Source: http://www.google.com/patents/US6777375?dq=%22melissa+white%22
Timestamp: 2016-05-03 06:25:27
Document Index: 473493099

Matched Legal Cases: ['art 3208', 'art 2250', 'art 2241', 'art 2650', 'art 3267', 'art 1900', 'art 2388']

Patent US6777375 - Stabilization and use of propargyl bromide - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsPropargyl bromide is effectively stabilized against shock or thermal decomposition by use therewith of an environmentally acceptable inert liquid solvent that forms an azeotrope with propargyl bromide....http://www.google.com/patents/US6777375?utm_source=gb-gplus-sharePatent US6777375 - Stabilization and use of propargyl bromideAdvanced Patent SearchPublication numberUS6777375 B2Publication typeGrantApplication numberUS 10/118,290Publication dateAug 17, 2004Filing dateApr 8, 2002Priority dateApr 8, 2002Fee statusPaidAlso published asUS20030194514Publication number10118290, 118290, US 6777375 B2, US 6777375B2, US-B2-6777375, US6777375 B2, US6777375B2InventorsRalph W. Magin, Robert C. Herndon, Jr., Mahmood Sabahi, Robert H. Allen, Noel H. Brantley, Hassan Y. Elnagar, Ronny W. LinOriginal AssigneeAlbemarle CorporationExport CitationBiBTeX, EndNote, RefManPatent Citations (19), Non-Patent Citations (16), Referenced by (3), Classifications (18), Legal Events (9) External Links: USPTO, USPTO Assignment, EspacenetStabilization and use of propargyl bromide
US 6777375 B2Abstract
That which is claimed is: 1. A stable propargyl bromide composition comprised of propargyl bromide and a stabilizing amount of
A) one or a mixture of at least about 50 wt % of C7-8 saturated hydrocarbons optionally along with up to about 50 wt %, based on the total weight of A), of (1) one or more C6 saturated hydrocarbons or (2) one or more C9 saturated hydrocarbons, or (3) both of (1) and (2); or B) a mixture of at least about 10 to about 90 wt % of one or more C6 saturated hydrocarbons and about 90 to about 10 wt % of one or more C9 saturated hydrocarbons, or C) (i) an antioxidant or an acid scavenger, or both, and (ii) toluene, one more xylene isomers, one or more non-cyclic ethers, tetrahydrofuran, dioxane, beta-ionone, ethanol, or a mixture of any two or more of the foregoing components (ii); and wherein said composition optionally is in a closed container under an atmosphere comprised of an inert gas. 2. A composition as in claim 1 wherein at least about 95 wt % of the total composition is a mixture of (i) propargyl bromide and (ii) A), B), or C).
The process is normally conducted at one or more temperatures in the range of about to 10 about 80� C. More preferably, the reaction is conducted in the range of about to 20 about 70� C.; most preferably, the temperature is in the range of about to 25 about 60� C. during the process of the invention.
It has been found possible to achieve still further advantages in connection with the manner in which the processes of the invention are carried out. More particularly, by cofeeding the reaction components, including the stabilizing agent, into the reactor or reaction zone, substantial additional advantages are obtained. The advantages of such cofeeding of the reaction components are that the temperature increase which happens during the reaction occurs more slowly, and that the temperature does not rise to as high a value as it does when phosphorus tribromide is added to a propargyl alcohol solution containing amine catalyst. This in turn is less demanding on cooling equipment. Typical high temperatures for a cofeed operation when adding phosphorus tribromide to a propargyl alcohol solution containing amine catalyst are about 40� C. to about 70� C.
50.6 wt %
67.3 wt %
69.6� C.
Literature values*
68 wt %
8770-172-1
LIMS 265234
67.0 wt %
33.0 wt %
68.8� C.
*Literature values are from Horsley, Azeotrope III, New York. TABLE 2
50.08 wt %
49.60 wt %
81 mmHg
48.68 wt %
50.77 wt %
18.0� C.
50.83 wt %
48.57 wt %
395 mmHg
52.66 wt %
46.82 wt %
54.73 wt %
44.77 wt %
67.81 wt %
31.77 wt %
72.23 wt %
2.01 wt %
25.77 wt %
73.76 wt %
2.06 wt %
24.18 wt %
396 mmHg
74.94 wt %
1.21 wt %
23.84 wt %
76.79 wt %
0.94 wt %
22.26 wt %
78.8� C.
Heptanes1 Starting
65.02 wt %
34.52 wt %
64.81 wt %
33.94 wt %
68.62 wt %
1.76 wt %
29.62 wt %
76.1� C.
