued for a period of 72 hours.
- Butadiene (10.8g.. 0.2 mole) is condensed into the reactor, and the reactor transferred to an oil bath at 6667C. Heating is continued for a period of 72 hours.
- the copolymer is characterized by molecular weight (3,500), OH end groups (1.21 wt%) and elemental analysis (Fe. Found: 3.9).
- the mole ratio of butadiene to monomer is from about 40 to 1 to about 80 to 1 for the monomer selected.
- the mole ratio in Examples Ill and 1V is also satisfactory when the monomer pentaerythritol acrylate tris (ferrocenoate) is selected for copolymer preparation.
- Burning Rate Data The hydroxy-terminated copolymer of butadiene and pentaerythritol methacrylate tris-(ferrocenate) containing 3.9% Fe. (prepolymer A of Table 1). providescenoate) may be used in place of the prepolymer, I butadieneand pentaerythritol methacrylate tris (ferrocenoate).
- suit-- able plasticizers include diisooctyl azelate; di-2- ethylhexyl azelate, and dipropylene glycol dipelargonate.
- the plasticizers noted above may be used with the copolymers of this invention in amounts from about 5 to about 25 weight percent of the propellant composition.
- the ammonium perchlorate may vary from about 50 to about 70 weight percent of the propellant composition.
- the copolymers of this invention may be used in propellant compositions in amounts from about 5 to about 30 weight percent.
- Aluminum metal from about 5 to about weight percent may be used in the propellant composition containing the copolymers of this invention.
- copolymers of this invention may be substituted for polybutadiene and the burning rate catalyst employed in a propellant composition since the copolymers contain a catalyst as an integral part thereof.
- the copolymers of this invention are particularly attractive as a source of catalysis for the propellant composition in order to avoid the problems associatedwith the use of liquid catalysts (e.g. problems, such as, loss by evaporation or migration within the propellant during storage).
- copolymer of claim 2 wherein said selected monomer is pentaerythritol methacrylate tris (ferrocenoate); said suitable solvent is toluene; said predetermined period of time is about 72 hours; said predetermined temperature is from about 66C to about 67C; and said suitable initiator is azo-bis-(2-methyl-5- 'hydroxyvaleronitrile 5.
- the copolymer of claim 4 characterized by a molecular weight in the range from about 3500 to about 4700, OH end groups from about 0.8 to l.2 weight percent, and Fe content from about 3.9 to about 6.9
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- 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The ferrocene-containing polymerizable monomers, pentaerythritol methacrylate tris (ferrocenoate) and pentaerythritol acrylate tris (ferrocenoate), are disclosed along with the pertinent preparative procedures therefor. The specified ferrocenecontaining monomers when copolymerized with butadiene serve as the propellant binder and catalyst for fast-burning composite propellants. The copolymers perform the functions of binder and catalyst in a propellant composition containing ammonium perchlorate, a plasticizer, and aluminum metal fuel.
Description
United States Patent 1191 Stevens et al.
[11 3,857,870 [451 Dec. 31, 1974 FERROCENE CONTAINING MONOMERS' AND COPOLYMERS [76] Inventors: Travis E. Stevens, 1510 Montdale Rd., S.E.', Huntsville, Ala. 35801; Samuel F. Reed, Jr., 4009 Medford Dr., S.E., Huntsville, Ala. 35802 [22] Filed: July 31, 1969 [21] Appl. No.: 849,254
OTHER PUBLICATIONS Levi, Ferrocene Polymers: 'An Annotated Bibliography, 'Plastics Technical Evaluation Center, Picatinny Arsenal, Dover, N..l., 1966, p. 1, TPl l4ou6.
Primary ExaminerLeland A. Sebastian Attorney, Agent, or Firm- -Edward .1. Kelly; Herbert Berl; Jack W. Voigt [5 7] ABSTRACT -The ferrocene-containing polymerizable monomers,
pentaerythritol methacrylate tris (ferrocenoate') and pentaerythritol acrylate tris (ferrocenoate), are disclosed along with the pertinent preparative procedures therefor. The specified ferrocene-containing monomers when copolymerized with butadiene serve as the propellant binder and catalyst for fastburning composite propellants. The copolymers perform the functions of binder and catalyst in a propellant composition containing ammonium perchlorate, a plasticizer, and aluminum metal fuel.
