GB2285624A - Glycidyl azide polymer azide - Google Patents

Glycidyl azide polymer azide Download PDF

Info

Publication number
GB2285624A
GB2285624A GB8902163A GB8902163A GB2285624A GB 2285624 A GB2285624 A GB 2285624A GB 8902163 A GB8902163 A GB 8902163A GB 8902163 A GB8902163 A GB 8902163A GB 2285624 A GB2285624 A GB 2285624A
Authority
GB
United Kingdom
Prior art keywords
azide
polymer
glycidyl
general formula
polar solvent
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.)
Granted
Application number
GB8902163A
Other versions
GB8902163D0 (en
GB2285624B (en
Inventor
Milton Bernard Frankel
Michael Alan Cunningham
Edgar Roland Wilson
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.)
Boeing North American Inc
Original Assignee
Rockwell International Corp
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 Rockwell International Corp filed Critical Rockwell International Corp
Publication of GB8902163D0 publication Critical patent/GB8902163D0/en
Publication of GB2285624A publication Critical patent/GB2285624A/en
Application granted granted Critical
Publication of GB2285624B publication Critical patent/GB2285624B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • 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
    • C06B45/105—The resin being a polymer bearing energetic groups or containing a soluble organic explosive
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C247/00—Compounds containing azido groups
    • C07C247/02—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton
    • C07C247/04—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton being saturated
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A glycidyl azide polymer azide is prepared by a process in which alpha -(2-chloroethyl)- omega -benzenesulfonyl polyepichlorohydrin is reacted with sodium azide in a polar solvent such as dimethylsulfoxide. The compound has a polyether structure with 2 - 10 repeating units and is azido-terminated.

Description

GLVCIDYL AZIDE POLYMER AZIDE Background of the Invention 1. Field of the invention This invention relates to a composition of matter and is particularly directed to an energetic azide terminated glycidyl azide polymer and a method for producing this compound.
2. DescriPtion of the Prior Art Solid propellants are generally formulated to include an oxidizer and fuel together with suitable binders and plasticizers to enhance the physical and chemical characteristics of the propellants. Most propellant systems utilize blunders and plasticizers containing energetic groups such as nitro (-N02), fluorodinitro (FC(NO2)2-). difluoroamino (-NF2) and others.
These azido plasticizers impart additional energy to propellant systems since each azido group present provides approximately 85 kcal/mole of energy to the system.
One functionally terminated azido polymer is taught by Wilson et al in U. S. Patent Application Serial No. 56.026 filed on June 1. 1987.
Another energetic azido polymer is described in U. S. Patent 4,268,450, incorporated herein by reference. In contrast to the present invention, both of the aforementioned polymers and the method of masking same, may be distinguished in part by the initiator groups and the repeating units present in the starting materials and final products. Applicants' invention provides a one-step synthesis in high yield of a glycidyl azide polymer azide which fulfills the needs of many propellant systems and is particularly useful as an energetic plasticizer for propellants and explosives.
Summarv of the Invention Accordingly there is provided by the present invention an energetic polymer comprising an azide-terminated aliphatic polymer.
Objects of the Invention Therefore it is an object of the present invention to provide a composition of matter useful in formulating solid propellants, explosives.
and the like.
Another object of the present invention is to provide an energetic azide-terminated azido plasticizer.
Yet another object of the present invention is to provide a single step process for producing the azide-terminated azldo plasticizer.
Detailed Descrivtion of the Invention The glycidyl azide polymer azide of thins invention is characterized in Table l as follows: TABLE l NAME: GLYCIDYL AZIDE POLYMER AZIDE STRUCTURE: FORMULA:
MOLECULAR WEIGHT: 508 ELEMENTAL ANALYSES: C H N Calculated: 33.07 4.72 49.61 Found: 34.38 5.14 49.30 INFRARED SPECTRUM: N3 (4.7) APPEARANCE: Light Yellow Liquid REFRACTIVE INDEX: 1.5138 at 25C DENSITY: 1.27 g/cc at 25C FREEZING POINT: -56C DSC: 205C (Onset of Exotherm) WEIGHT LOSS: 0.48X after 48 hrs. at 74C IMPACT SENSITIVITY: 40 in-lb ELECTROSTATIC SENSITIVITY: > 12.5 Joules FRICTION SENSITIVITY: > 36 Kq cm aHf (estimated): + 335 Kcal/mole SHIPPING CLASSIFICATION: Class B Explosive (25-35X Solution in CH2CL2) The glycidyl polymer azide of the general formula:
can be produced by the one-step process of reacting (2-chloroethyl) w-benrenesulfonyl polyepichlorohydrin of the general formula: (2)
with sodium azide in a polar solvent such as dimethylsulfoxide (OHIO), and wherein n of formulas (1) and (2) is an integer from 2 to lO.
The following example illustrates the invention.
EXAMPLE In a suitable reaction vessel, 2.750 ml of dimethylsulfoxide was heated under a nitrogen purge to 70-C. To this was added over a 15 minute period 2,090 grams (32.15 moles) of sodium azide. This mixture was then heated to 95-C and 2.511.2 grams (26.79 moles) of o-(2-chloroethyl)-o-benzenesulfonyl polyepichlorohydrin was added over four hours. No additional heat was required during the addition to maintain the temperature at from about 95 to about lOO-C.
After the addition was complete, the reaction mixture was heated an additional 12 hours at a temperature of from about 95 to about 1000C. The reaction mixture was then quenched with 6.5 liters of water. The resulting organic phase was separated, washed four times with ten liters of hot water, diluted to 20X solution in methylene chloride, dried over anhydrous sodium sulfate, and passed through a column of 2,000 grams of silica gel. Concentration of the solution gave 1,896.5 grams (83.9X) of the glycidyl polymer azide, the properties of which are set forth in Table 1 above.
It should be noted that the precise amounts, temperatures, times, solutions, means of addition, drowning procedures, number of washes.
extraction and stripping procedures which were used or may be used may all be varied to meet specific requirements and specific reactions. These parameters delineated herein are merely representative.
Obviously, many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

