US 3875602 A
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United States Patent 1 Miron Apr. 8, 1975 1 FLOATING DEVICE AND MARKER SYSTEM  Inventor: Roy Richardson IIui'lbut Miron, Old
 Assignee: American Cyanamid Company,
221 Filed: Jan.12, 1973  Appl.No.:323,002
 US. Cl. 9/8.3 R; 240/225  Int. Cl 1363b 21/52; B63b 51/04  Field of Search 9/83 E, 8.3 R; 250/462,
 References Cited UNITED STATES PATENTS 3,090,977 5/1963 Murray 9/83 R 3,360,426 12/1967 Cline 240/225 X 3,576,987 5/1971 Voight et a1. 240/225 3,584,211 6/1971 McKayrauhut.... 240/225 3,614,417 10/1971 Sanford 9/83 E 3,674,648 7/1972 Soli 240/225 X Primary Examiner-Trygve M. Blix Assistant Examiner-Gregory W. OConnor Attorney, Agent, or FirmGordon L. Hart; Charles J. Fickcy  ABSTRACT A device for providing chemiluminescent light from a chemical reaction of suitable compounds in the presence of a fluorescent compound, the device being a self-contained buoyant light unit.
6 Claims, 8 Drawing Figures 1 FLOATING DEVICE AND MARKER SYSTEM This invention relates to systems and devices for providing chemiluminescent light incorporating chemical components which react chemically and provide excitat'ion for a fluorescent compound.
This invention further relates to a buoyant light marker device and more particularly, to a buoy in combination with a tubular chamber containing means for producing chemical light.
Under certain circumstances, it is desirable to have a source of visible light which is not electrically activated. Light can be provided by chemical systems, wherein the luminosity is solely the result of chemical reaction without provision of any electrical energy. Such light is known as chemiluminescent light.
Chemiluminescent light may be useful where there is no source of electricity. For example, in emergencies where sources of electrical power have failed, a chemiluminescent system could provide light. Since the system requires no externally generated source of energy, devices can be made small and highly portable. Moreover, chemiluminescent light is cold light and can be used where the heat of conventional illumination is not desired. It is also useful where electrical means could cause a fire hazard, such as in the presence of inflammable agents. Chemiluminescent light is also effective under water since there are no electrical connections to short out. Thus it may be seen that chemiluminescent light can have many useful applications.
A principal object of the present invention is to pro vide systems and devices incorporating chemiluminescent components for the provision of chemiluminescent light.
A further object of this invention is to provide means for containing chemically reactive chemiluminescent components in a non-reactive condition and means to combine said components when desired to provide chemiluminescent light.
A further object is to provide a self-contained, highly portable chemiluminescent lighting device having all chemical components therein and in which the light is displayed.
Another object is to provide a chemiluminescent lighting device which is inexpensive to make, easy to activate and highly effective.
Another object of the invention is to provide a buoyant light device having a chemiluminescent lighting system.
These and other objects of the invention will become apparent as the description thereof proceeds.
This invention comprises a device for the storage and subsequent admixture and display of a multicomponent chemiluminescent system. The device consists essentially ofa buoy or float which is adapted to hold a sticklike self-contained chemical light device. These may be held in pocket like structures in the panel. The light stick tubular container is attached, and preferably in such a way that it is easily removable, to a buoyant float preferably adapted to adjust the buoyancy in such a way so that the chemical light container normally remains in an upright position above the surface of 'the liquid on which the device is floating. Each selfcontained chemical light device consists essentially of an elongated, transparent or translucent flexible outer tube and a ridged, breakable inner tube which runs parallel to the outer and which preferably is joined to the outer tube, or relatively fixed at its ends with respect to the inner tube. The inner tube is filled (wholly or in part) with one component of a two-component chemical lighting system. The outer tube is filled with the second component. The outer tube is capped at both ends with a closure which may contain a recess which fits around the inner tube to hold it in place and which, if desired, may serve as a closure for at least one end of the inner tube. Alternatively, the inner tube may be sealed separately and attached to the outer tube at the ends or along the longitudinal side in any convenient way.