70.26 wt %
29.28 wt %
66.71 wt %
1.82 wt %
31.47 wt %
73.03 wt %
1.57 wt %
25.40 wt %
78.7� C.
Isopar C2 Starting
70.03 wt %
0.47 wt %
66.7 wt %
1.34 wt %
32.0 wt %
20.8� C.
67.41 wt %
2.42 wt %
30.02 wt %
28.21 wt %
71.28 wt %
1.27 wt %
27.44 wt %
72.96 wt %
25.87 wt %
78.9� C.
67.31 wt %
0.23 wt %
31.53 wt %
66.45 wt %
4.85 wt %
1.31 wt %
27.39 wt %
71.97 wt %
4.44 wt %
2.46 wt %
21.13 wt %
79.6� C.
1Heptanes (VWR Chemical Company) contain, as determined by gas chromatography/mass spectroscopy: 36.8 area % n-heptane, 27.2 area % 3-methylhexane, 19.2 area % 2-methylhexane, with the remainder being other C7 isomers, with traces of C6 and C8 compounds. 2Isopar C (ExxonMobil Company) is a mixture, predominately of C8 isomers, and is about 80% isooctane. Example 2
The kettle was a 5-liter jacketed round bottom flask. Heat was applied to the kettle via a heating bath (1:1 ethylene glycol/water mixture). The heating bath temperature was 70� C. for all of the distillations in this Example. The heating bath was placed around the wall of the high pressure cell which allowed its operation without direct exposure to the distillation assembly. A Teflon-coated magnetic stir bar was used to help mix the contents of the kettle. The temperature of the kettle was monitored via a stainless steel thermocouple, and pressure was monitored via a stainless steel transducer. A 2-inch inner diameter vacuum-jacketed column packed with 36 inches of 0.24-inch 316 stainless steel Pro-Pak packing was used for the distillations of propargyl bromide from crude reaction product. For distillations of propargyl bromide from toluene solution, a 100 liter flask, a glass column, and approximately 8 feet of 0.24-inch 316 stainless steel packing (Pro-Pak�, Ace Glass Incorporated, Vineland, N.J.) were used.
1,3-dibromo-
2,3-dibromo-
142.8 g cyclohexane
1283.5 g
112.2 g 1660.5 g
1124.2 g
2.1 g cyclohexane
1195.3 g
1550.3 g
1011.3 g
0.88 g HCs1 4
1273.3 g
1598.2 g
860.6g
0.6 g HCs1, 0.4 g H2O
1124.4 g
1411.3 g
986.9 g
0.54 g HCs1, 0.37 g
start 3208 g
1373.0 g
1723.3 g
1200.8 g
0.77 g HCs1, 0.62 g
1754.3 g
1.1 g HCs1, 3.6 g H2O
0.7 g HCs1, 0.3 g H2O
start 2250 g
1002.6 g
0.2 g HCs1, 1.6 g H2O
872.0 g
0.4 g HCs1, 0.2 g H2O
start 2241 g
1042.3 g
1080.4 g
0.4 g HCs1, 1.9 g
0.1 g HCs1, 1.4 g
1012.9 g
1157.1 g
0.5 g HCs1, 2.7 g H2O
795.1 g
0.2 g HCs1 11
start 2650 g
1145.9 g
1395.9 g
0.8 g HCs1 distillate
6.6 g HCs1 12
2334.0 g
578.2 g
1972.3 g
0.4 g THF, 0.6 g
start 3267 g
2594.0 g
2293.2 g
0.5 g THF, 0.9 g
start 1900 g
1501.7 g
0.2 g HCs1 distillate
1496.3 g
start 2388 g
1330.5 g
703.7 g Isopar C2 distillate
1017.0 g
460.7 g Isopar C2 1HCs is an abbreviation for hydrocarbons. 2Isopar C (ExxonMobil Company) is a mixture, predominately of C8 isomers, and is about 80% isooctane. Example 3
Heavy walled 1.5 mL glass vials with Teflon-lined septum caps were used to oven age three-component propargyl bromide formulations. The septum caps were to provide a path of least resistance if a pressure build-up occurred. No such pressure build-up was ever observed, but some of the vials leaked. In these runs, temperatures of about 50� C. were used.
Very similar decomposition rates were seen at 110� C. for the toluene, Soygold 1000, and Exxsol D80 solutions. The results in DF9 were slightly different from the other solutions.
The only significant reaction occurring at 50� C. overtime is the isomerization of propargyl bromide to bromoallene. After 84 days, the bromoallene level increased from 0.26% to 0.57%.
