U.S. patent application number 14/800534 was filed with the patent office on 2016-04-14 for oleo resins and phosphate esters for use in pyrotechnic formulations.
The applicant listed for this patent is John L. Lombardi. Invention is credited to John L. Lombardi.
Application Number | 20160102029 14/800534 |
Document ID | / |
Family ID | 55654987 |
Filed Date | 2016-04-14 |
United States Patent
Application |
20160102029 |
Kind Code |
A1 |
Lombardi; John L. |
April 14, 2016 |
OLEO RESINS AND PHOSPHATE ESTERS FOR USE IN PYROTECHNIC
FORMULATIONS
Abstract
A pyrotechnic formulation, wherein that formulation includes a
tricyclic phosphate ester.
Inventors: |
Lombardi; John L.; (Tucson,
AZ) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Lombardi; John L. |
Tucson |
AZ |
US |
|
|
Family ID: |
55654987 |
Appl. No.: |
14/800534 |
Filed: |
July 15, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62024875 |
Jul 15, 2014 |
|
|
|
Current U.S.
Class: |
149/94 |
Current CPC
Class: |
C06D 7/00 20130101 |
International
Class: |
C06B 25/28 20060101
C06B025/28 |
Claims
1. A pyrotechnic formulation, comprising about 16.61 weight percent
triethanolamine Borate.
2. The pyrotechnic formulation of claim 1, further comprising:
acetoguanamine; and nitrocellulose.
3. A pyrotechnic formulation, comprising a tricyclic phosphate
ester having the structure: ##STR00017##
4. The pyrotechnic formulation of claim 3, further comprising:
acetoguanamine; and nitrocellulose.
5. A pyrotechnic formulation, comprising a tricyclic phosphate
ester having the structure: ##STR00018##
6. The pyrotechnic formulation of claim 5, further comprising:
acetoguanamine; and nitrocellulose.
7. A pyrotechnic formulation, comprising a tricyclic phosphate
ester having the structure: ##STR00019##
8. The pyrotechnic formulation of claim 7, further comprising:
acetoguanamine; and nitrocellulose.
9. A pyrotechnic formulation, comprising a tricyclic phosphate
ester having the structure: ##STR00020##
10. The pyrotechnic formulation of claim 9, further comprising:
acetoguanamine; and nitrocellulose.
11. A pyrotechnic formulation, comprising a tricyclic phosphate
ester having the structure: ##STR00021##
12. The pyrotechnic formulation of claim 11, further comprising:
acetoguanamine; and nitrocellulose.
13. A pyrotechnic formulation, comprising a tricyclic phosphate
ester having the structure: ##STR00022##
14. The pyrotechnic formulation of claim 13, further comprising:
acetoguanamine; and nitrocellulose.
15. A pyrotechnic formulation, comprising a tricyclic phosphate
ester having the structure: ##STR00023##
16. The pyrotechnic formulation of claim 15, further comprising:
acetoguanamine; and nitrocellulose.
17. A pyrotechnic formulation, comprising a tricyclic phosphate
ester having the structure: ##STR00024##
18. The pyrotechnic formulation of claim 17, further comprising:
acetoguanamine; and nitrocellulose.
19. A pyrotechnic formulation, comprising a tricyclic phosphate
ester having the structure: ##STR00025##
20. The pyrotechnic formulation of claim 19, further comprising:
acetoguanamine; and nitrocellulose.
21. A pyrotechnic formulation, comprising a tricyclic phosphate
ester having the structure: ##STR00026##
22. The pyrotechnic formulation of claim 21, further comprising:
acetoguanamine; and nitrocellulose.
23. A pyrotechnic formulation, comprising a tricyclic borate ester
having the structure: ##STR00027## wherein R1 is selected from the
group consisting of --CH.sub.2-- and --CH(CH.sub.3)--.
24. The pyrotechnic formulation of claim 23, further comprising:
acetoguanamine; and nitrocellulose.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This Non-Provisional Patent Application claims priority to a
U.S. Provisional Patent Application having Ser. No. 62/024,875,
filed Jul. 15, 2014, which is hereby incorporated by reference
herein.
FIELD OF THE INVENTION
[0002] Compositions of matter are disclosed where that composition
comprises an oleo resin and/or a phosphate ester.
SUMMARY OF THE INVENTION
[0003] Applicant has prepared Aminoborate esters by reacting
trialkanolamines and trialkyl borates.
