USH934H - Maleic anhydride adjunct to triphenylbismuthine to improve mechanical properties of hydroxy terminated binders - Google Patents
Maleic anhydride adjunct to triphenylbismuthine to improve mechanical properties of hydroxy terminated binders Download PDFInfo
- Publication number
- USH934H USH934H US07/551,106 US55110690A USH934H US H934 H USH934 H US H934H US 55110690 A US55110690 A US 55110690A US H934 H USH934 H US H934H
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- United States
- Prior art keywords
- tpb
- man
- triphenylbismuthine
- maleic anhydride
- ratio
- 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.)
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- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 title claims abstract description 96
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title abstract description 7
- 239000011230 binding agent Substances 0.000 title description 2
- 239000003380 propellant Substances 0.000 claims abstract description 49
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 229920005596 polymer binder Polymers 0.000 claims abstract description 5
- 239000002491 polymer binding agent Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical compound N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000035882 stress Effects 0.000 description 34
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 239000007767 bonding agent Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- -1 methylaziridinyl Chemical group 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- AMUBKBXGFDIMDJ-UHFFFAOYSA-N 3-heptyl-1,2-bis(9-isocyanatononyl)-4-pentylcyclohexane Chemical compound CCCCCCCC1C(CCCCC)CCC(CCCCCCCCCN=C=O)C1CCCCCCCCCN=C=O AMUBKBXGFDIMDJ-UHFFFAOYSA-N 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 description 1
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- UITKKKJYFZEYDQ-UHFFFAOYSA-N CC1N(C1)[PH2]=O Chemical compound CC1N(C1)[PH2]=O UITKKKJYFZEYDQ-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
-
- 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
- C08G18/08—Processes
- C08G18/089—Reaction retarding agents
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
-
- 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
-
- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/765—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
Definitions
- Prior art bonding agents including MT4 reaction product of 2.0 moles of tris 1(2 methylaziridinyl)phosphine oxide, 0.7 mole adipic acid, and 0.3 mole tartaric acid), HX752 (bis isophthaloyl 1(2 methyl) aziridine), and other type bonding agents have been employed individually in aging studies to determine effects on propellant physical properties.
- a hydroxy terminated propellant composition cured with a diisocyanate curing agent and containing MT4 as the bonding agent showed significant softening at high temperature (52° F. and 70° C.) aging.
- a propellant containing HX752 and cured with isophorone diisocyanate hardened severely under the same conditions.
- Applicant's coinvention with Henry C. Allen filed as Ser. No. 840,927 on Oct. 11, 1977, issued as U.S. Pat. No. 4,090,893, and assigned to The United States of America as represented by the Secretary of the Army, Washington, D.C., teaches and claims a bonding agent system for use in a hydroxy terminate polybutadiene propellant composition that is curable with a diisocyanate curing agent.
- This propellant contains a high solids loading of aluminum metal fuel and ammonium perchlorate oxidizer, and it employs a bonding agent system consisting of MT4, the reaction product of 2.0 moles of tris 1 (2 methyl aziridinyl) phosphine oxide, 0.7 mole adipic acid, and 0.3 mole tartaric acid in an amount from about 0.10 to about 0.20 weight percent of the propellant composition; HX752, bis isophthaloyl 1(2 methyl) aziridine in an amount from about 0.10 to about 0.20 weight percent of the propellant composition; and BIDE, butyliminodiethanol in an amount from about 0.02 to about 0.05 weight percent of the propellant composition.
- MT4 the reaction product of 2.0 moles of tris 1 (2 methyl aziridinyl) phosphine oxide, 0.7 mole adipic acid, and 0.3 mole tartaric acid in an amount from about 0.10 to about 0.20 weight percent of the propellant composition
- HX752 bis is
- the above hydroxy-terminated polybutadiene propellant composition employed an optional delay quick cure catalyst system (of each parts) of triphenylbismuthine, magnesium oxide Mg0 and maleic anhydride (MAN)(0-0.05% each).
- the delayed quick cured system with isophorone diisocyanate (IPDI) makes possible a longer pot like but a shorter cure time of only 2 days as compared to more than 5 days for propellants cured with dimeryl diisocyanate (DDI) and 14 days for propellants cured with IPDI without using a catalyzed cure.