72.4 wt %
18.1 wt % Toluene, 9.5 wt %
toluene-d8, 0.71 wt %
117 hr.
38.3 wt %
135 hr.
34.1 wt %
toluene-d8, sparged with N2 80 wt %
20 wt % Soygold1, sparged
73.5 wt %
with N2, 0.38 wt %
51.2 wt %
4.30 wt %
85 hr.
43.1 wt %
20 wt % DF#92, sparged
72.1 wt %
with N2, 0.76 wt %
33.8 wt %
13.8 wt %
20 wt % Exxsol D803,
sparged with N2, 0.36 wt %
63.9 wt %
57.0 wt %
35.8 wt %
29.4 wt %
196 hr.
15 wt % DF#92, 4 wt %
leaked; study stopped
25 wt % DF#92, 7 wt %
20 wt % Exxsol D803, 5
25 wt % Soygold1, 7 wt %
6_wt %
0.2_wt %
epoxidized soybean oil, 0.2
wt % bromoallene
0.3_wt %
˜1340
0.5_wt %
1Soygold 1000 is a methylated soybean oil product comprised of methylated soybean oil. 2DF#9 is a naphthalene depleted aromatic hydrocarbon fluid, obtained from ExxonMobil Chemical Corporation. 3Exxsol D80 consists mainly of non-aromatic hydrocarbons with an IBP of 200� C. minimum and a DP of 248� C. max. It is a product of ExxonMobil Chemical Corporation. Example 4
A group of samples was prepared, varying the amount of water, 2,6-di-tert-butyl-4-methylphenol (BHT), and epoxidized soybean oil (ESO) added to each propargyl bromide solution. Mesitylene was added as an internal standard for NMR spectroscopy. Deuterated benzene was also added as an internal NMR standard. The starting compositions were made up of 80 wt % propargyl bromide, 10 wt % mesitylene, the varying amounts of water, BHT, and ESO, and enough C6D6 to make the components add up to be 100 wt %. The oven-aging experiments were conducted by sealing each sample in an NMR tube and placing each sample in an oven, either an oven set at 50� C. or in an oven set at 60� C. The concentration of the components in the test solutions are shown in Table 5; the concentrations of the additives for each Run are shown in Table 5. “Low” water refers to less than 0.1 wt %.
Under conditions of low water at a temperature of 50� C., the presence of 3% ESO seems to favor the formation of 1-bromoallene. Under conditions of low water and a temperature of 60� C., the presence of 3% ESO has a beneficial effect but high BHT shows the greatest beneficial effect, regardless of the level of ESO.
BHT1 ESO2 Temp.
1BHT is 2,6-di-tert-butyl-4-methylphenol. 2ESO is epoxidized soybean oil. Example 5
Impact sensitivity was determined by loading the BAM sample assembly with 40 microliters of sample, being careful not to encase air in the assembly, then allowing the drop weight to strike the sample assembly. In some of the runs an air bath was used to heat the entire kuhner drop weight tester. The air bath consisted of a wooden and Plexiglas enclosure containing two finned strip heaters controlled by a temperature controller. A small fan was used to circulate the air inside the enclosure. This air bath could control the temperature to within �1� C. A temperature of 50� C. was used.
20 wt % Toluene
20 wt % A150ND1 no
20 wt % Soygold
10002 80 wt %
20 wt % Isopar M3 no
20 wt % Exxsol
D804 80 wt %
13 wt % A150ND1, no
1A150ND is a naphthalene depleted aromatic 150 hydrocarbon fluid. 2Soygold 1000 is a methylated soybean oil product comprised of methylated soybean oil 3Isopar M is a non-aromatic hydrocarbon fluid having a minimum IPB of 218� C. and a maximum DP of 257� C. and is a product of ExxonMobil Chemical Corporation. 4Exxsol D80 consists mainly of non-aromatic hydrocarbons with an IBP of 200� C. minimum and a DP of 248� C. max. TABLE 7
wt % Exxsol D801 no
wt % Exxsol D801 yes
98 wt %
wt % Soygold 10002 yes
wt % Soygold 10002 no
wt % DF#9
wt % Isopar M4 no
wt % Isopar M4 yes
wt % Cyclohexane
wt % n-Heptane
74.9 wt %
wt % Cyclohexane, 10 wt % Soygold 1000,
wt % ESO, 0.1 wt % BHT
wt % Cyclohexane, 10 wt % Exxsol D80,
wt % Cyclohexane, 10 wt % DF#9, 5 wt %
wt % Cyclohexane, 10 wt % toluene, 5 wt
wt % Cyclohexane, 10 wt % Isopar E4,
wt % Cyclohexane, 9.5 wt % Isopar E4,
wt % ESO, 0.5 wt % BHT
67.5 wt %
wt % Isopar C5, 1 wt % ESO, 0.5 wt %
BHT (at 50� C.)
