GB2280903A - Polymer curing - Google Patents
Polymer curing Download PDFInfo
- Publication number
- GB2280903A GB2280903A GB9215603A GB9215603A GB2280903A GB 2280903 A GB2280903 A GB 2280903A GB 9215603 A GB9215603 A GB 9215603A GB 9215603 A GB9215603 A GB 9215603A GB 2280903 A GB2280903 A GB 2280903A
- Authority
- GB
- United Kingdom
- Prior art keywords
- bis
- cyanomethyl
- bromo
- propanol
- hydrobromic acid
- 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
Links
Classifications
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7856—Nitrogen containing azo groups
-
- 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
- C07C247/12—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton being further substituted by carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/11—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton
- C07C255/12—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton containing cyano groups and hydroxy groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/63—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton
- C07C255/65—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms
- C07C255/67—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms having cyano groups and azido groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
3-bromo-2,2-bis(cyanomethyl)-1-propanol is a useful intermediate in the production of an energetic curative for energetic urethane systems, and is used to form 3-bromo-2,2-bis(cyanomethyl)-1-propyl tosylate prior to conversion to 2,2-bis(azidomethyl)-1,3-propane diisocyanate, the curative.
Description
"POLYMER CURING"
BACKGROUND OF THE INVENTION
The present invention relates to solid fuel propellants and gas generators, and to a process for curing associated energetic urethane systems. This invention also relates specifically to an azide dilsocyanate curative having specific application to the cur Ing of such energetic urethane systems.
In the manufacture of solid fuel propellants, including rocket propellants and gas generators, a polymeric substance such as glycidyl azide polymer (GAP) is frequently employed as a binder to hold together fuel, oxidizer, and other compounds making up the propellant or gas generator. A GAP energetic binder is described in
U.S. Patent 4,268,450 to Frankel et al., disclosure of which is hereby incorporated by reference.
Gas generators, such as gun propellants, may incorporate binders of nitrocellulose plasticized with GAP, such as disclosed in
U.S. Patent 4,288,262 to Flanagan et al.. hereb incorporated by reference.
The additlon of curing agents to such prepolymer systems causes cross-linking between the functional groups of the prepolymer, such as glycerol-initiated GAP prepolymer, resulting in a polymer. The polymers physical properties vary with the degree of cross-linkage. This degree can be varied by the amount and type of curing agent added. In general, it is desired to cure the prepolymers to a degree such that the resulting polymer has the physical properties of an elastomer.
Examples of known curing agents are isophorone diisocyanate, 3-nitraza-l,5-pentane dilsocyanate, and the biuret trimer of hexamethylene dilsocyanate (N-lOO), a polyfunctional isocyanate produced commercially by Mobay Chemical Company.
It is usually desired to suspend other compounds in the polymer binder composition. For instance, a solid rocket propellant composition could comprise such a polymer in which is blended a plasticizer, an oxidizer, and a fuel.
Examples of suitable fuels would be light metals and light metal hydrides. Examples of suitable ozidizers would be perchlorates and nitrates.
SUMMARY OF THE INVENTION
Accordingly, there is, provided by the present invention a curative for curing energetic urethane systems, a method for producing said energetic curative, and a process for utilizing said energetic curative in curing energetic urethane systems.
OBJECTS OF THE INVENTION
It is, therefore, an object of this invention to provide a method for curing energetic urethane polymer systems.
It is a further object of this invention to provide a novel azide dilsocyanate curative and a novel process for the preparation thereof.
Other objects and attendant advantages will be evident from the following description of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The objects of this invention are accomplished in the synthesis of a novel energetic azide diisocyanate curative 2,2-bis (azidomethyl)-1,3-propane diisocyanate (BAMPDI).
The synthesis of the energetic azide difsocyanate BAMPDI is accomplished, according to the present invention, In a 6-step reaction sequence.
The starting material is 3,3-bis(cyanomethyl) oxetane (1).
Treatment of the starting material (1) with aqueous hydrobromic acid gives 3-bromo-2,2-bis(cyanomethyl)-l-propanol (2), which is then converted to 3-bromo-2,2-bis(cyanomethyl)-l-propyl tosylate (3).