##STR00001##
[0004] Applicant has prepared pyrotechnic formulations, each of
which includes a different tricyclic borate ester.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] The invention will be better understood from a reading of
the following detailed description taken in conjunction with the
drawings in which like reference designators are used to designate
like elements, and in which:
[0006] FIG. 1 is a .sup.1H N MR of Nonivamide Reactant;
[0007] FIG. 2A is a .sup.1NMR of Nonivamide Reactant;
[0008] FIG. 2B is a .sup.13C NMR of Nonivamide Reactant;
[0009] FIG. 3A is a .sup.1H NMR of Nonivamide-Maleic Anhydride
Adduct;
[0010] FIG. 3B is a .sup.13C NMR of Nonivamide-Maleic Anhydride
Adduct;
[0011] FIG. 4A is a .sup.1H NMR of Nonivamide-Phthalic Anhydride
Adduct; and
[0012] FIG. 4B is a .sup.13C NMR of Nonivamide-Phthalic Anhydride
Adduct;
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0013] This invention is described in preferred embodiments in the
following description with reference to the Figures, in which like
numbers represent the same or similar elements. Reference
throughout this specification to "one embodiment," "an embodiment,"
or similar language means that a particular feature, structure, or
characteristic described in connection with the embodiment is
included in at least one embodiment of the present invention. Thus,
appearances of the phrases "in one embodiment," "in an embodiment,"
and similar language throughout this specification may, but do not
necessarily, all refer to the same embodiment.
[0014] The described features, structures, or characteristics of
the invention may be combined in any suitable manner in one or more
embodiments. In the following description, numerous specific
details are recited to provide a thorough understanding of
embodiments of the invention. One skilled in the relevant art will
recognize, however, that the invention may be practiced without one
or more of the specific details, or with other methods, components,
materials, and so forth. In other instances, well-known structures,
materials, or operations are not shown or described in detail to
avoid obscuring aspects of the invention.
[0015] The following examples are presented to further illustrate
to persons skilled in the art how to make and use Applicant's
borate ester compositions. These examples are not intended as a
limitation, how
[0016] Nonivamide and related oleoresin capsaicin (OC) compounds
are known non-lethal agents employed for protective as well as riot
and crowd control purposes. Such agents are typically dissolved
within solvents (e.g. alcohols, glycols, acetone etc.) and
contacted upon assailants via spraying or projectile means. They
are typically not dispersed and vaporized via pyrotechnic
propellants given their inherent limited thermal stability and
susceptibility towards decomposition when heated at high
temperatures associated with pyrotechnic propellant combustion
(e.g. sugar-chlorate, nitrate or perchlorate pyrotechnic systems
found within grenades, smoke pots etc.). In comparison to the
former, pyrotechnic devices offer a better means of delivering OC
agent in a controlled and more prolonged fashion. Hence there is
considerable advantages towards producing versions of OC which are
more thermally stable and hence more compatible with conventional
pyrotechnic propellants. One means of stabilizing OC entails
converting the phenolic hydroxyl on the molecule to a borate,
phosphate or carboxylate ester. Such esterification methods are
well known to those skilled in the art and include direct
esterification between the OC phenolic hydroxyl and boric,
phosphoric or carboxylic acid accompanied by water condensation
by-product removal, reaction of phenolic with corresponding acid
halide, acid anhydride or transesterification with borate,
phosphate or carboxylic derived ester having favorable leaving
groups. Such reactions may be conducted neat or within a solvent.
Examples of ester protected OC reactions are provided below.
EXAMPLE 1
OC Maleate Ester Synthesis
[0017] About 0.6230 g of N-vanillylnonivamide (Nonivamide,
synthetic capsaicin) (TCI America) was reacted neat at 8.degree. C.
with a slight molar excess (0.2097 g) of Maleic Anhydride (Huntsman
Chemical) for 15 minutes followed by cooling to room temperature
producing a transparent yellow colored viscous oil product. The
reaction progress was monitored using .sup.1H and .sup.13C Nuclear
Magnetic Resonance (NMR) Spectroscopy whereby downfield shifts in
the phenolic aromatic ring hydroxyl group proton and associated
carbon atom peaks was observed after maleic anhydride addition to
the melt. (See spectra and Table 4 below for NMR Spectral Shifts
obtained within deuterochloroform solution using an Anasazi
Instruments 90 MHz NMR Spectrometer.)
##STR00002##
EXAMPLE 2
OC Phthalate Ester Synthesis
[0018] A similar procedure was employed as Example 1 except 0.3580
g of N-vanillylnonivamide (TCI America) was reacted neat at
90.degree. C. with a slight molar excess (0.185 g) of Phthalic
Anhydride (Stepan Chemical Company) for 10 minutes which ultimately
yielded an off white solid product upon cooling to ambient
temperature. The reaction progress was monitored using .sup.1H and
.sup.13C Nuclear Magnetic Resonance (NMR) Spectroscopy whereby
downfield shifts in the phenolic aromatic ring hydroxyl group
proton and associated carbon atom peaks was observed after phthalic
anhydride addition to the melt. (See spectra and Table 4 below for
NMR Spectral Shifts obtained within deuterochloroform solution
using an Anasazi Instruments 90 MHz NMR Spectrometer.)
