Lapas attēli
PDF
ePub

Nitrates, carbonates, chlorides, or oxides of metals can be used to prepare the salts by the methods described earlier. Organic bases, e.g., amines, tetra-substituted ammonium hydroxides, phosphonium hydroxides, sulfonium hydroxides, arsonium hydroxides or halides, stibonium hydroxides or halides, aryldiazonium hydroxides or halides, amino acids (e.g., glycine), esters of amino acids, and similar types of bases can be employed. Heterocyclic bases, e.g., pyridine, quinoline, a,a-dipyridyl, piperazine, pyrrolidine, phenazine, morpholine, thiamorpholine and the like, are operable to form salts.

The following table illustrates representative salts which can be obtained by neutralizing the acids with a base or an appropriate salt in aqueous solution (Table IV):

[blocks in formation]

The process described above and illustrated in the examples are generic for the preparation of compounds of the invention as defined by Formula 1. The processes can be used alone or in combination to obtain the desired products. For example, H2S can be reacted, as described in Example 36; with hydrated H12B12HCl to obtain H2B12H6C14 (SH)2, with H2B12Hg(OH), to obtain a mixture of thiol substituted compounds, e.g. H2B12H,(OH), (SH), and H2B12H(OH), (SH)2 with H2B12H11F to obtain H2B12H8F (SH)3 and with H2B2H10(OCH3)2 to obtain H2B12H (SH)2 (OCH3)2. Similarly, hydrated H2B12H12 can be reacted as described in Example 13, parts D and E, with long chain a,-dihydro- and a,a,a-trihydroperfluoroalkanols, e.g. CF3(CF2);CH2OH, HCF2(CF2)3CH2OH, HCF2(CF2);CH2OH, and HCF, (CF2) CH2OH to obtain fluoroalkoxy substituted dodecaborates, e.g., H2B12H10 [OCH2(CF2)5CF3]2, H2B12H11OCH2(CF2)3CF2H, H2B12H10[OCH2 (CF2)5CF2H2, Li B12H1CH(CH3) C6H5, CaB12H1C3H7, SrB12I12, and H2B12H1OCH2 (CF2),CF2H. Polychloropoly fluoroalkanols can be employed in the reaction, e.g., CIFCCF, CFCICF2CF2CH2OH, to obtain H2B12HOCH2CF2CF2CFCICFCFCI. Monocyano substituted compounds can be obtained by contacting the crude reaction product obtained in Example E with liquid ammonia to prepare CS2B12H1C(O) NH2 and dehydrating the monoamide, as described in Example 37, part A, to obtain CS2B12H1CN. Reaction of this compound with CH CH2SSCĤ2C6H5, described in Example 8, part A, will yield Cs2 B12H9 (SCH2C6H5)2CN, a compound which can then be brominated as described in Example 3, part C, to obtain CS2B12H3Br. (SCH2CH3)2CN.

as

Further examples which illustrate the products obtained by the described processes are

and

[(C2H5)3NH2B12H6F6, Ag2B12F12, CS2B12F12
ZnB12Cl21 7H2O, [(C6H13)4N]2B12Cl12

(H3O) 2B12H2Bг10 6H2O, (H2O)2B12H2Bг10 4H2O
Na2 B12C110 (COOH)2, K2B12C110 (COOH)2
Rb2B12C110(COOH)2, Na2B12N10 (NCO)2

Liz B12H11CH (CH3) C6H5, CаB12H11C3H7, SrB12I12

HgB12Br12

The illustrations in the preceding paragraphs demonstrate the generic nature of the processes and their versatility to obtain a wide range of products which fall within the scope of the compounds of the invention.

Utility

The invention provides a broad class of new boron compounds which find applications in many fields.

The compounds of the invention are generically useful as components of fireworks compositions to impart a pleasing color and sparkle to the display.

