Патент USA US2404688код для вставки
Patented July 23,1946 1 2,404,688 UNITED STATES PATENT OFFICE} 2,404,688 7 ,7 READILY COMBUSTIBLE PLASTIC MATERIAL . Herman A. Bruson and George ‘B. Butler, Phila delphia, Pa., assignors to Rohm & Haas Com ' pany, Philadelphia, Pa., a corporation of Dela 3,1; ‘ ware No Drawing. Application January 21, 1944, 7 ‘Serial No. 513,197 4 Claims. 1 c This invention relates to explosive or readily combustible plastics and deals more particularly , . 2 - ~ zene, toluene,-or xyleneyor ethers, such as iso propyl ether, butyl ether, or the like, or mixtures of such solvents. with plastic polymers of Intro-compounds having the formula: , (01. 200-’l8) 7 1 w ' The esteri?cations involved may be performed Within the range of 50° C. to 150°C; although , both somewhat lower and higher‘ temperatures may be used, depending upon reactants, solvents, wherein R is a nitro- or polynitro-hydrocarbon radical from a monohydric nitroalcohol contain ing at least one nitro group for each four carbon atoms present therein and R’ is the hydrocarbon etc. ‘ There may be used in the .reaction mixture polymerization inhibitors, such as hydroquinone, pyrogallol, B-naphthol, etc. ‘ ' _ g The following examples illustrate this inven residue of a pry-unsaturated primary aliphatic al cohol. tion: The above nitro esters polymerize upon ex ] ~ ,_ 7 ' a ' ~ Example 1 ‘ posure to heat, light, air, and/or catalysts such 15 A‘ mixture of 78 grams (0.5 mol) of’maleici acid as benzoyl peroxide to form transparent plastics mono-allyl ester, 60 grams (0.5 mol) of 2-nitro—‘ ' varying from hard, glassy masses to tough, some l-butanol, .150‘ cc. of dry benzene, and 0.5 cciof what elastic, rubbery materials. concentrated sulfuric acid was boiled under a These new plastics burn in the air with great re?ux condenser attached to a water separator vigor and possess explosive properties. They are 20 for five hours, until‘ no more water collected in useful for the preparation of explosives, rockets, the trap. After the mixture had been cooled, ?ve fuses, ?ares, and the like, as combustible binders grams of powdered anhydrous sodium'carbonate or plasticizers for gun-cotton, TNT, picric acid, was added and the mixture stirred for one hour and other explosive compositions. at room temperature. The mixture was ?ltered As a monohydric nitroalcohol, there may be and the clear ?ltrate evaporated to'dryness in used 2-nitroethanol-1, 2-nitro-propanol-1, 2-nitro vacuo. \The residual oil was then distilled in‘ butanol-l, 2-nitro-2-methyl propanol-l, l-di vacuo. The allyl Z-nitrobutyl maleate nitrophenyl-2-nitro-2-methyl propanol-l, l-tri nitrophenyl-2-nitro-2~methy1 propanol-l, 2,4,6 trinitrophenylethanol, and other monohydric alcohols in which there is present at least one nitro group for each four or fewer carbon atoms. As a lay-unsaturated primary aliphatic alcohol, there may be used allyl, methallyl, propenyl, or crotyl alcohol, or methyl-vinyl carbinol, or the like. 39 distilled over at‘ 156°‘-163° C./2-3 mm. as a pale yellow oil. It serves as a colloiding agent for gun cotton and can also be polymerized to a trans parent‘plastic on heating with 1-2% of benzoyl peroxide at 95°-1_00° C. ' Example 2 The dibasic carboxylic nucleus may be obtained from maleic or fumaric acids or their acyl halides A mixture consisting of '72 grams of maleic acid or from maleic anhydride. mono-allyl ester, 56 grams of 2-nitro-2-methyl 40 The new esters of this invention are readily ob propanol, 150 cc. of benzene, and 0.5 cc. of con tainable in several ways. For example, maleic an centrated sulfuric acid was re?uxed for ?ve hours hydride can be ?rst esteri?ed with a nitroalcohol with’ water removal and worked up as described corresponding to group R and the resulting half in Example 1. The allyl 2-nitro-2-methyl propyl ester subsequently esteri?ed with the unsaturated maleate alcohol, R'OH, or the reverse procedure may be 45 N02 followed. According to another procedure, the acid chlo ride of the half ester of one alcohol is condensed with the other alcohol. ornd~oHl—0o0—oH=cH—ooo—oHl—oH=oHl H: Although the esters may be prepared in the ab 50 was obtained as a colorless oil which boiled at sence