The reaction, then, of the tosylate compound (3) with sodium azlde produces 2,2-bis(azidomethyl)-1,3-dicyanopropane (4). This is followed by hydrolysis of the 1,3-dicyanopropane (4) to yield 3,3 bis(azldomethyl )-glutaric acid (5), which is converted with phosphorous pentachioride to 3,3-bis(azidomethyl) glutaryl chloride (6). The novel azido dlisocyanate curative 2,2-bis(azidomethyl)-l, 3-propane diisocyanate (BAMPDI) is obtained by reacting the glutaryl chloride with an Inorganic azide to forum an intermediate di(acylazide), followed by decomposition and rearrangement to give the desired diisocyanate. The properties of BAMPDI are summarized in
Table I hereinbelow.
TABLE I
NAME: 2,2-BIS(AZIDOMETHYL)-l ,3-PROPANE OIISOCYANATE
STRUCTURE:
FORMULA: C7H8N802 APPEARANCE: Yellow Mobile Liquid
EQUIVALENT
WEIGHT: 125 (Theoretical = 118)
PURITY: 94.4X
BOILING
POINT: 70-C at 0.01 mm
IMPACT
SENSITIVITY: > 200 in-lb
FRICTION
SENSITIVITY: > 36 Kg - cm #H f : + 91 Kcal/mol (Est.)
ELEMENTAL
ANALYSIS: C H N
CALCULATED: 35.59 3.39 47.46
FOUND: 35.06 3.37 46.84
A more detailed explanation of the synthesis of BAMPDI Is hereinafter provided.
3-Bromo-2.2-Bis(Cvanomethvl)-1-ProDanol (2)
In a suitable reaction vessel, equipped with a stirrer, was admixed 9.6 grams (0.07 mole) of 3,3-bis(cyanomethyl) oxetane and 50 milliliters of water. To this mixture was added, dropwise, in 15 minutes, 14.6 grams of 47% hydrobromic acid (0.09 mole). The reaction mixture was stirred overnight at ambient temperature, and then refluxed for 4 hours. The organic phase was separated, dried, and concentrated to give 13.1 grams (85X) of white solid.
Elemental Analysis: Calculated for C7HgBrN20: C, 38.73; H, 4.18; N, 12.91.
Found: C, 38.76; H, 4.47; N, 12.59.
3-Bromo-2,2-Bis(Cyanomethyl)-l-ProDyl Toselate (3)
To a mixture of 12.8 grams (0.059 mole) of 3-bromo-2,2-bis (cyanomethyl)-l-propanol and 29.5 grams of pyridine, in a suitable container, was added, at from about 00 to about 5"C, a solution of 12.4 grams (0.06 mole) of p-toluenesulfonyl chloride in 15 milliliters of chloroform as a solvent. The reaction mixture was stirred at ambient temperature for about one week and quenched in 500 milliliters of water. The organic layer was separated; washed with water, dilute hydrochloric acid, and water; dried over anhydrous magnesium sulfate; and concentrated to give 17.9 grams (81.7X) of white solid, m.p. 86.8"C.
Elemental Analysis: Calculated for C14H15BrSO3:
C, 45.29; H, 4.07; N, 7.55.
Found: C, 45.24; H, 4.42; N, 7.09.
2.2-BisfAzldomethvl)-1 .3-Dicwanooronane (4)
A mixture of 17.9. grams (0.048 mole) of 3-bromo-2,2-bis (cyanomethyl)-l-propyl tosylate and 50 milliliters of dimethylsul oxide was heated to 65 C, and 9.4 grams (0.145 mole) of sodium azlde was added. The mixture was then heated at from 956 to 98 C for 22 hours and quenched in 800 milliliters of water. The aqueous phase was extracted with 3 x 25 milliliters of chloroform and washed with water to remove the dimethylsulfoxide. After drying over anhydrous magnesium sulfate, the solution was concentrated to give 6.4 grams (65.3%) of white solid, m.p. 68.50-69.50C.
Elemental Analysis: Calculated for C7H8N8:
C, 41.51; H, 3.95; N, 54.88.
Found: C, 41.21; H, 4.37; N, 54.70.