Each compound within the scope of Formula 1 con ains an anion which has boron as a common component. The presence of this element imparts a green color to a fireworks, rocket or flare display. The compounds of the invention can have a wide range of cations, designated as M, and it is thus possible to provide a broad range of colors in any display or flare by choice of the apporopriate cation. The compounds of the invention can be used in combination with oxidizing agents, e.g., lithium perchlorate, sodium nitrate, potassium permanganate, strontium peroxide, managnese dioxide, and the like, to provide the desired propulsive effect and color. The following combinations, in which the boroncontaining compounds can be form 5-25% by weight of the composition, are illustrative of compositions which can be used:

CS2B12H10F2-NaNO3, Na¿B12H6Bг6—LiNO3

CS2B12H1012-LINO3, CS2B12H6 (OH) 6-SrNO3-NaNO3
CS2 B12H11OCH3-KCIO3

CS2 B12H11SO2C6H5-KMnO4-NaNO3
[(CH3) N2B12H1NO2-NH,NO, KNO,

CS2B12H,Cl2(CN), NH,NO-LICIO

Tl2B12H10]C(O)OTI2-NaNO3-Sr NO3

CS2 B12H10[C(O) NH2]2-MnO2-NH4NO3
[CH3)4N2B12H10[C(O) OCH3]2-NaCIO, MnO2
[(CH3)4N]2B12H10 (NCO) 2-NaNO3-KNO3

and the like. These examples are not limiting but are illustrative of types of compositions which are possible for use in the above field. Other ingredients can be and frequently are present in these combinations, e.g., carbon and sulfur.

The compounds of the invention are useful in the field of high energy fuels. For this purpose, partially substituted compounds are preferred, i.e., compounds having one to five substituents on the dodecarborate anion. The compounds can be used in combination with oxidizing agents, e.g., nitric acid, fluorine oxide and the like. They can be used in solution in hydrazine or N,N-dialkyl hydrazines, e.g., N,N-dimethylhydrazine. To illustrate, combinations which can be employed nclude H2B12H10[C(O) NH2]2 in N,N-dimethylhydrazine, (NH2NH3)2B12H11OH in hydrazine and the like. The acids in the above examples form hydrazinium salts in solution and they are not present as the free acids. In compositions as described above the dodecarborate salt can be present in form about 5-50% by weight of the solutions.

The compounds of the invention, exclusive of the fully halogenated products, are useful as impregnating agents in the preparation of resistors. To illustrate, a secton of a cotton string is immersed in a nearly saturated solution of NaBHCH (CH3)2 in aqueous alcohol. The string is withdrawn from the solution and the solvent is removed by drying in air. A free flame is applied to the dried impregnated string and it burns to yield a coherent ash which in size and shape resembles the original string. The residual skeleton is of sufficient coherence to permit embedding in parraffin. The section of residue, so treated, shows a resistance of about 300 ohms/cm. The residue from the control section of string is very small and shapeless and it cannot be handled.

Highly halogenated compounds, e.g., the salts of B12Br12 anion, are useful as impregnating agents for retarding the combustion of cellulosic products. To illustrate, filter paper which has been treated with an aqueous solution of (NH4)2B12Br12 and dried, does not burn freely when touched with a free flame. The nitrated and nitroso-substituted compounds are useful as explosives or detonating agents.

In the group of compounds which fall within the scope of Formula 1, the component M represents a range of groups which are readily interchangeable by metathetic reactions as described earlier. All of the salts which fall within the scope of Formula 1 can be used to prepare the group of acids represented generically as H2B12H12-yXy or, in aqueous solution, as (H3O)2B12H12-yXy by passing aqueous or alcoholic solutions of the salts through an acidic ion-exchange resin as described earlier. The acids of this group, exclusive of compounds in which X is an amine group, are strong acids and they are useful in industrial applications where it is desired to avoid contamination from sulfate, chloride, bromide, chlorate, phosphate, and like strong acid anions. Thus, the acids are useful for etching metals, such as steel, and for rust removal, for pickling, for scale removal and for similar metal processing operations.

The acids, described above, are useful as catalysts in the preparation of esters, e.g., in the reaction of alcohols and organic carboxylic acids, to improve the yields of the desired esters. The acids of the invention are employed for this purpose in the same manner as p-toluene-sulfonic acid, sulfuric acid or alcoholic hydrogen chloride.

Aqueous solutions of the acids are generically useful as agents for absorbing noxious basic materials from the air, e.g., traces of ammonia, lower alkyl amines and the like. To illustrate, air contaminated with methylamines is passed through an aqueous solution of H2B12H10(OH)2, H2B12H10(OCH3)2, H2B12Cl2, and the like, and the amines are removed.

The acids and many of the salts, particularly the alkali metal and alkaline earth metal salts, are useful as sequestering agents for heavy metals. Thus, a mixture of hydrocarbons in the boiling range of gasoline which contains a copper salt of an organic acid (copper stearate), is thoroughly agitated with aqueous ammoniacal solutions of any of the alkali metal or alkaline earth metal salts of the anion (B12H12), e.g., CS2B12H11SO2C6H5, Nа2B12H10(OH)2.