Claims (3)

1. A glycidyl azide polymer azide of the general formula:
produced by the one-step process of reacting -(2-chloroethyl)-ca-benzenesulfonyl polyepichlorohydrin of the general formula:
with sodium azide in a polar solvent. and wherein n of formulas (1) and (2) is an integer from 2 to lO.
2. The product by process of Claim l wherein the polar solvent utilized in the production of the azide product is dimethylsulfoxide.
3. The composition of matter of the general formula:
3. The composition of matter of the general formula:
Amendments to the claims have been filed as follows 1. A glycidyl azide polymer azide of the general formula:
produced by the one-step process of reacting -(2-chloroethyl )--benzenesulfonyl polyepichlorohydrin of the general formula:
with sodium azide in a polar solvent, and wherein n of formulas (1) and (2) is an integer from 2 to 10.
2. The product by process of Claim 1 wherein the polar solvent utilized in the production of the azide product is dimethylsulfoxide.
GB8902163A 1988-02-01 1989-02-01 Glycidyl azide polymer azide Expired - Fee Related GB2285624B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US15059088A 1988-02-01 1988-02-01

Publications (3)

Publication Number Publication Date
GB8902163D0 GB8902163D0 (en) 1995-04-12
GB2285624A true GB2285624A (en) 1995-07-19
GB2285624B GB2285624B (en) 1996-03-20

Family

ID=22535204

Family Applications (1)

Application Number Title Priority Date Filing Date
GB8902163A Expired - Fee Related GB2285624B (en) 1988-02-01 1989-02-01 Glycidyl azide polymer azide

Country Status (3)

Country Link
AU (1) AU663679B1 (en)
FR (1) FR2707979A1 (en)
GB (1) GB2285624B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5565650A (en) * 1990-05-25 1996-10-15 Minnesota Mining And Manufacturing Company Non-detonable poly(glycidyl azide) product
CN115028829A (en) * 2022-06-21 2022-09-09 西安近代化学研究所 1,2, 3-triazole-4-methylene nitrate modified azide adhesive, and synthesis method and application thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2799762B3 (en) * 1999-10-15 2002-05-17 Poudres & Explosifs Ste Nale GLYCIDYL POLYAZOTURES COMPRISING AN ACYLOXY TERMINATION AND AN AZIDE TERMINATION
CN111474258B (en) * 2020-04-17 2022-09-06 湖北航天化学技术研究所 Method for measuring branching degree of azido glycidyl polyether

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4268450A (en) * 1977-08-08 1981-05-19 Rockwell International Corporation Energetic hydroxy-terminated azido polymer

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5565650A (en) * 1990-05-25 1996-10-15 Minnesota Mining And Manufacturing Company Non-detonable poly(glycidyl azide) product
CN115028829A (en) * 2022-06-21 2022-09-09 西安近代化学研究所 1,2, 3-triazole-4-methylene nitrate modified azide adhesive, and synthesis method and application thereof
CN115028829B (en) * 2022-06-21 2023-06-09 西安近代化学研究所 1,2, 3-triazole-4-methylene nitrate modified azide adhesive, synthesis method and application

Also Published As

Publication number Publication date
GB8902163D0 (en) 1995-04-12
GB2285624B (en) 1996-03-20
AU663679B1 (en) 1995-10-19
FR2707979A1 (en) 1995-01-27

Similar Documents

Publication Publication Date Title
US4268450A (en) Energetic hydroxy-terminated azido polymer
EP0120668B1 (en) Azido nitramine
EP0471489B1 (en) Process of producing improved poly(glycidyl nitrate)
EP0212161B1 (en) Process for preparing 1,5-diazido-3-nitrazapentane
EP0274213B1 (en) Process for the preparation of alkyl azide-substituted, hydroxy-terminated polyethers
EP1240234B1 (en) Polymerization of poly(glycidyl nitrate) from high purity glycidyl nitrate synthesized from glycerol
US5801325A (en) High performance large launch vehicle solid propellants
US4781861A (en) Azide-terminated azido compound
GB2285624A (en) Glycidyl azide polymer azide
Wen et al. Progress in synthesis and properties of oxetane–based energetic polymers
US5359012A (en) Glycidyl azide polymer
KR20200021710A (en) Synthesis of tkx-50 using insensitive intermediate
US4329522A (en) 1,3,5,7-Tetranitroadamantane and process for preparing same
US3907907A (en) 2-Fluoro-2,2-dinitroethyl substituted polyethers
US4472311A (en) Method of preparing 1,1,1-azidodinitro compounds
US4522756A (en) Alkyl, azido, nitro ethers and method of preparation
AU599800B2 (en) Azide-terminated azido compound
EP0403727A2 (en) Glycidyl azide polymer esters
US6323352B1 (en) Polyglycidyl azides comprising an acyloxy terminal group and an azide terminal group
AU636514B2 (en) Azide-terminated azido compound
US6861501B1 (en) Process for making stable cured poly(glycidyl nitrate) and energetic compositions comprising same
US5013856A (en) 1,5-diazido-3-nitrazapentane and method of preparation thereof
US3344167A (en) Difluoraminoalkyl nitrates
US3813305A (en) High burning rate nf propellants
US3784422A (en) 2,3-bis(difluoroamino) propyl 2,2-dinitro-propyl carbonate, useful in propellants

Legal Events

Date Code Title Description
PCNP Patent ceased through non-payment of renewal fee

Effective date: 19960620