To operate the device, the outer, flexible tube of the light stick is bent causing the inner inflexible tube to fracture and thus mix the two components and initiative light production in the sticks. The outer trans1ucent tube thus becomes a lighted wand for display purposes, and it is inserted in the buoy for use.
It is clear that two or more inner tubes could be employed to store separately the components of a three or multiple-component chemical lighting system.
The chemiluminescent system of this invention thus comprises the device as described accommodating the admixture of at least two chemiluminescent components and providing for the admixture in the device of at least two chemiluminescent components comprising either (a) a component containing a chemiluminescent compound and a second component containing a hydroperoxide compound, either or both components containing a diluent, or (b) a dry solid component containing both a solid chemiluminescent compound and a solid hydroperoxide compound and a second component comprising a solvent for said solid chemiluminescent compound and said solid hydroperoxide compound. Any other necessary ingredients for the production of chemiluminescent light, or for lifetime control, or for intensity improvement, or for storage stabilization must of course either be included in one of the two system components or included as additional components. in particular with the preferred oxalic-type chemiluminescent compounds of this invention, a fluorescent compound must be included in the system.
The preferred chemiluminescent light is obtained in this invention by the reaction of a hydroperoxide with a chemiluminescent composition which, in combination, comprises a chemiluminescent compound selected from the group consisting of (1) an oxalic-type anhydride of the type disclosed and claimed in the copending application, Ser. No. 485,920, now U.S. Pat. No. 3,399,130 which is hereby incorporated by reference, (2) an oxalic-type amide of the type disclosed and claimed in copending applications, Ser. Nos. 520,052 now U.S. Pat. No. 3,442,815 and 547,782. now abandoned, refiled as Ser. No. 844,557 on July 24. 1969, subsequently abandoned and refiled as Ser. No 211,810 on Dec. 23, 1971 and still pending which are hereby incorporated by reference, (3) an oxalic-type O-acylhydroxylamine of the "type disclosed and claimec in copending application, Ser. No. 547,761, now abandoned and refiled as Ser. No. 886,395 on Dec, 18, 196. and still pending and (4) an oxalic-type ester discloset and claimed in application, Ser. No. 491,896, aban doned and refiled as Ser. No. 619,140 on Feb. 28, 196' now U.S. Pat. No. 3,597,362 in the presence of a fluo rescer compound, and a solvent. Other suitable chemi luminescent compounds are 3-aminophthalhydrazide 3,4,5-tripheny1imidazole, 10,10-dia1ky1-9,9
iacridinium salts, and 9-chlorocarbonyl- 10- iethylacridinium chloride. The latter is disclosed and iaimed in copending application, Ser. No. 427,459 ow U.S. Pat. No. 3,352,791. All of the foregoing proide chemiluminesence when reacted with a hydroperxide compound in the presence of a base. Other cheiiluminescent materials are described by K. D. Gundrman, Angew. Chemie., lnt. Ed., 4, 566/1965.
The preferred chemiluminescent compound of this ivention is an oxalic-type ester selected from the roup consisting of (a) an ester of an oxalic-type acid ii an alcohol characterized by acid ionization constant I water greater than 1.3 X l, and (b) a vinyl ester f an oxalic-type ester. Similarly, in a preferred emodiment thereof, the alcohol would be an aromatic alohol substituted by a substituent characterized by a ositive Hammett sigma value. The preferred species of xalic-type esters include bis(substitutedhenyl)oxalate such as bis(2-nitrophenyl)oxalate, bis(- ,4-dinitrophenyl)oxalate, bis(2,6-dichloro-4-nitrohenyl)oxalate, bis(3-trifluoromethyl-4-nitrophenyloxalate, bis(2-methyl-4,6-dinitrophenyl)-oxalate, bisl,2-dimethyl-4,6-dinitrophenyl )oxalate, bis( 2,4- ichlorophenyl)oxalate, bis(2,5-dinitrophenyl)oxalate, is(2-formyl-4-nitrophenyl)oxalate, bis(pentachlorohenyl)oxalate, bis( 1,2-dihydro-2-oxo-lyridyl)glyoxal, bis-N-phthalmidyl oxalate. The preerred sub-species is bis(pentachlorophenyl)-oxalate.