The new compounds, particularly the acids, alkali and the like. The hydrocarbon layer, which is separated from the aqueous reagent, is completely free of deleterious copper salt.

The new compound, particularly the acids, alkali metal, alkaline earth metal and ammonia salts, are useful as sequestering agents for metals in aqueous media. Thus, copper, nickel, cobalt, zinc and cadmium are removed from aqueous solutions of salts containing these metals by mixing the solutions with ammoniacal solutions of the acids and alkali metal, alkaline earth metal and ammonium salts. The substituted ammonium salts and, in general, all of the nitrogen-base salts as well as phosphonium and sulfonium salts are useful in the field of sequestering agents to remove undesirable metals from aqueous or hydrocarbon media.

To illustrate, a mixture of h drocarbons in the boiling range of gasoline, which contains in solution a copper salt of an organic acid (copper stearate), is thoroughly agitated with an aqueous ammoniacal solution of NaB12H2Cl10. The hydrocarbon layer, which is separated from the aqueous reagent, is completely free of the deleterious copper salt. Similar results can be obtained employing [(CH3),N]2B12H10 [OC(O) H2, CS2B12H11OCH2CH2OCH,, and the like.

The compounds of the invention, especially in the form of salts, are useful as surface-active agents, particularly as wetting agents. To illustrate, a glass surface coated with a film of a silicone is not wetted when brought into contact with water. The addition of a small quantity of dicesium cyclohexylundecahydrododecaborate to the water results in immediate wetting of the glass surface, i.e., the treated water spreads rapidly over the surface of the glass.

The silver salts, i.e., the compounds of Formula 1, where M is Ag, are sensitive to light and they are useful in the photographic arts. To illustrate, the cesium salt, Cs2B12H11OC(O)H, is reacted with silver nitrate to obtain Ag2B12H11OC(O)H. An alcoholic solution of the silver salt is prepared in subdued light and a strip of pure cellulose sheet is immersed to half its length in the solution. The strip is removed and dried in the absence of light. When exposed to light, the treated pure cellulose sheet is immersed to half its length in the solution. The strip is portion of the strip turns dark, while the untreated portion is not affected.

The foregoing detailed description has been given for clearness of understanding only and no unnecessary limitations are to be understood therefrom. The inven

tion is not limited to the exact details shown and described, for obvious modifications will occur to those skilled in the art.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A compound of the formula M,(B12H12-yXy) wherein M is a cation having a valence of 1-4; X is a monovalent element other than hydrogen, or a radical, said X being capable of bonding to the carbon of a benzene nucleus by replacement of a hydrogen bonded to said carbon; and when more than one X group is present the X's can be different; y is a positive whole number of 1 through 12, inclusive; and a and b are positive whole numbers of 1 through 3, inclusive.

2. A compound of claim 1 wherein X comprises halogen.

3. A compound of claim 1 wherein X comprises hydrocarbon.
4. A compound of claim 1 wherein X comprises acyl.
5. A compound of claim 1 wherein X comprises nitro.

6. A compound of claim 1 wherein X comprises amino.

7. A compound of claim 1 wherein X comprises hydroxyl.

8. A compound of claim 1 wherein X comprises carboxyl.

9. A compound of claim 1 wherein X comprises isocyanato.

10. A compound of claim 1 wherein X comprises hydrocarbyloxy.

11. A compound of claim 1 wherein X comprises halohydrocarbyloxy.

12. A compound of claim 1 wherein X comprises hydrocarbyloxyhydrocarbyloxy. 13. A compound of claim 1 wherein X comprises hydroxylhydrocarbyloxy.

14. A compound of claim 1 wherein X comprises hydrocarbon carbonyloxy. 15. A compound of claim 1 wherein X comprises cyano.

16. A compound of claim 1 wherein comprises hydrocarbyloxycarbonyl. 17. A compound of claim 1 wherein X comprises carbamyl.

18. A compound of claim 1 wherein X comprises thiol.

19. A compound of claim 1 wherein X comprises hydrocarbylmercapto. 20. A compound of the formula M2[B12H10(COOH)2] wherein M is a cation selected from the class consisting of hydrogen, alkali metals, and tetramethylammonium.