##STR00003##
EXAMPLE 3
OC Succinate Ester Synthesis
[0019] The same neat melt reaction approach was employed as the
former except 0.3118 g of N-vanillylnonivamide (TCI America) was
reacted with 0.1099 g of Succinic Anhydride (TCI America) at
110.degree. C. for 15 minutes. A white colored solid product
resulted upon cooling the melt to room temperature and NMR Spectral
analysis verified phenolic hydroxyl reaction with this acid
anhydride.
TABLE-US-00001 TABLE 4 .sup.1H Peak Chemical .sup.13C Peak Chemical
Compound Shift (ppm) Shift (ppm) Nonivamide Reactant 6.14 145.36
Nonivamide - Maleic 6.36 147.05, 145.30 Anhydride Adduct Nonivamide
- Phthalic 6.30 146.91, 145.20 Anhydride Adduct
[0020] Applicant has further found that certain [2.2.2] tricyclic
phosphate esters, i.e.
[0021] organophosphate cage compounds impart low combustion
temperatures to phosphate-containing obscurant formulations.
Applicant reacts polyol 1 with phosphorus oxychloride 2 with to
form organophosphate tricyclic compound 3.
##STR00004##
EXAMPLE 4
R1=CH.sub.2--OH
[0022] In certain embodiments, polyol 1 comprises pentaerythritol,
wherein Applicant forms tricyclic compound 6.
##STR00005##
EXAMPLE 5
R1=CH.sub.2--O--CH.sub.2--(C.sub.4H.sub.6PO.sub.4)
[0023] In certain embodiments, polyol 1 comprises
dipentaerythritol, wherein Applicant forms tricyclic phosphate
ester 8.
##STR00006##
EXAMPLE 6
R1=CH.sub.3
[0024] In certain embodiments, polyol 1 comprises trimethylolethane
9, wherein Applicant forms tricyclic phosphate ester 10.
##STR00007##
[0025] EXAMPLE 7
R1=H
[0026] In certain embodiments, polyol 1 comprises
trimethylolmethane 11, wherein Applicant forms tricyclic phosphate
ester 12.
##STR00008##
EXAMPLE 8
R1=NH.sub.2
[0027] In certain embodiments, polyol 1 comprises
Tris(hydroxymethyl) Aminomethane 13, wherein Applicant forms
tricyclic phosphate ester 14.
##STR00009##
EXAMPLE 9
R1=NO.sub.2
[0028] In certain embodiments, polyol 1 comprises
Tris(hydroxymethyl) Nitromethane 15, wherein Applicant forms
tricyclic phosphate ester 16.
##STR00010##
EXAMPLE 10
[0029] In this Example 10, Applicant has reacted tricyclic
phosphate ester comprising a pendent hydroxyl group 6 with
phosphorus oxychloride 2 to give phosphate ester 17.
##STR00011##
EXAMPLE 11
[0030] In this Example 11, Applicant has reacted tricyclic
phosphate ester comprising a pendent hydroxyl group 6 with
phosphorus oxychloride 2 to give phosphate ester 18.
##STR00012##
EXAMPLE 12
[0031] In this Example 12, Applicant has reacted tricyclic
phosphate ester 18 with melamine 19 to give phosphate ester 20.
##STR00013##
EXAMPLE 13
[0032] Applicant has prepared Aminoborate esters by reacting
trialkanolamines and trialkyl borates. Borate ester 21 reacts
amino-triol 22 to give a tricyclic aminoborate ester 23.
##STR00014##
EXAMPLE 14A
[0033] Table 5 recites one embodiment of Applicant's pyrotechnic
formulation.
TABLE-US-00002 TABLE 5 Concentration Component Function (Wgt. %)
Melamine Obscurant 20.81 Acetoguanamine Obscurant 30.81 Potassium
Chlorate Oxidizer 34.08 Sucrose Fuel 13.55 Nitrocellulose Binder
0.75
EXAMPLE 14B
[0034] Applicant reacted triethanolamine with boric acid to give
tricyclic aminoborate ester 24. Table 6 recites a pyrotechnic
formulation comprising tricyclic aminoborate ester 24. In certain
embodiments, Applicant's pyrotechnic formulation comprises about
16.61 weight percent Triethanolamine Borate 24.