3.3-Bis(Azldomethvl)-Glutaric Acid (5)
A solution of 29.6 grams (0.15 mole) of 2,2-bis(azidome- thyl)-1,3-dicyanopropane, 150 millimiters of water, and 57.3 grams (0.87 mole) of 85% potassium hydroxide was refluxed for 24 hours, cooled, and acidified with concentrated hydrochloric acid. The solid product was collected, washed with water, and drled to give 23.7 grams (67.5X) of product, m.p. 1230-1240C.
Elemental Analysis: Calculated for C7HloN604: C, 34.71; H, 4.16; N, 34.70.
Found: C, 34.41; H, 4.67; N, 35.16; 3.3-Bis(Azidomethl) Glutaryl Chloride (6)
To a mixture of 8.9 grams (0.037 mole) of 3,3-bis(azidomethyl)-glutaric acid, 15 milliliters of dry benzene, and 0.07 grams of zinc chloride was added, portionwise, 15.4 grams (0.074 mole) of phosphorous pentachloride in l hour, with cooling, to maintain the reaction temperature at about 10 to about 200C. The reaction mixture was stirred overnight at ambient temperature, filtered, and concentrated to give 10.3 grams (100%) of yellow liquid.
Elemental Analysis: Calculated for C7H8Cl2N602:
C, 30.11; H, 2.87; Cl, 25.45; N, 30.11.
Found: C, 30.59; H, 3.10; Cl, 24.48; N, 29.71.
Z.L-Bis(Azidomethyl )-1.3-Propane D1isocYanate (BAMPDI)
A solution of 9.3 grams (0.14 mole) of sodium azide in 37 milliliters of water was cooled in an ice-bath, and a solution of 5.0 grams (0.018 mole) of 3,3-bis(azidomethyl) glutaryl chloride and 25 milliliters -of ethylene dichloride was added, dropwise. This reaction mixture was stirred for 10 minutes followlng the addition of the second solution above. The organic phase was separated and dried over anhydrous magnesium sulfate. The solution was slowly heated to 50 C, causing the intermediate dlazide to decompose, liberating nitrogen. The solution was finally heated to reflux to complete the decomposition, and concentrated to give 3.8 grams (90X) of yellow liquid.
Elemental Analysis: Calculated for C7H8N802:
C, 35.59; H, 3.39; N, 47.46.
Found: C, 35.06; H, 3.37; N, 46.84.
As previously indicated, the curative of the present invention, when utilized in energetic urethane systems, will affect the pot life, i.e., the handling time available between the mixing and when the cure begins to set up, dependent upon the specific mater lals used, the mixing and curing temperature, and size of other components, such as fuel and the like.
Mixing of the urethane system is normally carrled out at room temperature or such higher temperature as needed to provide a viscosity sufficiently low to allow thorough mixing. Depending on factors such as desired cure time, curing temperature of the system can vary. However, curing temperature is typically held within the range of ambient room temperature to 1400F, with a preferred range of llOe to 130F.
The process, according to the present invention, for producing an energetic urethane system, which system includes at least a binder, a plasticizer, an oxidizer, and a fuel, comprises:
(a) admixing a binder, plasticizer, oxidizes, and a fuel;
(b) introducing an azide diisocyanate curative 2,2-bis (azidomethyl)-1 ,3-propane dlisocyanate; and
(c) curing said energetic urethane system.
In summary, a novel azide diisocyanate curative, method of preparation, and utilization in a curing process have been developed.
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 other than specifically described.
Claims (8)
1. A composition of matter, 3-bromo-2,2-bis(cyanomethyl) -l-propanol.
2. A method to produce 3-bromo-2,2-bis(cyanomethyl)-l-propanol comprising admixing and reacting 3,3-bis(cyanomethyl) oxetane with hydrobromic acid.
3. The method of claim 2, wherein the hydrobromic acid is 47% hydrobromic acid, and the reaction mixture was stirred overnight at ambient temperature, and then refluxed for 4 hours.
4. A composition of matter, 3-bromo-2,2-bis(cyanomethyl) -l-propyl tosylate.
5. A method to produce 3-bromo-2,2-bis(cyanomethyl)-l-propyl tosylate comprising combining and reacting a mixture of 3-bromo-2 , 2-bis(cyanomethyl ) -1-propanol, pyridine, and p-toluenesulfonyl chloride.