5 Claims, No Drawings 4 1 CONTAINING 'MONOMER'S AND COPOLYMERS FERROCENE tial esterification ofpentaerythritol are known. Two
derivatives of pentaerythritol which serve as the starting compounds for. the preparation of the ferrocene containing monomers of this invention are pentaerythritol arsenite methacrylate and pentaerythritol arsenite acrylate.
The term polymerizable monomer is well known. The term when applied to the propellant art generally means a compound useful in propellants because. it is capable of forming an elastic tough rubbery polymer by condensation or polymerization reactions in the propellant mix. The resulting rubbery polymer functions as a binder forthe propellant charge. The binderprovides strength for the propellant charge or grain. Many of the prior art compounds have been concerned with binder materials. The present trend has been to increase the performance of propellants by employing an energetic binder material, improved oxidizer, and'burning rate catalyst. I
The prior art esters of polymerizable compounds have been employed as energetic binder materials having oxidizing and plasticizing capabilities. The term enprocess is 'a complex process requiring a proper bal-' ance of fuel, oxidizer, and catalysts. The'oxygen'content of a number of energetic binders of the prior art enables those binders to contribute to the oxidizing capability of the propellant composition in addition to the binder and catalyst which does not evaporate during propellant processing or migrate in the finished propellant.. I
SUMMARY OF THE INVENTION The ferrocene-containing monomers, pentaerythritol methacrylate tris (ferrocenoate) and pentaerythritol acrylate tris (ferrocenoate) are produced from pentaerythritol arsenite methacrylate and pentaerythritol arsenite acrylate respectively as the starting compounds.
The "monomers become constituents of copolymers of DESCRIPTION OF THE PREFERRED EMBODIMENTS The starting compound, pentaerythritol arsenitemethacrylate, formsone ofthe monomers of this invention and may be produceda's follows.
To a clear solution of 10.4 grams (0.050 mole) of. pentaeryth'ritol arsenite in 20 milliliters of acetonitrile.
and 8 milliliters of triethylamine is added drop wise a mixture of'5.5g.(0.05 2 mole)ofmethacryloyl chloride 1 v and 5 ml. of acetonitrile. The addition requires about 15 minutes while thetemperature is maintained at about 35C to about 40C by external cooling. The mix ture is stirred at 50C for 2 hours, then the solvent is rebinding cap'abilty of the'prop'ellant composition. ,Each I active ingredient in a propellant composition contributes to oneor more functions of the propellant system.
'Naturally, a multi-functionalingredient offers distinct advantages.
Generally, a burning rateadditive' has been required for use in the prior art propellant compositions to obtainincreased burning rates. These additives or catalysts have included metallic oxides and organo-metallic compounds. .Ferrocene and n-butyl ferrocene have been utilized as burning rate catalysts. The liquid ferrocene compounds have been effective in promoting The present invention has as its principal object to provide ferrocene-containing monomers which can be polymerized to form an energetic binder having a burning rate catalyst as an integral part thereof.
Another object is to provide copolymerization prodnets of ferrocene containing monomers and butadiene which serves as energetic binder and burning rate catalyst for propellant compositions.
A'further object of this invention is to provide a propellant composition having a combination energetic moved at reduced pressure, and the residue is dried at ambient temperature and l millimeter of pressure for 3-0 minutes. The residue-is extracted with three 100 ml. portions of hot ligroin (each containing 5 mg. of hydroquinone). The extracts are concentrated and chilled and the product removed by filtration. The solid obtained is recrystallized from ligroin to g'ive 5.40 grams of the monomer, pertaerythritol arsenite methacrylate, m.p. 83C to 845C.
Another starting compound pentaerythritol arsenite acrylate, forms anothermonomer-and may be produced as follows.
To a mixture of 10.4g. (0.050 mole) of pentaerythritol arsenite and 10 ml. ofacetonitrile is added 4.5 ml.
(0.065 mole) of acrylic acid followed by 24 ml. (0.175
mole) of triethylamine.- When the exotherm from't-he ,addition of the amine (the reaction temperature should not be allowed to exceed 20C) is subsided, 7.7 ml.