The peroxides employed in the components of this ivention may be any hydroperoxide compound. Typial hydroperoxides include t-butylhydroperoxide, eroxybenzoic acid, and hydrogen peroxide. Hydrogen eroxide is the preferred hydroperoxide and may be mployed as a solution of hydrogen peroxide in a solent or as an anhydrous hydrogen peroxide compound uch as perhydrate of urea (urea peroxide), perhydrate f pyrophosphate (sodium pyrophosphate peroxide), erhydrate of histidine (histidine peroxide), sodium erborate, sodium peroxide, and the like. Whenever .ydrogen peroxide is contemplated to be employed, ny suitable compound may be substituted which will roduce hydrogen peroxide.
The peroxide concentration may range from about 5 molar down to about preferably about 2 molar lown to about 10' molar. The ester of this invention nay be added as a solid or in admixture with a suitable olid peroxide reactant or in a suitable diluent, or alteriatively dissolved directly in a solution containing the ieroxide reactant.
Typical diluents, which additionally may be used in onjunction with the necessary diluent of this invenion, are those which do not readily react with a peroxde such as hydrogen peroxide, and which do not react vith an ester of oxalic acid.
Where a solvent is employed with the hydroperoxideontaining component of this invention said solvent an be any fluid which is unreactive toward the hydroeroxide and which accommodates a solubility of at east 0.01 M hydroperoxide. Typical solvents for the lydroperoxide component include water; alcohols, uch as ethanol or octanol; ethers, such as diethyl :ther, diamyl ether, tetrahydrofuran, dioxane, dibutylliethyleneglycol, perfluoropropyl ether, and 1,2- limethoxyethane; and esters, such as ethyl acetate, :thyl benzoate, dimethyl phthalate, dioctylphthalate, ropyl formate. Solvent combinations can, of course, )e used as concentrations of the above with aromatic anisole, tetralin, and polychlorobiphenyls, providing said solvent combination accommodates hydroperoxide solubility. However, when oxalic-type chemiluminescent materials are used, strong electron donor solvents such as dimethyl formamide, dimethyl sulfonide, and hexamethylphosphoramide should not, in general, be used as a major solvent component.
Where a solvent is employed with a component containing the chemiluminescent material any fluid can be used providing said fluid solubilizes at least 0.01 M concentration of the chemiluminescent material and is unreactive toward the chemiluminescent material. Typical solvents include ethers, esters, aromatic hydrocarbons, chlorinated aliphatic and aromatic hydrocarbons, such as those cited in the preceding paragraph. For oxalic-type chemiluminescent compounds, hydroxylic solvents such as water or alcohols and basic solvents such as pyridine should not be employed since such solvents used in general, react with and destroy oxalic-type chemiluminescent compounds. Solvent combinations may, of course, be used but such combinations when used with oxalic-type chemiluminescent compounds should not include strong electron donor solvents.
When a component comprising a solid chemiluminescent compound and a solid hydroperoxide is used, the solvent or solvent composition comprising the second component may vary broadly. Said solvent, however, should preferably dissolve at least 0.02 M concentrations of both the hydroperoxide and the chemiluminescent compound, and for oxalic-type chemiluminescent compounds, strong electron donor solvents should be avoided as major solvent components.
The fluorescent compounds contemplated herein are numerous; and they may be defined broadly as those which do not readily react on contact with the peroxide employed in this invention, such as hydrogen peroxide, likewise, they do not readily react on contact with the chemiluminescent compound.
A fluorescent compound is required for light emission when the prepared oxalic-type chemiluminescent compound of the invention is employed. For other types of chemiluminescent compounds a fluorescer is not required but may be used to shift the wavelength of emitted light toward the red region of the spectrum so as to change the color of emitted light. Fluorescent compounds for use with oxalic-type chemiluminescent compounds should be soluble in the reactive solvent at least to the extent of 0.0001 moles per liter.