- m-TMXDI meta-tetramethylxylene diisocyanate
- IPDI isophorone dissocyanate
- TMXDI and p-TMXDI were in reaction injection molding (RIM) which permits the manufacture of urethane parts which require no post-painting.
- RIM reaction injection molding
- the isomers of either TMXDI which are naturally white (or can be pigmented any desired color) are light stable; and if scratched or damaged in use, they retain their integral color.
- Triphenylbismuthine (TPB) has been used singly in propellants to obtain higher modulus and/or stress values in composite propellants with isocyanate cured hydroxy terminated polymer binders.
- TPB has been widely accepted for the designated benefits it provide; however, since the cost of TPB is in the range of $1.08 per gram, an adjunct to TPB having only a fractional part of the cost of TPB and which imparts equal or improved benefits to the mechanical properties in hydroxyterminated binders would be attractive in view of present budget restraints to reduce cost.
- TPB triphenylbismuthine
- m-TMXDI m-tetramethylxylenediisocyanate
- FIG. 1 depicts the increase in stress and modulus values achieved from use of 1:1 TPB:MAN in m-TMXDI cured propellant compositions.
- FIG. 2 depicts the increase in stress and modules values achieved from use of 1:1.5 TPB:MAN in m-TMXDI cured propellants.
- Table I depicts physical property data of IPDI cured propellants with TPB and MAN in amounts from 0.02 TPB to 0.025% and 0% MAN to 0.03% wherein the ratio of TPB:MAN varies from 1:0, 1:1 and 1: 1.5.
- Table II depicts the effect on mechanical properties of various concentration in percent TPB used in m-TMXDI cured propellants.
- Table III depicts the effect of TPB concentrations and MAN concentrations and the TPB:MAN ratios on mechanical properties of m-TMXDI cured propellants.
- FIGS. 1 and 2 depict stress and modulus respectively.
- modulus increased 47% with the addition of 0.03% MAN; WITH 0.025% EACH TPB and MAN, the modulus increased by 13%.
- Higher modulus at elevated environmental temperatures can be important in preventing propellant grain slump and deformation.
- the addition of MAN to the propellant formulations caused no significant change in stress at -40° C. This is important because low stress capability at low temperatures can result in grain fracture during storage or ignition in a cold environment.
- FIGS. 1 and 2 (Curves A and B, stress and modulus), respectively show the effect on mechanical properties of increasing concentrations of 1:1 and 1:1.5 TPB to MAN, respectively. It is evident that to obtain maximum stress with the 1:1 ratio, 0.035% TPB is required whereas the same maximum stress is reached with 0.025% TPB with 1:1.5 TPB to MAN.
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Abstract
Maleic anhydride, MAN, as an adjunct to triphenylbismuthine (TPB) yields roved benefits to the mechanical properties of isophorone diisocyanate cured hydroxy terminated polymer binders. Results from several propellant mixes indicate that both pot life and mechanical properties are affected not only by the concentration of TPB catalyst used, but also by the ratio of TPB to MAN. The ratio of TPB to MAN from about 1 to 0.5 to about 1 to 1.5 produces interesting results in the values of stress, strain, and modulus as shown in the data set forth in the specification and as graphically depicted in the drawing. The weight percent of MAN ranges from about 0.0125 percent to about 0.0375 percent, and the weight percent of TPB ranges from about 0.015 percent to about 0.035 percent.
Description
The invention described herein may be manufactured, used, and licensed by or for the Government for governmental purposes without the payment to me of any royalties thereon.
Earlier aging studies for hydroxy terminated polybutadiene propellants indicated mild to severe hardening or softening during high temperature aging. Further studies indicated that the changes during high temperature aging was attributed to reaction results of the bonding agents.
Prior art bonding agents including MT4 reaction product of 2.0 moles of tris 1(2 methylaziridinyl)phosphine oxide, 0.7 mole adipic acid, and 0.3 mole tartaric acid), HX752 (bis isophthaloyl 1(2 methyl) aziridine), and other type bonding agents have been employed individually in aging studies to determine effects on propellant physical properties. A hydroxy terminated propellant composition cured with a diisocyanate curing agent and containing MT4 as the bonding agent showed significant softening at high temperature (52° F. and 70° C.) aging. A propellant containing HX752 and cured with isophorone diisocyanate hardened severely under the same conditions.