(0.060 mole) of. benzene-sulfonyl chloride in 10 ml. of
acetonitrile is added over a 15 minute period. The reaction mixture is cooled to keep the temperature below 30C during the addition; after the benzenesulfonyl chloride addition, the mixture is stirred'at30C for l hour, .The solvent is then removed at reduced pressure and the residue dried at ambient temperature and 'l millimeter of pressure for 30 minutes. The residue is extracted three times with 200 ml. of'hot ligroin con- Pentaerythritol methacrylate tris (ferrocenoate) .and pentaerythritol acrylate'tris (ferrocenoate) are monomers which are prepared as set forth hereinbelow under Example 1 and 11. The specified monomers when copolymerized with butadiene form binders that provide in addition to the binder function the function of catalysis for the propellant system wherein used. Example 111 and Example IV are illustrative of the procedures for preparation of the copolymers of this invention. Table 1 sets forth burning rates of uncured composite propellants using the hydroxy-terminated copolymer of butadiene and pentaerythritol methacrylate tris (ferrocenoate) as compared with a propellant using unmodified hydroxy-terminated polybutadiene, and a propellant using n-butyl ferrocene, a standard burningrate-promoter. Similarly, the copolymer of pentaerythritol acrylate tris (ferrocenoate) and butadiene may be used as the binder and catalyst for a propellant composition. I
EXAMPLE I Preparation of Pentaerythritrol Methacrylate Tris (ferrocenoate) A 2.20 g. (8 mole) sample of pentaerythritol arsenite methacrylate and mg. of dicyanobenzoquinoneis stirred with ml of acetone and 6 ml of water for minutes at C. The solution is filtered, and the filtrate is stripped to dryness. The residue, in methylene chloride, is dried over calcium sulfate. The solution is again stripped to dryness, and the residue taken up in 8 ml methylene chloride and 8 ml of chlorobenzene. This methacrylate tris (ferrocenoate), 1.14g, m.p. 109-1 12C.
um Analysis W Calculated for C H Fe O C. 60.0; H. 4.80; Fe. 19.94.
Found: C. 59.7; H. 4.80; Fe. 20.9
EXAMPLE 11 Preparation of Pentaerythritol Acrylate tris (ferrocenoate) 1 The procedure outlined in Example 1 above is followed using 1.71 g of pentaerythritol monoacrylate (prepared by hydrolysis of pentaerythritol arsenite acrylate) and 10 g. of ferrocenoyl chloride. The organic residue obtained upon evaporation of the organic solvents is re-crystallized from methanol. The yield is pens ljst i qttfi-(tetressaeetelt 1. .255 F I-P- l07-109C.
Analysis Calculated for C H Fe O C. 59.60; H. 4.64; Fe. 20.3.
Found: C. 59.1: H. 4.59; Fe. 19.7.
EXAMPLE 111 Copolymerization With Butadiene Introduce to a glass-high-pressure reactor (Aerosol tube): 30 ml. of toluene. 2.1 12g (0.0084 mole) azo-bis- (2-methyl-5-hydroxy-valeronitrile) as initiator. and 2.1g (0.0025 mole) pentaerythritol methacrylate tris- (ferrocenoate). The reactor is attached to a vacuum line and deaerated by three alternate freeze-thaw cycles. Butadiene (10.8g.. 0.2 mole) is condensed into the reactor, and the reactor transferred to an oil bath at 6667C. Heating is continued for a period of 72 hours. On cooling the-solvent is removed by evaporation and the copolymer reprecipitated by dissolving in ether followed by the addition of methanol. After'decanting the solvents, the copolymer is stripped of excess solvents on arotatory evaporator and finally dried at 70-75C. under reduced pressure (1 mm) for a period of 24 hours. The yield of liquid copolymer is 7.1
'g The copolymer is characterized by molecular weight (3,500), OH end groups (1.21 wt%) and elemental analysis (Fe. Found: 3.9).