##STR00015##
TABLE-US-00003 TABLE 6 Concentration Component Function (Wgt. %)
Potassium Chlorate Oxidizer 33.46 Sucrose Fuel 13.2 Melamine
Obscurant Component 21.68 Triethanolamine Borate Obscurant
Component 16.61 Acetoguanamine Obscurant Component 14.21
Nitrocellulose Pellet Binder 0.83
EXAMPLE 14C
[0035] Applicant reacted triisopropanolamine with boric acid to
give tricyclic aminoborate ester 25. Table 7 recites a pyrotechnic
formulation comprising tricyclic aminoborate ester 25.
##STR00016##
TABLE-US-00004 TABLE 7 Concentration Component Function (Wgt. %)
Potassium Chlorate Oxidizer 33.46 Sucrose Fuel 13.2 Melamine
Obscurant Component 21.68 Triisopropanolamine Borate Obscurant
Component 16.61 Acetoguanamine Obscurant Component 14.21
Nitrocellulose Pellet Binder 0.83
[0036] In certain embodiments, Applicant's pyrotechnic formulation
comprises about 17 weight percent Triethanolamine Borate 25.
EXAMPLE 15
[0037] Applicant has replaced the triethanolamine Borate component
from EXAMPLE 14/TABLE 5 with each of the tricyclic phosphate esters
disclosed hereinabove. TABLE 8 summarizes Applicant's tricyclic
phosphate ester pyrotechnic compositions.
[0038] In one embodiment, Applicant replaces 16.61 grams of
triethanolamine borate with 16.61 grams of tricyclic phosphate
ester 6. In one embodiment, Applicant replaces 16.61 grams of
triethanolamine borate with 16.61 grams of tricyclic phosphate
ester 8. In one embodiment, Applicant replaces 16.61 grams of
triethanolamine borate with 16.61 grams of tricyclic phosphate
ester 10. In one embodiment, Applicant replaces 16.61 grams of
triethanolamine borate with 16.61 grams of tricyclic phosphate
ester 12. In one embodiment, Applicant replaces 16.61 grams of
triethanolamine borate with 16.61 grams of tricyclic phosphate
ester 14. In one embodiment, Applicant replaces 16.61 grams of
triethanolamine borate with 16.61 grams of tricyclic phosphate
ester 16. In one embodiment, Applicant replaces 16.61 grams of
triethanolamine borate with 16.61 grams of tricyclic phosphate
ester 17. In one embodiment, Applicant replaces 16.61 grams of
triethanolamine borate with 16.61 grams of tricyclic phosphate
ester 18. In one embodiment, Applicant replaces 16.61 grams of
triethanolamine borate with 16.61 grams of tricyclic phosphate
ester 20.
TABLE-US-00005 TABLE 8 Concentration Component Function (Wgt. %)
Potassium Chlorate Oxidizer 33.46 Sucrose Fuel 13.2 Melamine
Obscurant Component 21.68 Tricyclic Phosphate Ester Obscurant
Component 16.61 Acetoguanamine Obscurant Component 14.21
Nitrocellulose Pellet Binder 0.83
[0039] In one embodiment, Applicant's pyrotechnic formulation
comprises about 17 weight percent of tricyclic phosphate ester 6.
In one embodiment, Applicant's pyrotechnic formulation comprises
about 17 weight percent of tricyclic phosphate ester 8. In one
embodiment, Applicant's pyrotechnic formulation comprises about 17
weight percent of tricyclic phosphate ester 10. In one embodiment,
Applicant's pyrotechnic formulation comprises about 17 weight
percent of tricyclic phosphate ester 12. In one embodiment,
Applicant's pyrotechnic formulation comprises about 17 weight
percent of tricyclic phosphate ester 14. In one embodiment,
Applicant's pyrotechnic formulation comprises about 17 weight
percent of tricyclic phosphate ester 16. In one embodiment,
Applicant's pyrotechnic formulation comprises about 17 weight
percent of tricyclic phosphate ester 17. In one embodiment,
Applicant's pyrotechnic formulation comprises about 17 weight
percent of tricyclic phosphate ester 18. In one embodiment,
Applicant's pyrotechnic formulation comprises about 17 weight
percent of tricyclic phosphate ester 20.
[0040] In one embodiment, Applicant's pyrotechnic formulation
comprises about 17 weight percent of tricyclic borate ester 24. In
one embodiment, Applicant's pyrotechnic formulation comprises about
17 weight percent of tricyclic borate ester 25.
[0041] While the preferred embodiments of the present invention
have been illustrated in detail, it should be apparent that
modifications and adaptations to those embodiments may occur to one
skilled in the art without departing from the scope of the present
invention.
* * * * *