of solvents other than the reactants them 162°-163° C./2 mm. It polymerizes to a trans selves, it is preferred that a solvent be used. parent, plastic, readily combustible mass when Suitable for this purpose are chlorinated sol heated with 1-2% by weight of benzoyl peroxide vents, such as carbon tetrachloride or ethylene at 100° C. It may also be copolymerized. with an dichloride; hydrocarbons, such as naphtha, ben 55 equal weight of di-(-2-nitro-2-methyl propyl) 2,404,688 4 3 Example 6 maleate in the presence of 2% by weight of ben zoyl peroxide to a combustible polymer. Example 3 To a solution of 2,4,6-trinitrophenylethanol in v'70 cc. of hot dry benzene, there was gradually added 7.5 grams of the acid chloride of fumaric A mixture consisting of 78 grams of maleic acid acid mono-allyl ester, mono-allyl- ester, .53 grams of 1-nitro.-'-propano1‘-2, 150 cc. of benzene, and one gram of concentrated sulfuric acid was boiled under re?ux for eight: dissolved in 20 cc. of dry benzene. The mixture was boiled for several hours, cooled, and the product washed with water, dilute sodium car hours while the water formed was continually re moved by a water separator. After the mixture‘ was cooled, the product was Washed thoroughly bonate solution, and ?nally with water, then with water and the solvent distilled ‘off. The re sidual oil was distilled in vacuo to yield allyl l evaporated to dryness in vacuo. The residual oil was puri?ed by-several washings with hot alco nitro-isopropyl maleate CHzNOg hol and ?nally'dried in vacuo at 90° C. 15 The trinitrophenylethyl allyl fumarate CH5-—CH—O-—C 0-oH=oH—oo0-0H-.-—oH=oH¢ as a pale yellow oil which boiled at 160° C./2 mm. When heated at 100° C. with 1—2% by weight "of benzoyl peroxide, it polymerized to a dark 20 brown, thermoplastic, readily combustible resin. NO: which was obtained polymerized when heated with benzoyl peroxide (1%) at 100° C. to; a soft, Example 4 By using 0.5 mol of maleic acid mono-methallyl pliable, non-tacky resin. The corresponding maleate is obtained by heat ester in place of the maleic acid mono-allyl ester 25 in Example 2, the corresponding methallyl 2-ni ing one molecular equivalent each of maleic an hydride and 2,436-trinitrophenylethanol at 80° C. tro-Z-methyl propyl maleate in benzene solution for several hours, then add ing an excess of allyl alcohol, a small amount 30 (1 cc.) of concentrated sulfuric acid, and re?ux ing until no more water is evolved, then cooling, Washing, and evaporating off the solvent. and excess allyl alcohol. It is a brown oil whichalso 158°-159° C./1—2 mm. when heated with 2% by polymerizes as above to an explosive plastic. weight of benzoyl peroxide at 95°-100° C., it We claim: polymerized to a clear, yellowish, combustible 35 1. A readily combustible plastic polymer of an plastic. ester having the formula Example 5 isv obtained as a colorless oil which boils at A mixture of 0.5 mol each of 2-nitro-2-methyl propanol and maleic acid monopropargyl ester in wherein R is a, nitro hydrocarbon radical having 150 cc. of benzene was boiled in, the presence of 40 one to ten carbon atoms» and containing at least One nitro group i'or each‘four carbon atoms pres 0.5 cc. of concentrated sulfuric acid for ?ve to ent in said hydrocarbon‘ radical, only one'nitro six hours under a re?ux condenser attached to group being present on any single carbon atom a Water trap. After it Was washed and dried, the thereof, and R’ is the hydrocarbon residue'of‘ a product was distilled in vacuo to yield 2-nitro-2 45 monohydric ray-unsaturated primary aliphatic al methyl propyl propargyl maleate cohol of not over four carbon atoms. CHs CHs-(E-CHr-OCO——-CH=CH——COO~—CH2—CECH N02 2. A resinous polymer-of 2‘,4-,6'-trinitrophenyl ethyl allyl maleate. 3. A resinous‘polymer or 2-nitro"-2'-meth-yl pro as a colorless oil which boiled at l45°-155° C./2-3 50 pyl allyl maleate. mm. A sample of the oil was mixed with 2% by weight of benzoyl. peroxide and polymerized at 100° C. to a thick syrup. This syrup was coated onto a sheet of steel and heated at 100° C. until 55 a clear, hard, polymer ?lm was formed. 4. A resinous polymer of 1-nitro-isopropyl- allyl maleate. HERMAN A. BRUSON. GEORGE B. BUTLER.