EXAMPLE IV In a similar reaction to that set forth in Example 111, 5.4 g. (0.1) butadiene is copolymerized with 2.1g (0.0025 mole) of pentaerythritol methacrylate tris- (ferrocenoate) in toluene with 0.756 g. (0.003 mole) azo-bis-(Z-rncthyl-5-hydroxy-valcronitrile) as initiator to give 4.2 g. (56%) of the copolymer analyzing as follows: molecular weight (4,700). OH end groups (0.8 weight%) and elemental analysis (Fe. Found 6.9%).
As noted in Examples 111 and IV the mole ratio of butadiene to monomer is from about 40 to 1 to about 80 to 1 for the monomer selected. The mole ratio in Examples Ill and 1V is also satisfactory when the monomer pentaerythritol acrylate tris (ferrocenoate) is selected for copolymer preparation.
Burning Rate Data The hydroxy-terminated copolymer of butadiene and pentaerythritol methacrylate tris-(ferrocenate) containing 3.9% Fe. (prepolymer A of Table 1). providescenoate) may be used in place of the prepolymer, I butadieneand pentaerythritol methacrylate tris (ferrocenoate).
Table 1 Burning Rates of Uneured Composite Propellants Prepolymcr /1 Plaslici zcr "/1 NH ,ClOf/r A17: Additive "/1 R at R,, at
' 750 psi 1500 psi HTPB" 10 lsodeeyl 10 0.54 0.84
Pelargonate A ls'odecyl 70 10 0.71 0.97
- Pclargonale HTPB" ll lsodeeyl 70 10 NBF**.2 0.71 0.97
Pelargonate Unmodified hydroxy-terminated polyhutadlenc.
" n hutyl ferrocenc. a standard burning-rate promoter.
mark, Emolein from Emery Industries, Inc. Other suit-- able plasticizers include diisooctyl azelate; di-2- ethylhexyl azelate, and dipropylene glycol dipelargonate.
The plasticizers noted above may be used with the copolymers of this invention in amounts from about 5 to about 25 weight percent of the propellant composition. The ammonium perchlorate may vary from about 50 to about 70 weight percent of the propellant composition. The copolymers of this invention may be used in propellant compositions in amounts from about 5 to about 30 weight percent. Aluminum metal from about 5 to about weight percent may be used in the propellant composition containing the copolymers of this invention. v
The copolymers of this invention may be substituted for polybutadiene and the burning rate catalyst employed in a propellant composition since the copolymers contain a catalyst as an integral part thereof. The copolymers of this invention are particularly attractive as a source of catalysis for the propellant composition in order to avoid the problems associatedwith the use of liquid catalysts (e.g. problems, such as, loss by evaporation or migration within the propellant during storage).
We claim: 1 -l. A polymerizable monomer selected from pentaerythritol methacrylate tris (ferrocenoate) and pentaerythritol acrylate tris (ferrocenoate) reacted with butadiene to form a copolymer.
2. The copolymer of claim 1 wherein said butadiene and said selected monomer are reacted in the presence of a suitable initiator contained in a suitable'organic solvent for a predetermined period of time and at a predetermined temperature; said butadiene and said selected monomer being present in a mole ratio of butadiene to monomer from about 40 to l to about 80 to l.
3. The copolymer of claim 2 wherein said selected monomer is pentaerythritol acrylate tris (ferrocenoate); said suitable solvent is toluene; said predetermined period of time is about 72 hours; said predetermined temperature is from about 66C to about 67C; and said suitable initiator is azo-bis-(2-methyl-5- hydroxy-valeronitrile).
4. The copolymer of claim 2 wherein said selected monomer is pentaerythritol methacrylate tris (ferrocenoate); said suitable solvent is toluene; said predetermined period of time is about 72 hours; said predetermined temperature is from about 66C to about 67C; and said suitable initiator is azo-bis-(2-methyl-5- 'hydroxyvaleronitrile 5. The copolymer of claim 4 characterized by a molecular weight in the range from about 3500 to about 4700, OH end groups from about 0.8 to l.2 weight percent, and Fe content from about 3.9 to about 6.9
weight percent.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5,857,870 Dated 12/31/7h Inventor(s) Travis E. Stevens et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
On the Cover Sheet, item should read Assignee:
United States of America as r'espresnted by the Secretary of the Army.
