US2583509A - Solvents containing nitriles - Google Patents

Description

Patented Jan. 22, 1952 Howard Hartough, litmam and fHowardW. SheldonyWoodh'ury, N J., axssignorslt'o Soconyf- Vacuum? Oil Compan ration of New York i y, Incorporated,` agcorpo- Application Qctoberis,,1947;Seria1No. 180,208`

The presentiinvention relates tousolvents` for natural and synthetic resins, gums, etccand, more particularly,v to composite solvents e of: more than linear -kauri-butanol number.` i

As pointed out by. W. J. Sweeney andJ. A; Tilton in Industrial v.and Engineering Chemistry for June 1934, Them widespread use of#` synthetic resins-for example thesphenolformaldehyde and thealkyd, or Glyptal typeshas created demands4 for naphthas of `1 higher. solvency-than; the common run of `petroleum solventsmarketed in the past. While .'the. `coal-"tar solventssuch-as toluene and high-flash naphtha possess fhigh solvencyk powers,` they i have i' certain objectionable properties,Y in particular :poor odor.

The gum kauri-butanol test is frequently utilized by both.; theoiLQrener" and the trade for evaluating solvent naphthas.` Thistest consists essentially of titrating grams f `of a standard gum kauri solution (100 grams of'gumkauridissolved in llgrauis-onfbutanol)` ina 200 centimeter Ehrlenmeyer flask with the solvent to be tested;l The end point is reached Whenthe normally clear liquid acquires a slight turbidity.

This is determinedby placing aprinted page (10- i point print) "beneath the -ilaskI and notingwhen the print, asviewed;` through the solution, just becomes blurred. 'I'he number of cubic centimeters of` solvent-required to produce` this end point is called the kami-butanolvalue\of the solvent. i i

It has nowbeen discovered' thatthewkauributanol values of solvents can be enhanced in more than a linear proportion by combining recognized solvents with aromatic nitriles. This is surprising since it is to be expected that a mixture of two solvents would have a kauri-butanol value closely approximating the weighted average of the kauri-butanol values of the solvent and the aromatic nitrile. For example, the kauributanol value for benzene is 103 and that for benzonitrile is 122. It would be expected that a blend containing 50 volume per cent of each Would have a kauri-butanol value of 115. However, a blend containing 50 volume per cent of benzene and 50 volume per cent of benzonitrile has a kauri-butanol value of 139. Accordingly, it is an object of the present invention to provide a multicomponent solvent having a kauributanol value greater than the calculated weighted average kauri-butanol value for the components. It is another object of the present invention to provide multicomponent solvents containing an amount of an organic nitrile effective to produce a kami-butanol value for the multicomiclaim. (C1. 10s-311) 2 ponent solventgreater thanthe calculated weightedhaverage of fthefkauri-butanolvaluesz: off the components. Will become apparenttoL those skilled infthe artfrom the followingv description takenin conjuncf tionrwith the drawings in which, i

Figure 1Y is a graph of the `observed:andra/leu-` lated rlrauri-butanol values; forV various mixtures` benzeneand benzonitrile; Y Figure 2 is a` graph of lthe'observed and `(salou--` lated' kauri-butanol values for f various :mixtures of r1-hexane andfbenzonitrile; Y

Figure 3 is a graph off'the observed andcalculated kauri-butanoli values, for various: mixtures cfibenzonitrile` and an aromatic petroleum stock having a boiling range of 275 degreestof375fde,.` greesA Fahrenheit and comprisingL a .mixture ofA polyalkyl benzenes paraflins.` andlnaphthenes,