wt % 1,3-dichloropropene
wt % Propargyl alcohol
4Isopar E is a non-aromatic hydrocarbon fluid having a minimum IBP of 113� C., a 50% recovered temperature in the range of 116-128� C., and a maximum DP of 143� C. and is a product of ExxonMobil Chemical Company. 5Isopar C (ExxonMobil Company) is an isoparaffinic hydrocarbon mixture, predominately of C8 isomers, and apparently contains about 80% of isooctane. Example 6
50% Go/No
audible report, smoke, and soot
20 wt % Exxsol D80
5-96 cm
20 wt % Soygold 1000
20 wt % A150
<5 cm4 smoke and soot
20 wt % Isopar M
smoke and soot; faint “pop” in three trials
20 wt % Cyclohexane
smoke and soot; faint “pop” in two trials
13 wt % A150ND, 7 wt %
<5 cm6 smoke seen in four trials; soot seen in two
10 wt % Exxsol D80, 10 wt %
faint audible report, smoke, char
31 wt % Isopar C, 1 wt %
5 & 96 cm
64.9 wt %
20 wt % Exxsol D80, 10 wt %
smoke and soot; faint “pop”
50 wt % Exxsol D80
100 wt % Soygold 1000
“Go” as low
“Go” trials: white smoke, discoloration of
100 wt % Cyclohexane
5 & 10 cm
smoke, discoloration of liquid
Nitromethane (99+%; Aldrich)
6.5-12.5 cm
all “Go” trials: audible report and smoke;
4One test out of seven was a “no” from 5.0 cm. 6One test out of five was a “no” from 5.0 cm. TABLE 9
Sample composition (n2 atm.)
90.2 &
≧96 cm1 all “Go” results:
audible report,
10 wt % toluene, 10 wt % cyclohexane, 5 wt %
>96 cm
10 wt % Soygold 10003, 10 wt % cyclohexane, 5
wt % epoxidized soybean oil, 0.1 wt % BHT2 14
10 wt % Exxsol D804, 10 wt % cyclohexane, 5 wt %
epoxidized soybean oil, 0.1 wt % BHT2 15
10 wt % DF#95, 10 wt % cyclohexane, 5 wt %
epoxidized soybean oil, 0.1 wt % BHT2 21
31 wt % Isopar C6, 1 wt % epoxidized soybean oil,
Faint audible
1At 96.0 cm, two of eleven experiments resulted in “go”. The remaining nine experiments, and an additional two experiments at 90.2 cm, resulted in “no”. Example 7
150 cm yes; smoke, soot
100 cm yes; smoke, soot;
150 cm yes; soot-like
125 cm yes; soot-like
100 cm yes; smoke and
100 cm yes; soot-like
yes; soot-like
23 wt % Aro-
matic 1501,
7 wt % epoxidized
nitromethane*
1Aromatic 150 is more than 99% pure naphthalene-depleted C9-11 aromatic hydrocarbons (CAS 70693-06-0). *For each “yes” result, the rupture disc burst and/or the piston forcefully pushed out the compression cell. TABLE 11
of O2 with N2 80 cm
N2 30 cm
no; slight dis-
N2 100 cm
Differential scanning calorimetry (DSC) tests were performed on propargyl bromide formulations to determine the combustion (exothermic peak) temperature and melting (endothermic) temperature of each formulation. A Differential Scanning Calorimeter (TA Instruments, model 2910) was utilized. The material was placed into the sample holder of the calorimeter, and heated at a rate of 10� C. per minute. For this heating rate, the temperature at which maximum heat output rate occurred was defined as the peak exothermic temperature of the sample. Both the onset temperature and maximum heat output rate temperature were recorded. If the onset exotherm is less than 100� C., the material is regarded as being too hazardous to ship. The onset and exothermic peak temperature results for the propargyl bromide formulations tested are shown in Table 12.