Typical suitable fluorescent compounds for use in the present invention are those which have a spectral emis sion falling between 330 millimicrons and 1000 millimicrons and which are at least partially soluble in any of the above diluents, if such diluent is employed. Among these are the conjugated polycyclic aromatic compounds having at least three fused rings, such as anthracene, substituted anthracene, benzanthracene, phenanthrene, substituted phenanthrene, naphthacene, substituted naphthacene, pentacene, substituted pentacene, and the like. Typical substituents for all of these are phenyl, lower alkyl, chlorine, bromine, cyano, alkoxy (C,Cm), and other like substituents which do not interfere with the light-generating reaction contemplated herein.
Numerous other fluorescent compounds having the properties given hereinabove are well known in the art. Many of these are fully described in Fluorescence and Phosphorescence", by Peter Pringsheim, Interscience Publishers, Inc. New York, NY. 1949. Other fluorescers are described in The Colour Index," Second Edition, Volume 2, The American Association of Textile Chemists and Colorists, 1956, pp. 2907-2923. While only typical fluorescent compounds are listed hereinabove, the person skilled in the art is fully aware of the fact that this invention is not so restricted and that numerous other fluorescent compounds having similar properties are contemplated for use herein.
A fluorescent oxalic-type ester, such as the oxalic acid ester of 2-naphthol-3,6,8-trisulfonic acid, does not require a separate fluorescent compound to obtain light. Other typical fluorescent oxalic acid esters include esters. of oxalic acid (1) 2-carboxyphenol, (2) 2-carboxy-6rhydroxyphenol, (3) 1,4-dihydroxy-9, diphenylanthracene, and (4) 2-naphthol. Thus, a reactant including a fluorescent oxalic-type ester would thereby include at least one fluorescent compound.
It has been found that the molar (moles per liter of diluent) concentrations of the major components of the novel composition herein described may vary considerably. It is only necessary that components be in sufficient concentration to obtain chemiluminescence. The ester of oxalic acid molar concentration normally is in the range of at least about 10 to 5 molar, preferably in the range of at least about 10 to about 1 molar; the fluorescent compound is present in the range from about 10 to 5, preferably 10 to 10 molar; and the diluent must be present in a sufficient amount to form at least a partial solution of the reactants involved in the chemiluminescent reaction. If the ester is liquid, it may serve as either the sole diluent or a partial diluent.
The wavelength of the light emitted by chemiluminescence of the compositions of this invention, i.e., the color of the light emitted, may be varied by the addition of any one or more energy transfer agents (fluorescers) such as the known fluorescent compounds discussed at length above.
The wavelength of the light emitted by the composition ofthis invention will vary, depending upon the particular fluorescent component employed in the reaction.
Additionally, it has been found that the superior intensity of chemiluminescence is obtained when the final mixture producing the luminescence is maintained at a temperature of between about -40C. and 75C., preferably between about C. and 50C. However, temperature is not critical and the luminescence of Applicants process is not limited to these ranges.
The lifetime and the intensity of the chemiluminescent light obtained with the preferred oxalic-type chemiluminescent compounds of this invention can be regulated by the use of certain regulators such as:
1. By the addition of base to the chemiluminescent composition. Both the strength and the concentration of the base are critical for purposes of regulation.
2. By the variation of hydroperoxide. Both the type and the concentration of hydroperoxide are critical for the purposes of regulation.
3. By the addition of water.
4. By the addition of a catalyst which changes the rate of reaction of hydroperoxide. with the oxalic-type ester. Catalysts which accomplish that objective include those described in M. L. Bender, Chem. Revs, Vol. 60, p. 53 (1960). Also, catalysts which alter the rate of reaction or the rate of chemiluminescence include those accelerators of copending application, Ser. No. 577,595, abandoned and refiled as Ser. No. 675,141 on Oct. 13, 1967, also abandoned and refiled as Ser. No. 115,734 on Feb. 16, 1971 and decelerators of copending application, Ser. No. 577,615 abandoned and refiled as Ser. No. 648,932, also abandoned and refiled as Ser. No. 56,198 now US. Pat. No. 3,691,085.