Signed and sealed this 3rd day of June 1975.
(SEAL) Attest:
. C. I-(ARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5,857,870 Dated 12/51/7 Inventor(s) Travis E. Stevens et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
On the Cover Sheet, item should read Assignee:
United States of America as respresnted by the Secretary of the Army.
Signed and sealed this 3rd day of June 1975.
(SEAL) Attest:
. V C. B-TARSTL'XLL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks
Claims (5)
1. A POLYMERIZABLE MONOMER SELECTED FROM PENTAERYTHRITOL METHACRYLATE TRIS (FERROCENOATE) AND PENTAERYTHRITOL ACRYLATE TRIS (FERROCENOATE) REACTED WITH BUTADIENE TO FORM A COPOLYMER.
2. The copolymer of claim 1 wherein said butadiene and said selected monomer are reacted in the presence of a suitable initiator contained in a suitable organic solvent for a predetermined period of time and at a predetermined temperature; said butadiene and said selected monomer being present in a mole ratio of butadiene to monomer from about 40 to 1 to about 80 to
3. The copolymer of claim 2 wherein said selected monomer is pentaerythritol acrylate tris (ferrocenoate); said suitable solvent is toluene; said predetermined period of time is about 72 hours; said predetermined temperature is from about 66*C to about 67*C; and said suitable initiator is azo-bis-(2-methyl-5-hydroxy-valeronitrile).
4. The copolymer of claim 2 wherein said selected monomer is pentaerythritol methacrylate tris (ferrocenoate); said suitable solvent is toluene; said predetermined period of time is about 72 hours; said predetermined temperature is from about 66*C to about 67*C; and said suitable initiator is azo-bis-(2-methyl-5-hydroxyvaleronitrile).
5. The copolymer of claim 4 characterized by a molecular weight in the range from about 3500 to about 4700, OH end groups from about 0.8 to 1.2 weight percent, and Fe content from about 3.9 to about 6.9 weight percent.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00849254A US3857870A (en) | 1969-07-31 | 1969-07-31 | Ferrocene containing monomers and copolymers |
US00144283A US3847958A (en) | 1969-07-31 | 1971-05-18 | Ferrocene-containing monomers |
US144280A US3867213A (en) | 1969-07-31 | 1971-05-18 | Ferrocene-containing monomers and copolymers |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00849254A US3857870A (en) | 1969-07-31 | 1969-07-31 | Ferrocene containing monomers and copolymers |
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US3857870A true US3857870A (en) | 1974-12-31 |
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ID=25305412
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US00849254A Expired - Lifetime US3857870A (en) | 1969-07-31 | 1969-07-31 | Ferrocene containing monomers and copolymers |
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US (1) | US3857870A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5486302A (en) * | 1991-01-17 | 1996-01-23 | Cpi Engineering Services, Inc. | Lubricant composition for fluorinated refrigerants used in compression refrigeration systems |
US20060069211A1 (en) * | 2004-09-30 | 2006-03-30 | Zuifang Liu | Ionic hydrophilic high molecular weight redox polymers for use in enzymatic electrochemical-based sensors |
-
1969
- 1969-07-31 US US00849254A patent/US3857870A/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
Levi, Ferrocene Polymers: An Annotated Bibliography, Plastics Technical Evaluation Center, Picatinny Arsenal, Dover, N.J., 1966, p. 1, TP114ou6. * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5486302A (en) * | 1991-01-17 | 1996-01-23 | Cpi Engineering Services, Inc. | Lubricant composition for fluorinated refrigerants used in compression refrigeration systems |
US5612299A (en) * | 1991-01-17 | 1997-03-18 | Cpi Engineering Services, Inc. | Lubricant composition for fluorinated refrigerants used in compression refrigeration systems |
US20060069211A1 (en) * | 2004-09-30 | 2006-03-30 | Zuifang Liu | Ionic hydrophilic high molecular weight redox polymers for use in enzymatic electrochemical-based sensors |
US7351770B2 (en) * | 2004-09-30 | 2008-04-01 | Lifescan, Inc. | Ionic hydrophilic high molecular weight redox polymers for use in enzymatic electrochemical-based sensors |
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