21. A compound of the formula M2[B12H10 (NH2)2] wherein M is a cation selected from the class consisting of hydrogen, alkali metals, and tetramethylammonium. 22. A compound of the formula M2B12C112 wherein M is a cation selected from the class consisting of hydrogen, alkali metals, and tetramethylammonium. 23. A compound of the formula M2B12 (OH) 12 wherein M is selected from the class consisting of hydrogen, alkali metals, ammonium and tetramethylammonium. 24. A compound of the formula M2B12H10 (NCO), wherein M is selected from the class consisting of alkali metals and tetramethylammonium.

25. A compound selected from the class consisting of H2B12Cl12 and hydrates thereof.

26. A compound selected from the class consisting of H2B12Br12 and hydrates thereof.

27. A compound selected from the class consisting of H2B12I12 and hydrates thereof.

28. The compound of the formula Ag2B12Cl12. 29. The compound of the formula Ag2B12Br12. 30. The compound of the formula Ag2B12I12. 31. The compound of the formula

CS2B12H10(OCH2CH2OCH3)2

32. The compound of the formula CS2B12H10(SCH3)2.

33. The compound of the formula

(NH4)2B12H10(CONH2)2

34. The compound of the formula

[(CH3),N]2B12H10(NCO)2

35. A compound of the formula M2(B12H12y-Xy) wherein M is a cation having a valence of 1-4; X is a monovalent substituent selected from the group consisting of halogen, hydrocarbon, acyl, nitro, amino, hydroxyl, carboxyl, isocyanato, hydrocarbyloxy, halohydrocarbyloxy, hydrocarbyloxyhydrocarbyloxy, hydroxyhydrocarbyloxy, hydrocarbon carbonyloxy, cyano, hydrocarbyloxycarbonyl and carbamyl; and when more than one X group is present the X's can be different; y is a positive whole number of 1 through 12, inclusive; and a and b are positive whole numbers of 1 through 3, inclusive.

[blocks in formation]

Hawthorne et al.: "Journal of the American Chemical Society," vol. 82, p. 3228 (June 1960).

Knoth, et al.: "Journal of the American Chemical Society," vol. 84, pp. 10561057 (Mar. 20, 1962).

OSCAR R. VERTIZ, Primary Examiner

G. O. PETERS, Assistant Examiner

23-361; 260-606.5

U.S. Cl. X.R.

EXHIBIT D

REPLACEMENT PENDING

Major changes in Patent Office operating methods are likely to result from the recent forced resignation of U.S. Commissioner of Patents Robert Gottschalk. Gottschalk was eased out for several reasons, including a tendency to bypass the assistant commissioners.

Morale at the Patent Office reportedly has improved since Gottschalk left, but organizationally the agency is in a shambles. The jobs of deputy commissioner, assistant commissioner for legal affairs and assistant commissioner for patent examination-all key posts-are unfilled.

Moreover, the research and development office, which Gottschalk downgraded, is mired in a squabble with the NATIONAL Bureau of Standards over electronic methods of storing and retrieving technical information. Gottschalk's predecessor, William Schuyler, established the R&D unit under an assistant commissioner. But Gottschalk eliminated that post and the operation went downhill.

Seeking Replacement: A successor for the job is not likely to be named until fall. Betsy Ancker-Johnson, Assistant Secretary of Commerce for Science and Technology, has been searching the business and legal communities for a replacement. Some observers, however, say the available talent is thin.

Two women have been mentioned as candidates-Washington patent attor neys Margaret Lawrence and Mary Sears. Both are available for the post and could find favor with Ancker-Johnson, an outspoken proponent of high-ranking jobs for women.

The job of commissioner calls for strong managerial capabilities—a trait considered scarce among patent lawyers. Former Assistant Commissioner Richard Wall, who resigned last month in a dispute with Gottschalk, says. "The next commissioner has to be a good administrator or show signs of becoming one. To bring in someone just because he is backed by the patent bar isn't adequate anymore."

Gottschalk and Wall had wrangled over policies affecting the patent examining corps. They also had personality differences. Gottschalk wanted to eliminate Wall's system of setting quotas for patent examiners and rewarding them for exceeding their targets. Under that system, patent pendency time dropped from 31 months to 24-and Wall claims it could have been down to 18 months within three years.

Gottschalk, claiming that quotas were bad for workers' morale, preferred to rely on the old-fashioned sense of professionalism.

The acting Patent Office chief is Rene Tetgmeyer, a former assistant commissioner for legal affairs. But Ancker-Johnson is handling the upper-level policy matters as well as fighting off moves in Congress, led by Senator John

« iepriekšējāTurpināt »