Acrylic acid explosions

Degenerate Explosion it was a free radical autocatalytic process and control was difficult, but manageable. The main disadvantage was that it produced as much or more acrolein as propylene oxide. Because no market existed for acrolein at that time, the project was abandoned. Within two years, the acrylic market developed and a new project was initiated to make acrolein and acrylic acid by vapor-phase catalytic oxidation of propylene. 

The most common poly(alkenoic acid) used in polyalkenoate, ionomer or polycarboxylate cements is poly(acrylic acid), PAA. In addition, copolymers of acrylic acid with other alkenoic acids - maleic and itaconic and 3-butene 1,2,3-tricarboxylic acid - may be employed (Crisp Wilson, 1974c, 1977 Crisp et al, 1980). These polyacids are prepared by free-radical polymerization in aqueous solution using ammonium persulphate as the initiator and propan-2-ol (isopropyl alcohol) as the chain transfer agent (Smith, 1969). The concentration of poly(alkenoic add) is kept below 25 % to avoid the danger of explosion. After polymerization the solution is concentrated to 40-50 % for use. 

During the experimental large scale continuous polymerisation of acrylic acid in aqueous solution in presence of an initiator and a moderator, failure of one of the feed pumps led to an unusually high concentration of monomer in solution. This led to runaway polymerisation which burst a glass vent line and the escaping contents ignited and led to an explosion and fire. 

REPPE PROCESS. Any of several processes involving reaction of acetylene (1) with formaldehyde to produce 2-butync-l,4-diol which can be converted to butadiene (2) with formaldehyde under different conditions to produce propargyl alcohol and, form this, allyl alcohol (3) with hydrogen cyanide to yield acrylonitrile (4) with alcohols to give vinyl ethers (5) with amines or phenols to give vinyl derivatives (6) with carbon monoxide and alcohols to give esters of acrylic acid (7) by polymerization to produce cyclooctatetraene and (8) with phenols to make resins. The use of catalysis, pressures up to 30 atm, and special techniques to avoid or contain explosions are important factors in these processes. 

In the 1930s, the Reppe group developed commercial processes for the production of carboxylic acids and esters by the carbonylation of alkynes and alkenes using metal carbonyls [4], In particular, an industrial process for producing acrylic acid or ester by the carbonylation of highly explosive acetylene, catalysed by extremely toxic Ni(CO)4, was established (eq. 1.3). 

PEP-2 PEP-3 PIPE = mixtures of PETN and Gulf Crown Oil (USA) perchlorate d ammonium 17 perchlorate de barium 29 perchlorate explosives 247 perchlorate de guanidine 157 perchlorate d hydrazine 182 perchlorate de lithium 205 perchlorate de potassium 263 perchlorate de sodium 292 percussion cap percussion primer 95 201 202 247 267 288 289 perforation of oil and gas wells 247 perle d allumage = squib 43, 236 Perlit = picric acid (german) 256 permissibles permitted explosives 14 75 86 88 248 370 peroxides 31 170 252 346 371 peroxide de benzoyle 31 peroxide de tricycloacetone 346 peroxide de zinc = zinc peroxide 371 Perspex = acrylic acid methylester polymer (same as Plexiglas ... 

High-brisance crystalline explosives, such as RDX or octogen, can be embedded in curable or polyadditive plastics such as polysulfides, polybutadiene, acrylic acid, polyurethane, etc. The mixture is then cured into the desired shape. Other components such as aluminum powder can also be incorporated. The products obtained can be of any desired size, and specified mechanical properties can be imparted to them, including rubber-like elasticity (-> LX and -> PBX). They can also be shaped into foils. 

DOT CLASSIFICATION 8 Label Corrosive DOT Class 8 Label Corrosive, Poison SAFETY PROFILE Confirmed human carcinogen. A poison. Moderately toxic by inhalation. A corrosive irritant to skin, eyes, and mucous membranes. A very dangerous fire hazard by chemical reaction with reducing agents and carbohydrates. A severe explosion hazard by chemical reaction with acetic acid, acetic anhydride, acetonitrile, acrolein, acrylic acid, acrylonitrile, aUyl... 

By very carefully controlling the reaction of pentaerythritol in nitric acid, PETRJN (Figure 3.29) instead of PETN can be obtained. PETRIN is not a particularly desirable explosive, but because of the hydroxyl group left on the last of the outer carbons, this material has one particularly useful feature. The hydroxyl can be reacted to the acid group in acrylic acid to form a polymerizable material, PETRJN-acrylate. PETRJN-acrylate polymer, a plastic, is used as an energetic binder in some composite rocket propellants. 

In 2006, two groups independently reported the novel asymmetric synthesis of tamiflu (106). Corey et al. reported a short enantioselective pathway for the synthesis of 106 from 1,3-butadi-ene and acrylic acid shown in O Scheme 22 [ 111 ]. The key steps of the synthesis are (1) Diels-Alder reaction of 1,3-butadiene (146) and trifluoroethyl acrylate (147) in the presence of chiral ligand 148 developed in the laboratory [112], (2) the introduction of two amino groups in tamiflu (106) without using potentially hazardous and explosive azide reagents, and (3) a novel S nBr4 - catalyzed bromoacetamidation. 

The federal government fined the company 3 million dollars for the various citations in relation to the accident.122 Hoechst is another company that has had repeated problems a serious pollution problem at Griesheim, Germany in 1993, as well as seven major incidents, mostly in Europe, between January 1995 and June 1996, including leaks of acrylic acid and a fire and explosion in an acetic acid plant at Clear Lake, Texas a fire in a 2-ethylhexanol plant in Oberhausen, Germany and problems with the methanol plant in Edmonton, Alberta, Canada.123... 

ACRYLIC ACID, 2-ETHYLHEXYL-ESTER (103-11-7) CnHjoOj Combustible liquid. Forms explosive mixture with air [explosion limits in air (vol %) 0.8 to 6.4 flashpoint 180°F/82°C oc autoignition temp 496°F/258°C Fire Rating 2]. Unless inhibited, contact with heat, sunlight, contaminants, or peroxides may cause hazardous polymerization. Reacts violently ivith strong oxidizers, with risk of fire and explosions. Incompatible with strong acids, alkalis, aliphatic amines, alkanolamines, nitrates. The uninhibited monomer vapor may block vents and confined spaces by, forming a solid polymer material. On small fires, use AFFF, foam, dry chemical, or COj extinguishers. 

ACRYLIC ACID, 2-HYDROXYPROPYL ESTER (999-61-1) CsH.oOj CH2 = CHCOOCHjCHOHCH3 Combustible liquid. Forms explosive mixture with air [explosion limits in air (vol %) 1.6 to uel unknown flash point 149°F/65 °C Fire Rating 1]. Unless inhibited (200 ppm hydroquinone recommended). 

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