While acids are not in general accelerators for oxalictype chemiluminescent reactions it should be noted specifically that acids are accelerators for the oxalic amide chemiluminescent compounds of copending application, Ser. No. 547,782.
More specifically, the advantages obtained by the incorporation of a catalyst of Ser. No. 577,595 may be obtained in conjunction with the objects of this present invention, by employing, according to the copending application, an ionized salt having a cation selected from (a) an organic quaternary cation selected from the group consisting of ammonium, arsenic, and phosphorous, and (b) alkali metal having an atomic weight above 22, the salt of said cation preferably being soluble in an organic solvent and preferably being characterized by a property of forming cation-aggregates when reacted with the oxalic-type ester and a hydroperoxide. One of the advantages is the fact that an excessive amount of the chemiluminescent agent may be employed whereby a higher quantum yield may be obtained when the ionized salt is employed, in contrast to systems not employing the accelerator whereby such systems would be limited to a much lower maximum concentration of chemiluminescent agent which would continue to increase rather than decrease the total quantum yield of chemiluminescent light.
Similarly, within the scope of the present invention is the concurrent employment of one or more decelerators either alone or in the composition of this invention, or in conjunction with one of more of the accelerators discussed in the preceding paragraphs. By employing one of the accelerators of the preceding paragraph, it would be possible to employ a greater total concentration of the chemiluminescent agent while concurrently would be possible to employ a decelerator which would prolong the period during which the light of high intensity is obtained from the chemiluminescent reaction. Such decelerators set forth in the copending application, Ser. No. 577,615, include for example a compound such as oxalic acid.
When oxalate-type chemiluminescent compounds are used in a solution component it may be desirable to include a stabilizing agent such as those described in copending application, Ser. No. 614,397 abandoned and refiled as Ser. No. 56,084 on June 29, 1970 now US. Pat. No. 3,718,599.
The chemical compounds, components and their reactions for providing chemiluminescent light are described in copending, commonly assigned applications, Ser. Nos. 442,802; 442,818, and those previously mentioned, and as such they do not form a part of the present invention.
The invention may be better understood by reference to the drawings in which FIG. 1 shows one outer flexible tube for one embodiment of the chemiluminescent light stick,
FIG. 2 shows the inner, rigid tube,
FIG. 3 shows one embodiment of an assembled stick,
FIG. 4 shows the method of activation of the stick,
FIG. shows the use of two interior tubes in a light stick,
FIG. 6 shows a light stick molded to have one end closed,
FIG. 7 shows a complete buoyant device having a solid float means, and
FIG. 8 shows a buoyant device with an inflatable float means.
Referring to FIGS. 1 and 2, the device comprises a flexible tube 1 partly threaded at 2 to receive a threaded plug 3 to close opening 4 of tube 1. A second plug 5 is provided to close opening 6 at the opposite end of tube 1 by a press fit. Both plugs 3 and 5 have a bore 7 for receiving a tube 8 ofa rigid, breakable material.
In FIG. 3, the assembled device is shown, with tube 8 fitted in plugs 3 and 5, which are in turn fitted into openings 4 and 6 of tube 1, holding tube 8 substantially parallel to the longitudinal axis of tube 1 and relatively fixed with respect to the ends of tube 1. Tube 8 is filled with one component of the chemiluminescent system, previously described, for example the chemiluminescent compound in a diluent.
Tube 1 is filled with the second component, described previously, such as a hydrogen peroxide solution and a fluorescent compound.
Tube 1 is a flexible, transparent or translucent material, having sufficient rigidity to maintain a shape, such as polyethylene, polypropylene, teflon and the like. Tube 7 is a rigid, breakable or frangible material such as glass, or a relatively brittle thermoset resin, e.g., thin walled bakelite or other suitable material and need not be transparent or translucent. Plugs 3 and 5 may be any suitable material such as plastic or wood. Plastics are particularly suitable in view of their ease of fabrication.