Applicant's coinvention with Henry C. Allen filed as Ser. No. 840,927 on Oct. 11, 1977, issued as U.S. Pat. No. 4,090,893, and assigned to The United States of America as represented by the Secretary of the Army, Washington, D.C., teaches and claims a bonding agent system for use in a hydroxy terminate polybutadiene propellant composition that is curable with a diisocyanate curing agent. This propellant contains a high solids loading of aluminum metal fuel and ammonium perchlorate oxidizer, and it employs a bonding agent system consisting of MT4, the reaction product of 2.0 moles of tris 1 (2 methyl aziridinyl) phosphine oxide, 0.7 mole adipic acid, and 0.3 mole tartaric acid in an amount from about 0.10 to about 0.20 weight percent of the propellant composition; HX752, bis isophthaloyl 1(2 methyl) aziridine in an amount from about 0.10 to about 0.20 weight percent of the propellant composition; and BIDE, butyliminodiethanol in an amount from about 0.02 to about 0.05 weight percent of the propellant composition.
The above hydroxy-terminated polybutadiene propellant composition employed an optional delay quick cure catalyst system (of each parts) of triphenylbismuthine, magnesium oxide Mg0 and maleic anhydride (MAN)(0-0.05% each). The delayed quick cured system with isophorone diisocyanate (IPDI) makes possible a longer pot like but a shorter cure time of only 2 days as compared to more than 5 days for propellants cured with dimeryl diisocyanate (DDI) and 14 days for propellants cured with IPDI without using a catalyzed cure.
Applicant's U.S. Pat. No. 4,913,753 teaches that an amount from about 0.5% to about 2.0% weight percent of meta-tetramethylxylene diisocyanate (m-TMXDI) is effective in extending propellant pot life and yielding a propellant composition which is less sensitive to temperature change as compared with an isophorone dissocyanate (IPDI) cured composite rocket propellant composition. The domestically produced m-TMXDI is made by a non-phosgenation process developed by American Cyanamid Company's research laboratories. The original proposed application, prior to applicant's patent, for m-TMXDI and p-TMXDI was in reaction injection molding (RIM) which permits the manufacture of urethane parts which require no post-painting. The isomers of either TMXDI which are naturally white (or can be pigmented any desired color) are light stable; and if scratched or damaged in use, they retain their integral color. Triphenylbismuthine (TPB) has been used singly in propellants to obtain higher modulus and/or stress values in composite propellants with isocyanate cured hydroxy terminated polymer binders. TPB has been widely accepted for the designated benefits it provide; however, since the cost of TPB is in the range of $1.08 per gram, an adjunct to TPB having only a fractional part of the cost of TPB and which imparts equal or improved benefits to the mechanical properties in hydroxyterminated binders would be attractive in view of present budget restraints to reduce cost.
Maleic anhydride, MAN, as an adjunct to triphenylbismuthine (TPB) yields improved benefits to the mechanical properties of isophorone diisocyanate cured hydroxy terminated polymer binders. Results from several propellant mixes indicate that both pot life and mechanical properties are affected not only by the concentration of TPB catalyst used, but also by the ratio of TPB to MAN. The ratio of TPB to MAN from about 1 to 0.5 to about 1 to 1.5 produces interesting results in the values of stress, strain, and modulus as shown in the data set forth hereinbelow and as graphically depicted in the drawing.
Higher modulus and stress values are obtained by using MAN as an adjunct to TPB in a cure catalyst system for hydroxyterminated polymers cured with isocyanate curatives. Equivalent mechanical properties of propellants containing a reduced amount of TPB when supplemented with MAN, as compared to those propellants containing TPB without MAN, are obtained.
The composite rocket propellants containing hydroxyterminated polymers cured with m-tetramethylxylenediisocyanate (m-TMXDI) as disclosed and claimed in applicant's U.S. Pat. No. 4,913,753, issued Apr. 3, 1990 and assigned to United States of America as represented by the Secretary of the Army, Washington, D.C., was further tested with TPB: Man in ratios from 1:1 to 1:1.5 to show the improvements to modulus and stress values which is achieved when this domestically produced and recently qualified isocyanate curative for propellant is used as specified.
FIG. 1 depicts the increase in stress and modulus values achieved from use of 1:1 TPB:MAN in m-TMXDI cured propellant compositions.
FIG. 2 depicts the increase in stress and modules values achieved from use of 1:1.5 TPB:MAN in m-TMXDI cured propellants.