100 wt % 0
wt % Aromatic 150, 4 wt
wt % Aromatic 150, 7 wt
Time-to-Reaction
23 wt % Aromatic
20 sec smoke
unchanged, no
150, 7 wt %
50 sec smoke + fire
10 sec smoke
60 sec smoke + fire
12 sec smoke
70 sec smoke + fire
13 wt % Aromatic
14 sec smoke
90 sec no smoke
13 sec smoke
85 sec no smoke
Propargyl bromide formulations were tested to determine their sensitivity to detonative shock while confined in a heavy steel tube. Each formulation was placed in an uncapped steel cylinder, 4 inches long, having a 1.5 inch outer diameter and a 0.5-inch inner diameter. The witness plate, 3 inches�3 inches�0.75 inches thick, is positioned at the bottom end of the tube while a pentolite booster is placed at the top end of the tube. A blasting cap is utilized to initiate the booster. The reaction is considered positive if a hole is punched through the witness plate and/or if the steel cylinder (pipe container) is fragmented entirely. The results for the propargyl bromide formulations tested are summarized in Table 14.
No dam-
wt % Aromatic 150,
wt % epoxidized
split, but
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Searle & Co.Use of amino acyl amino propargyl diol compounds for treatment of glaucomaUS5874576Dec 11, 1996Feb 23, 1999Givaudan-Roure (International) SaLight screening agentsUS6319611Oct 25, 1999Nov 20, 2001The University Of Southern MississippiCyclopentadiene derivatives for carbon-carbon compositesGB742865A Title not availableGB756674A Title not availableGB925147A Title not availableGB942348A Title not availableGB1132417A Title not available* Cited by examinerNon-Patent CitationsReference1Author Unknown; "Toxic & Hazardous Industrial Chemical Manual For Handling and Disposal"; International Technical Information Inst.; Date Unknown; p. 441.2Barrons, Keith C.; "Methyl Bromide Alternative: Propargyl Bromide"; Farm Chemicals International; Nov. 2000; pp. 35-36.3Brandsma, et al.; "Improved Procedures For Bromopropadiene and Iodopropadiene"; Synthetic Communications, vol. 21; No. 1; 1991; pp. 69-72.4Coffee, Robert D. et al.; "Explosibility and Stabilization of Propargyl Bromide"; Eastman Kodak Co.; Loss Prevention., Symp. 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(Translated from Zhurnal Organicheskoi Khimii, vol. 21; No. 11; Nov. 1985; pp. 2328-2333.14Wang, D. et al.; "Atmospheric Volatilization of Methyl Bromide, 1,3-dicloropropene, and Propargyl Bromide Through Two Plastic Films: Transfer Coefficient and Temperature Effect"; Atmospheric Environment; vol. 33; 1999; pp. 401-407.15Wu, Yuh-Wern et al.; "Photorearrangement of Propargyl Bromide as a Probe to Study Propargylic and Allenic Radicals by Infrared Matrix Isolation Technique"; Journal of The Chinese Chemical Society, 1998; vol. 45; pp. 307-312.16Yates, S.R. et al.; "Volatility, Adsorption, and Degradation of Propargyl Bromide as a Soil Fumigant"; J. Agric. Food Chemistry; 1998; vol. 46; pp. 755-761.Referenced byCiting PatentFiling datePublication dateApplicantTitleUS9169178Sep 16, 2013Oct 27, 2015Bromine Compounds Ltd.Manufacturing of stabilized propargyl bromideUS20040176474 *Mar 9, 2004Sep 9, 2004Bromine Compounds Ltd.Pest control compositionsWO2014045278A1Sep 16, 2013Mar 27, 2014Bromine Compounds Ltd.Manufacturing of stabilized propargyl bromide* Cited by examinerClassifications U.S. Classification504/356, 514/745International ClassificationC07C17/16, A01N29/02, C07C17/42, C07C17/386, C07C21/22Cooperative ClassificationC07C17/16, A01N29/02, C07C17/42, C07C17/386, Y10T428/13, C07C21/22European ClassificationC07C17/386, C07C17/42, A01N29/02, C07C17/16, C07C21/22Legal EventsDateCodeEventDescriptionJun 17, 2004ASAssignmentOwner name: ALBEMARLE CORPORATION, VIRGINIAFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MAGIN, RALPH W.;HERNDON, ROBERT C., JR.;SABAHI, MAHMOOD;AND OTHERS;REEL/FRAME:014747/0902;SIGNING DATES FROM 20020618 TO 20020709Oct 14, 2004ASAssignmentOwner name: DEAD SEA BROMINE COMPANY LIMITED, ISRAELFree format text: NEW ASSIGNMENT;ASSIGNOR:ALBEMARLE CORPORATION;REEL/FRAME:015246/0903Effective date: 20041005Nov 4, 2004ASAssignmentOwner name: DEAD SEA BROMINE COMPANY LIMITED, ISRAELFree format text: CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNMENT THAT CONVEYED 100% RIGHTS TO DEAD SEA BROMINE COMPANY LIMITED. 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