the polyalkyl benzenes being predominantly di` methyl benzenes; andff i y Figure Al isa graph of `observed and calculated kauri-butanol values for various mixturesof benzonitrile and anintermediate petroleum naphthal aromatic hydrocarbons mixedwith benzonitrile have Va slope ioramountsof benzonitrile up tov50 volume per cent diierent than the slopes of curves for mixtures of aliphatic or predominantly aliphatic solvents and up to 50 volume per cent of benzonitrile. Thus, for example, the kami-butanol value for a volume per cent benzene-10 volume per cent benzonitrile mixture is while the calculated value is 105. This represents an increase of 19 per cent of the calculated kauributanol value. Similarly, the observed kauributanol value for a 90 volume per cent aromatic petroleum stock-10 volume per cent benzonitrile mixture is 98 while the calculated value is 83 or an increase of 18 per cent. On the other hand, the observed kauri-butanol value for a 90 volume per cent intermediate naphtha-l volume per cent benzonitrile mixture is 48 While the calculated value is 45; an increase of about 7 per cent. Similarly, the calculated kauri-butanol value for a 90 volume per cent n-hexane-lO volume per cent benzonitrile mixture is 36 and the observed value is 36. The following table provides a com- 55 parison of the effect of adding varying amounts Other objects and advantages l of benonitrile, an aromatic nitrile to various solvents.

butanol value of the mixture being the sum of the kauri-butanol values of each component Benzene, Aromatic petroleum stock, Intermediate naptha, n-hexane, kauri-butanol value kami-butanol value kami-butanol value kauri-butanol value Vol. Per Vol. Per Centgrnzo- SClent t m e o, ven Y Per cent Per cent v Percent 1 Per cent f obs. cal` inc. obs. cal. ma obs. cal. Vinc. obs. cal. ine

100 103 79 36 28 2 98 115 103 11. 7 83 80 3. 7 39 39 29,. 29 5 95 120 104 15. 4 88 481. 8. 6 40 40 31 31 90 125 105 19. 0VV 99 83 19. 3 i 48 45 6.7 36 36 80 132 107 22. 2 115 88 30. 7 06 54 22. 2 50 45 11. 1 70 135 109 V18. 2 128 92 39. 2 88 62 25. 8 75 55 36. 4 60 138 111 23. 2 137 96 42. 7 108 70 54. 3 100 65 53. 9 50 139 113 20.8 142 100 42. 0 127 80 58.8 118 74 59. 5 40 138 114 21. 0, 144 108 33. 3 139 88 57. 3 133 83 60. 3 30 137 116 18. 1 141 109 29. 4 145 96 51. 0 140 93 50. 5 20 133 118 12. 7 136 113 20. 4 145 105 38. 1 141 102 38. 3 10 130 120 8. 3 129 117 10. 3 140 114 22. 8 136 112 21. 4 0 122 122 122 122 122 122 122 122 The data presented in the table together with 20 multiphed by the volume per cent of said comthe graphs of Figures 1 to 4 establish that for non-aromatic or predominantly non-aromaticV solvents the minimum amount of added aromatic nitrile to produce a practical increase in the kauri-butanoi value is about 20 volume per cent. However, for aromatic or predominantly aromatic solvents the minimum amount of added aromatic nitrile to produce a practical increase in the kauri-butanol value is about 2 to about 10 volume per cent. Accordingly, the minimum effective concentration of aromatic ntrile in the multicomponent solvent is about 2 volume per centV when the basic solvent is predominantly aromatic in nature and about 20volume per cent when the basic solvent is predominantly nonaromatic in nature. It is also to be noted that concentrationsof aromatic nitrile in excess of about '70 volume per cent of the total multicomponent solvent are ineffective to produce enhanced kauri-butanol values when the basic solvent is predominantly aromatic in character whereas concentrations as high as 80 volume per cent of the multicomponent solvent are eiective to produce enhanced kauri-butanol values when thebasic solvent is predominantly non-aromatic in character. Thus, the novel multicomponent solvent comprises an aromatic nitrile and one or more hydrocarbons, the mixture containing a concentration of aromatic nitrile effective to produce kauri-butanol values at least 10 per cent greater than the calculated kauri-butanol value Y of the mixture, the calculated kaurponent in vthe multicomponent solvent.

We claim: i

A multicomponent solvent for resins, gums, and the like which consists essentially of a predominantly aromatic hydrocarbon solvent for resins,

gums, and the like and benzonitrile, said benzo- REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Y Date Number Name 2,388,082 Roediger Oct. 30, 1945 2,450,639 Denton etal. Oct. 5, 1948 2,508,215

Bishop May 16, 1950 OTHER REFERENCES Journal of Chemical Society, Article by Martin and Collie, pp. 26587-65 (1932).

Journal American Chemical Society, vol 24, 1902, Bozert and Hand, pp. 1031-1032.

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