Higher modulus and/or stress values are obtained for composite propellants with isocyanate cured hydroxy terminated polymer binders when triphenylbismuthine and maleic anhydride (MAN) are used in ratios from 1:1 TPB:MAN to 1:1.5 TPB:MAN in predetermined amounts each. MAN permits a reduction in the amount of TPB. The cost comparison of $1.08 per gram for TPB compared to a cost of $0.005 per gram of MAN translates to a savings from 46% to 64% for the specified ratio of TPB:MAN used.
Table I depicts physical property data of IPDI cured propellants with TPB and MAN in amounts from 0.02 TPB to 0.025% and 0% MAN to 0.03% wherein the ratio of TPB:MAN varies from 1:0, 1:1 and 1: 1.5.
Table II depicts the effect on mechanical properties of various concentration in percent TPB used in m-TMXDI cured propellants.
Table III depicts the effect of TPB concentrations and MAN concentrations and the TPB:MAN ratios on mechanical properties of m-TMXDI cured propellants.
TABLE I __________________________________________________________________________ PHYSICAL PROPERTY DATA OF IPDI CURED PROPELLANTS __________________________________________________________________________ PROPELLANT ID: TPB 0.02 TPB 0.02 TPB 0.02 0.025 MAN 0.00 0.02 0.03 0.025 IPDI STRESS, psi 76 93 82 +60° C. STRAIN, max/brk 37.5 38.6 28.3 30.7 37.5 39.0 MODULUS 412 607 466 STRESS, psi 113 111 133 120 +25° C. STRAIN, max/brk 38.9 40.6 40.6 42.3 32.0 34.4 36.0 40.9 MODULUS 542 608 808 670 STRESS, psi 307 320 323 300 -40° C. STRAIN, max/brk 41.1 47.7 40.6 48.6 37.3 50.3 44.7 52.0 MODULUS 5407 5630 6206 6206 __________________________________________________________________________
TABLE II __________________________________________________________________________ EFFECT OF TPB CONCENTRATION ON MECHANICAL PROPERTIES __________________________________________________________________________ % TPB None 0.015 0.025 0.035 0.045 STRESS, psi 107 107 115 122 123 STRAIN, 32.6/37.6 41.9/46.5 40.0/42.9 40.2/42.0 34.7/35.3 +25° C. max/brk MODULUS 664 542 652 680 762 __________________________________________________________________________
TABLE III __________________________________________________________________________ EFFECT OF TPB CONCENTRATION AND TPB/MAN RATIO ON MECHANICAL PROPERTIES __________________________________________________________________________ TPB TO MAN RATIO 1:0.5 1:1 1:1.5 TPB 0.015% MAN 0.015% MAN 0.0225% STRESS, psi 118 151 +25° C. STRAIN, max/brk 35.9/38.2 35.2/37.8 MODULUS 637 956 TPB 0.025% MAN MAN MAN 0.0125% 0.025% 0.0375% STRESS, psi 128 139 162 +25° C. STRAIN, max/brk 33.2/33.8 35.4/38.7 27.3/27.5 MODULUS 724 777 1092 TPB 0.035% MAN MAN 0.035% 0.0525% STRESS, psi 162 164 +25° C. STRAIN, max/brk 31.8/34.4 21.3/23.1 MODULUS 1025 1418 __________________________________________________________________________
Further discussions and correlations of the data of Tables I, II, and III are set forth hereinbelow, and the results achieved in improved mechanical properties are depicted graphically in FIGS. 1 and 2. Curves A and B of FIGS. 1 and 2 depict stress and modulus respectively.
TABLE I, Physical Property Data of IPDI Cured Propellants shows the effect on mechanical properties of isophorone dissocyanate (IPDI) cured propellants with the addition of 0.02 and 0.03% MAN with 0.02% TPB. Modulus at 25° C. increased 12% with 0.02% MAN. With 0.03% MAN modulus increased 49% and stress increased 18% over that of the baseline formulation which contained no MAN. At 25° C., the composition containing 0.02% TPB and 0.03% MAN had 21% greater modulus and 9% greater stress than the composition containing 0.025% each of the TPB and MAN. At 60° C., modulus increased 47% with the addition of 0.03% MAN; WITH 0.025% EACH TPB and MAN, the modulus increased by 13%. Higher modulus at elevated environmental temperatures can be important in preventing propellant grain slump and deformation. The addition of MAN to the propellant formulations caused no significant change in stress at -40° C. This is important because low stress capability at low temperatures can result in grain fracture during storage or ignition in a cold environment.