As shown in FIG. 7, a light stick is used with a float 10. Float 10 is formed from a buoyant material, such as wood, plastic and the like, either as a solid or hollow shell-like structure. If float 10 does not have sufficient weight it should incorporate a ballast material at its base. Float 10 has a receptacle 12 for holding light stick A. If desired, a reflective member or coating 14 can be put on top of float 10 to amplify the light emitted by light sticks A. The reflective layer could be a separated metallic foil layer or a coating of aluminum paint or the like material on float 10. Alternatively, float 10 itself may be a metallic material. Light stick A may fit into receptacle 12 by pressure or any suitable clamping means not shown.
To activate the device and provide light, tube 1 of a light stick A if flexed slightly as shown in FIG. 4. Tube 7, which is rigid, has its ends fixed in parallel relation to plugs 3 and 5 in recesses 7 is bent and broken at a number of points 9 allowing its contents to admix with that of tube 1 to being about the chemiluminescent reaction andn to obtain a chemiluminescent light emission visible through tube 1. When the light stick has been illuminated, the device will provide an illuminating float or marker.
As shown in FIG. 5, the device may have more than one breakable tube 8, so that more than two chemilu minescent components may be kept separated. Such a system is useful where rate regulators such as acidic or basic materials may be used in the reaction.
The color of the light emission will depend on the type of fluorescent compound and its spectral response. However, the visible color could be varied by using a colored plastic for tube 1 or colored panel numbers 11 or 12.
Referring to FIG. 8, as an example of another embodiment of the invention, it may be seen that the buoyant member 20 which may be made of various materials is hollow, has an opening 22 with a suitable type of closure 24 for the addition of liquid or other type ballast 26. The buoyant container 20 is fitted with a socket-like receptacle 28 to receive a tubular light stick B with chemical light producing means. Light stick B is slightly modified in shape so that it has a pointed end 30. As indicated, the inside of the socket-like recepta-- cle 28 having a nipple or protrusion 32 for engaging an opening 34 in extension of the tubular light stick B. This is designed so that the light stick end is engaged in the receptable 28 in such a way that it is easily removable.
Float 20 could be a collapsable plastic bag, which is partially filled with fluid ballast through opening 22, then inflated through the same opening with air after which the opening 22 is closed with closure 24 which must then be air-tight.
The construction of the light sticks may be varied so long as the basic requirements are maintained. For example, tube 8 could be open at one end and a recess 7 could be the means for closing it. In addition, one end of tube 1 could be molded closed with a recess 7 as shown in FIG. 6. Moreover, tube 8 could be fitted within tube 1 in any suitable manner, so long as its ends are relative fixed with respect to the ends of tube 1.
The invention provides a device for providing visible light whenever and whereever desired, independent of conventional electrical lighting methods and without the hazards and limitations of electrical lighting. The chemiluminescent lighting systems can be especially useful in emergency situations where all other forms of lighting have failed. The systems do not have the fire of ignitable lighting devices such as candles, gas, or oil lights.
It will be readily apparent that the chemiluminescent device is not confined to emergency lighting, however. It can be used at any time where a cold, safe illuminating means is desired. It is also useful to provide illumination where electrical illumination is unavailable. The device is highly portable and can be used for signalling or marking.
While certain specific embodiments and preferred modes of practice of the invention have been described, it will be understood that this is solely for illustration, and that various changes and modifications of the invention may be made without departing from the spirit of the disclosure or the scope of the appended claims.
1. A light marker device adapted to float on a liquid surface comprising a weighted buoyant float and a tubular member containing chemical means for producing light, the tubular member having an extension, the said float having a socket-like receptacle therein with a protrusion thereon adapted for receiving and removably engaging the tubular chemical light producing means, the tubular member extension having an opening to engage the protrusion in the socket-like receptacle of the float.
2. The device of claim I where the float has means for varying the buoyancy through the addition or re moval of a ballast material.
4. The device of claim 3 comprising a pair of concentric tubes.
5. The device of claim 3 wherein said inner tube means comprises more than one tube.
6. The device of claim 3 wherein said buoyant member comprises a reflective material adjacent said light stick.