6. The method of claim 5, wherein the p-toluenesulfonyl chloride is in a solvent.
7. The method of claim 5, wherein the reaction mixture was stirred at ambient temperature for one week and then quenched in water, followed by organic layer separation and concentration.
8. A method according to claim 5, 6 or 7 wherein the reaction mixture was stirred at ambient temperature for one week and then quenched in water, followed by organic layer separation and concentration.
8. The method of claim 6, wherein the solvent is chloroform.
Amendments to the claims have been filed as follows 1. A composition of matter, 3-bromo-2,2-bis(cyanomethyl)-i propanol.
2. A method to produce 3-bromo-2,2-bis (cyanomethyl)-l- propanol comprising admixing and reacting 3,3-bis (cyanomethyl) oxetane with hydrobromic acid.
3. A method according to claim 2, wherein the hydrobromic acid is 47% hydrobromic acid, and the reaction mixture was stirred overnight at ambient temperature, and then refluxed for 4 hours.
4. A composition of matter, 3-bromo-2,2-bis(cyanomethyl)-2- propyl tosylate.
5. A method to produce 3-bromo-2,2-bis(cyanomethyl)-l-propyl tosylate comprising combining and reacting a mixture of 3-bromo2,2-bis (cyanomethyl) -1-propanol, pyridine, and p-tolenesulfonyl chloride.
6. A method according to claim 5, wherein the ptoluenesulfonyl chloride is in a solvent.
7. A method according to claim 6, wherein the solvent is chloroform.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US56297290A | 1990-08-06 | 1990-08-06 | |
| FR9110999A FR2706890A1 (en) | 1990-08-06 | 1991-09-05 | 1,3-Diisocyanato-2,2-bis(azidomethyl)propane and its intermediates and application to the vulcanisation of a system containing energising (energy-providing) urethanes |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9215603D0 GB9215603D0 (en) | 1994-10-26 |
| GB2280903A true GB2280903A (en) | 1995-02-15 |
| GB2280903B GB2280903B (en) | 1995-06-28 |
Family
ID=26228934
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9215603A Expired - Fee Related GB2280903B (en) | 1990-08-06 | 1991-07-29 | Polymer curing |
| GB9116295A Expired - Fee Related GB2280902B (en) | 1990-08-06 | 1991-07-29 | Polymer curing |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9116295A Expired - Fee Related GB2280902B (en) | 1990-08-06 | 1991-07-29 | Polymer curing |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU653317B1 (en) |
| FR (1) | FR2706890A1 (en) |
| GB (2) | GB2280903B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009000892A3 (en) * | 2007-06-27 | 2009-03-26 | Univ Gent | Functionalised polyurethanes |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4288262A (en) * | 1978-03-30 | 1981-09-08 | Rockwell International Corporation | Gun propellants containing polyglycidyl azide polymer |
| US4707199A (en) * | 1983-10-17 | 1987-11-17 | The United States Of America As Represented By The Secretary Of The Army | Non nitroglycerin-containing composite-modified double-base propellant |
| CA1305164C (en) * | 1987-06-22 | 1992-07-14 | Milton B. Frankel | Energetic azido curing agents |
-
1991
- 1991-07-29 GB GB9215603A patent/GB2280903B/en not_active Expired - Fee Related
- 1991-07-29 GB GB9116295A patent/GB2280902B/en not_active Expired - Fee Related
- 1991-08-05 AU AU82522/91A patent/AU653317B1/en not_active Ceased
- 1991-09-05 FR FR9110999A patent/FR2706890A1/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009000892A3 (en) * | 2007-06-27 | 2009-03-26 | Univ Gent | Functionalised polyurethanes |
| US8889799B2 (en) | 2007-06-27 | 2014-11-18 | Recticel N.V. | Functionalised polyurethanes |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9215603D0 (en) | 1994-10-26 |
| GB2280903B (en) | 1995-06-28 |
| GB9116295D0 (en) | 1994-10-26 |
| GB2280902B (en) | 1995-06-28 |
| AU653317B1 (en) | 1994-09-29 |
| GB2280902A (en) | 1995-02-15 |
| FR2706890A1 (en) | 1994-12-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19950928 |