A series of mixes with tetramethylxylenediisocyanate (m-TMXDI) as the curing agent showed the effects of varying both the concentration of TPB and MAN and the ratio of TPB to MAN. Table II shows the results of increasing TPB when TPB alone is used. Maximum stress increased with increasing concentration of TPB up to 0.035%. At 0.035% TPB maximum stress valued was 14% above the max stress of the uncatalyzed propellant. No further increases in max stress occurred beyond 0.035% TPB but modulus continued to increase and strain values decreased.
Results from several mixes employing m-TMXDI suggest that both pot life and mechanical properties are affected not only by the concentration of TPB catalyst used, but also by the ratio of TPB to MAN. To quantify this effect, a series of mixes was made in which the concentration of TPB and the TPB to MAN ratio was varied. Results are tabulated in TABLE III, Effect of TPB Concentration and TPB/MAN Ratio on Mechanical Properties.
All values, stress, strain, and modulus of propellant containing 0.015% TPB with 0.0225% MAN (a 1 to 1.5 ratio) were higher than those of the propellant containing 0.025 TPB and 0.0125% MAN (a 1 to 0.5 ratio). Its stress and modulus values were also higher than those of the propellant containing 0.025% each of TPB and MAN, while their strain values were equivalent. Equivalent stress and comparable modulus values were obtained with 0.025% TPB with 1 to 1.5 of TPB to MAN and a 1 to 1 ratio of 0.035% TPB to MAN. Greater increase in stress and modulus was demonstrated by increasing the concentration of MAN with 0.015% TPB. Stress increased 28% and modulus 50% at 25° C. when the ratio of TPB to MAN was changed from 1:1 to 1:1.5 with 0.015% TPB. Strain remained the same. With 0.025% TPB stress and modulus increased 17 and 40%, respectively, with the change from 1:1 to 1:1.5 TPB:MAN, with 0.035%, stress and modulus increased 1 and 38%, respectively, with the same ratio change. In both of these last two cases, strain was significantly reduced.
In further reference to the Figures of the Drawing, FIGS. 1 and 2, (Curves A and B, stress and modulus), respectively show the effect on mechanical properties of increasing concentrations of 1:1 and 1:1.5 TPB to MAN, respectively. It is evident that to obtain maximum stress with the 1:1 ratio, 0.035% TPB is required whereas the same maximum stress is reached with 0.025% TPB with 1:1.5 TPB to MAN.
In conclusion, higher modulus and stress values are obtained by using MAN as an adjunct to TPB in a cure catalyst system for hydroxyterminated polymers cured with isocyanate curatives. By the use of MAN with TPB the concentration of TPB can be reduced yet equivalent mechanical properties of propellants containing TPB without MAN can be attained. The resulting cost savings is readily recognized since the cost comparison of TPB:MAN is $1.080/gram:$0.005/gram.
Claims (4)
1. A composite propellant composition comprising oxidizer an isocyanate curing agent selected from isophorone diisocyanate and tetramethylxylenediisocyanate; a hydroxyterminated polymer binder; and triphenylbismuthine in a weight percent range from about 0.015 to about 0.035 having improved, higher modulus and/or stress values which employs in said composite propellant composition a cure catalyst system consisting of maleic anhydride in a weight percent range from about 0.0125 percent to about 0.0375 percent in combination with said triphenylbisumthine, said weight percent ranges of said triphenylbismuthine and said maleic anhydride being selected to provide a ratio of said weight percent ranges of said triphenylbismuthine and said maleic anhydride from about 1 to 0.5 to about 1 to 1.5.
2. The composite propellant composition as defined in claim 1 wherein the ratio of said maleic anhydride to said triphenylbismuthine of said cure catalyst system is from about 1:1 to about 1:1.5 at a weight percent of 0.02 and 0.02 and 0.02 and 0.03 respectively which yields higher modulus and stress values as compared with a composite propellant composition which contains only 0.02 weight percent triphenylbismuthine and as compared with said composite propellant composition which contains 0.2 weight percent each of said triphenylbismuthine and said maleic anhydride.
