Патент USA US2407131код для вставки
Patented Sept. 3, 1946 ‘ e ‘ ~ 2,407,131 UNITED STATES PATENT OFFICE ' ' ‘2,407,131 - ' ' PLASTICS . Herman A. Bruson and George B.~.Butler,».\Phila->' delphia, Pa., assignors to Rohm & Haas Com pany, Philadelphia, Pa., a. corporation o£ Dela ware . ' No Drawing. Application January 21, 1944, . Serial No. 519,193 9- Claims. (01. zen-set" 4 1 ‘ 2 This invention) relates to explosive or readily 26 grams (0.10‘ mol) of 2,4,6-trinitrophenyleth combustible». plastics» and deals more particularly anolI added irrso‘li‘d“ form. Stirring was-‘continued, with trinitrophenylethyl esterst of. acrylic or of- and the reaction mixture heated gradually to methacrylic acid- and polymers. thereof. re?ux and re?uxed for one-half hour. After the , I It is already known that traces of polynitro- 5? mixture had been‘ cooled, the solution was washed aromatic compounds, such as trinitrobenzene or thoroughly‘ with 10%‘ NazCO'a‘ and water, and the trinitrotoluene, will, inhibit or entirely suppress benzene was removed under vacuum on a steam the polymerization of“ acrylic or methacrylic bath. The residue was a resinous material, but, esters, for example, methyl acrylate or methyl after: washing with. dilute potassium hydroxide methacrylate. _It' was surprising to discover, 10'? solution, it became a crystalline" solid.“ Itrwas‘ therefore, that’the trirritro'phenyletl’iyl- esters of recrystallized from methanol and melts, when acrylic or methacrylic acid polymerize readily to pure, at 70° C. On heating at 100° C. with 1-5% hard, tough plastics when these esters are heated of benzoyl peroxide, it polymerized to a hard, with organic polymerization catalysts such as brown resin which melts at 8‘0°‘-90‘°' C‘. peroxides, for‘ example, benzoyl peroxide. The 15' ‘ " nitroplastics thus‘ obtained are useful for the Example 2 preparation: of military explosives. 2;4,6-txinitrophenylethyl> In carrying out thisrinvention, it has been found methccrylate.-—(A)> To 10.4 grams (0.04 mol) of‘ 2,4;6-trinitrophenyh advantageous to prepare the monomeric esters ethanol was added 9.2 grams (0.06 mol) of meth by esterifying 2,4,6-t1‘initr0Dh6nylethanol with 20 acrylic anhydride, and. the reaction mixture was the acid chloride or anhydride of acrylic or meth- heated for one hour in an oil bath at l10°‘-120° C. acrylic acid respectively The 2,4,6-trinitrophenylethanol used is obtained by condensing After the mixture had been cooled, the resinous product was washed with .1 N sodium hydroxide TNT (trinitrotoluene) with formaldehyde. The solution to remove the excess anhydride and the monomeric esters obtained are crystalline solids 25 acid formed in the reaction. After a thorough having the general formula: 1'1 (I? washing with cold water, the product became N0, solid. I pure ester melts at 94° C. CHFC__C_O_CH,OH, _NO, . . The Analysis: Found: C=44.3%; H=3.60%; N= 30 13.05%. Calculated for C12H11O8N3: NO, . It was recrystallized from ethanol. . 3,39%; ?lglfgggfa?dagei?ler °f the gmup c‘ms‘stmg "f C=44.3.%; H= N=12.9%. On heating the ester at 1102120" 0. with 2-5% The polymerization of these esters can be car- M gifsgegzgilsi?emmde’ 1t polymenzes w a’ brown’ ried out at a temperature at which they are ?uid, "0 i. e., at or somewhat above their melting points, ' ‘ . . (B) 5'2 grams (9021mm) of z’é?lgnng’ro' preferably at 95°—120° C., or in solution, as, for example, in acetone at the boiling point thereof. The peroxides which can be used include benzoyl, la’uroyl or other organic peroxide The polymer_ to phenylethant’l was dlsso Ved.m 50 Sc‘ of W en Zene by heatmg’ and .a solptlqn of '1 grams (0'02 mol) of methacrylyl “910MB m 20 0020f dry pen zene was added dropwise to the re?uxing 80111131011.‘ ization can also be carried out in aqueous suspen- R'ta?uxmg was con?rmed’ for 13w‘; h?urs' After?he sion 01, emulsion’ in which case ammonium per_ mixture had been cooled, the so ut1on was was ed sulfate can be used as polymerization catalyst. The following examples illustrate this inven- w'llth iqueous Sada‘ sglutlora ang Witter am?) the so Ven remove un er re use p esstlre n 8' tion: 1 Example 1 _ 2,4,6-trinitrophenylethyl acrylate.—To a vigorously stirred suspension of 21 grams (0.1 mol) _ 4a steam bath. The product was recrystallized from ethanol and it melts at 94° C. It polymerizes in the same way as the product prepared by the anhydride method described above. These resins‘ burn with considerable vigor. of phosphorus pentachloride in 50 cc. of dry ben- 50 When a ?ame is applied, they become ?uid be zene was added 14.5 grams (0.2‘ mol) of acrylic fore igniting, but, after ignition, they burn con acid from a dropping funnel While the temperatinuously, leaving only a small carbonaceous res ture was kept vbelow 10° C. The reaction mixture idue. They are soluble in ketones' but are in was then heated in a Water bath at 30°'-35° C. for soluble in alcohols, hydrocarbons, and chlorinated one-half hour. It was then cooled to 20° C. and 55 solvents. They are partcularly valuable as bind 2,407,131 3 4 ers for other explosives in the manufacture of 5. A polymer of an ester having in its mono meric form the formula: fuses, rockets, incendiary bombs, and related military‘ explosives. N01 We claim: 1. As a new compound, a substance having in its monomeric form the formula: . N02 R O 6. A polymer of an ester having in its mono 10 meric form the formula: N0; N02 | CH: wherein R is a member of the group consisting of hydrogen and methyl. . V 2. As a new compound, a substance having in 15 its monomeric form the formula: N0: 7. As a new compound, the ester: N0: CH:=CH—OO 0-CH1CH 1?“ N01 N02 > 3. As a new compound, a substance having in 20 N03 wherein R. is a member of the group consisting its monomeric form the formula: of hydrogen and methyl. 8. As a new compound, the ester: 25 4. A polymer of an ester having in its mono meric form the formula: 30 NO: N02 9. As a new compound, the ester: N02 0 N02 . OH: I t I 011,:(1-00 o CHaCH No, 35 N02 wherein R is a member of the group consisting of hydrogen and methyl. HERMAN A. BRUSON. GEORGE E. BUTLER.