3. The composite propellant composition and the improvement as defined in claim 1 wherein said ratio of said triphenylbismuthine to said maleic anhydride is 1:1 and said weight percent of said triphenylbismuthine and said maleic anhydride is 0.035% of each which yields higher modulus and higher stress values as compared with said composite propellant composition containing said 1:1 ratio at weight percents of 0.015 and 0.025 respectively of said triphenylbismuthine and maleic anhydride.
4. The composition propellant composition as defined in claim 1 wherein said ratio of said triphenylbismuthine to said maleic anhydride is 1:1.5 and said weight percent of said triphenylbismuthine and said maleic anhydride is 0.025 and 0.0375% respectively which yields higher modulus and higher stress values as compared with said composite propellant composition containing said 1:1.5 ratio at weight percents of 0.015 and 0.0225 respectively of said triphenylbismuthine and maleic anhydride.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US07/551,106 USH934H (en) | 1990-07-09 | 1990-07-09 | Maleic anhydride adjunct to triphenylbismuthine to improve mechanical properties of hydroxy terminated binders |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US07/551,106 USH934H (en) | 1990-07-09 | 1990-07-09 | Maleic anhydride adjunct to triphenylbismuthine to improve mechanical properties of hydroxy terminated binders |
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USH934H true USH934H (en) | 1991-07-02 |
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Application Number | Title | Priority Date | Filing Date |
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US07/551,106 Abandoned USH934H (en) | 1990-07-09 | 1990-07-09 | Maleic anhydride adjunct to triphenylbismuthine to improve mechanical properties of hydroxy terminated binders |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0853603A1 (en) * | 1995-10-03 | 1998-07-22 | Atlantic Research Corporation | Molded gas generating compositions containing a quick cure hydroxyl-terminated binder system and process for producing the same |
US6024810A (en) * | 1998-10-06 | 2000-02-15 | Atlantic Research Corporation | Castable double base solid rocket propellant containing ballistic modifier pasted in an inert polymer |
CN108117467A (en) * | 2017-12-25 | 2018-06-05 | 湖北航天化学技术研究所 | A kind of method and HTPB propellant for reducing HTPB propellant solidification temperature |
CN108164377A (en) * | 2017-12-25 | 2018-06-15 | 湖北航天化学技术研究所 | Improve the method and product of TMXDI-HTPB Propellant Processing Characteristics |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4090893A (en) | 1977-10-11 | 1978-05-23 | The United States Of America As Represented By The Secretary Of The Army | Bonding agent system for improved propellant aging and low temperature physical properties |
US4913753A (en) | 1989-09-25 | 1990-04-03 | The United States Of America As Represented By The Secretary Of The Army | TMXDI, curing agent for hydroxy terminated propellant binders |
-
1990
- 1990-07-09 US US07/551,106 patent/USH934H/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4090893A (en) | 1977-10-11 | 1978-05-23 | The United States Of America As Represented By The Secretary Of The Army | Bonding agent system for improved propellant aging and low temperature physical properties |
US4913753A (en) | 1989-09-25 | 1990-04-03 | The United States Of America As Represented By The Secretary Of The Army | TMXDI, curing agent for hydroxy terminated propellant binders |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0853603A1 (en) * | 1995-10-03 | 1998-07-22 | Atlantic Research Corporation | Molded gas generating compositions containing a quick cure hydroxyl-terminated binder system and process for producing the same |
EP0853603A4 (en) * | 1995-10-03 | 2000-11-22 | Atlantic Res Corp | Quick cure hydroxyl-terminated binder system for gas-generating compositions |
US6024810A (en) * | 1998-10-06 | 2000-02-15 | Atlantic Research Corporation | Castable double base solid rocket propellant containing ballistic modifier pasted in an inert polymer |
CN108117467A (en) * | 2017-12-25 | 2018-06-05 | 湖北航天化学技术研究所 | A kind of method and HTPB propellant for reducing HTPB propellant solidification temperature |
CN108164377A (en) * | 2017-12-25 | 2018-06-15 | 湖北航天化学技术研究所 | Improve the method and product of TMXDI-HTPB Propellant Processing Characteristics |
CN108117467B (en) * | 2017-12-25 | 2020-10-20 | 湖北航天化学技术研究所 | Method for reducing curing temperature of butylated hydroxytoluene propellant and butylated hydroxytoluene propellant |
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