TERT-BUTYLHYDROPEROXIDE

Tert-Butyl Hydroperoxide is a water-white liquid. tert-Butyl hydroperoxide (tBuOOH) is an organic peroxide widely used in a variety of oxidation processes, for example, Sharpless epoxidation. It is normally supplied as a 69–70% aqueous solution.  It is used to introduce the peroxy group into organic molecules, as a reagent in radical substitution reactions, and catalyst in polymerization reactions.

CAS NO: 75-91-2 
EC NUMBER: 200-915-7

IUPAC NAMES: 
2-hydroperoxy-2-methylpropane
2-methylpropane-2-peroxol
Hydroperoxide, 1,1-Dimethylethyl
t-Butyl hydroperoxide
Tert-butyl hydroperoxide
tert-Butyl hydroperoxide
tert-butyl hydroperoxide
tert-butyl hydroperoxide
tert-butyl hydroperoxide (upper limit: 72% w/w; typical concentration: 70% w/w)

SYNONYMS: 
TERT-BUTYL HYDROPEROXIDE;75-91-2;TBHP;T-Butyl;hydroperoxide;tert-Butylhydroperoxide;Perbutyl H;t-Butylhydroperoxide;2-Hydroperoxy-2-methylpropane;Cadox TBH;1,1-Dimethylethyl hydroperoxide;Hydroperoxide, 1,1-dimethylethyl;tert-Butyl hydrogen peroxide;Terc. butylhydroperoxid;Hydroperoxyde de butyle tertiaire;Hydroperoxide, tert-butyl;Slimicide;DE-488;Tertiary butyl hydroperoxide;Trigonox a-75;Trigonox A-W70;TBHP-70;NSC 672;Tertiary-butyl hydroperoxide;1,1-Dimethylethylhydroperoxide;tert-Butyl-hydroperoxide;Dimethylethyl hydroperoxide;T-Hydro;tBuOOH;t-BuOOH;UNII-955VYL842B;tert-Butyl hydroperoxide solution;CHEBI:64090;955VYL842B;tert-Butyl Hydroperoxide (70% Solution in Water);MFCD00002130;Tert-Butyl hydroperoxide, 70% solution in water;Caswell No. 130BB;Trigonox A-75 [Czech];terc.Butylhydroperoxid [Czech];CCRIS 5892;HSDB 837;terc.Butylhydroperoxid;terc. Butylhydroperoxid [Czech];tert Butylhydroperoxide;EINECS 200-915-7;DE-488;BRN 1098280;Hydroperoxyde de butyle tertiaire [French];AI3-50541;Kayabutyl H;tert-BuOOH;Hydroperoxide, 1,1-dimethylethyl-;tBOOH;Perbutyl H 69;Perbutyl H 69T;Perbutyl H 80;Luperox TBH 70X;t-butyl-hydroperoxide;terbutyl hydroperoxide;tert-butyhydroperoxide;tert-C4H9OOH;Trigonox A-W 70;t-butyl hydrogenperoxide;t-butyl-hydrogenperoxide;tert.-butylhydroperoxide;tert.butyl hydroperoxide;tertiarybutylhydroperoxide;tertbutylhydrogen peroxide;t-butyl hydrogen peroxide;tert.-butyl hydroperoxide;ACMC-1BM3U;DSSTox_CID_4693;tert-butylhydrogen peroxide;EC 200-915-7;DSSTox_RID_78866;DSSTox_GSID_31209;tertiary butyl hydro peroxide;Hydroperoxide,1-dimethylethyl;Trigonox A-80 (Salt/Mix);UN 2093 (Salt/Mix);UN 2094 (Salt/Mix);USP -800 (Salt/Mix);CHEMBL348399;NSC672;DTXSID9024693;tert-Butyl hydroperoxide (8CI);tert-Butyl hydroperoxide, >90% with water [Forbidden];WLN: QOX1&1&1;tert-Butyl-hydroperoxide solution;NSC-672;2-Methyl-prop-2-yl-hydroperoxide;ZINC8585869;CC(C)([OH+][O-])C;Tox21_200838;ANW-43954;Aztec t-butyl Hydroperoxide-70, Aq;tert-Butyl hydroperoxide solution, CP;AKOS000121070;2-$l^{1}-oxidanyloxy-2-methylpropane;NCGC00090725-01;NCGC00090725-02;NCGC00090725-03;NCGC00258392-01;Hydroperoxide, 1,1-dimethylethyl (9CI);tert-Butyl Hydroperoxide (70% in Water);tert-Butyl hydroperoxide, >90% with water;B3153;FT-0657109;Q286326;J-509597;tert-Butyl hydroperoxide solution, ~5.5 M in decane;F1905-8242;tert-Butyl hydroperoxide solution (TBHP), 70% in H2O;tert-Butyl hydroperoxide solution, 5.0-6.0 M in decane;tert-Butyl hydroperoxide solution, 5.0-6.0 M in nonane;Luperox(R) TBH70X, tert-Butyl hydroperoxide solution, 70 wt. % in H2O;tert-Butyl hydroperoxide solution, ~80% in di-tert-butyl peroxide/water 3:2;tert-Butyl hydroperoxide solution, packed in FEP bottles, ~5.5 M in decane (over molecular sieve 4??);tert-Butyl hydroperoxide solution, packed in FEP bottles, ~5.5 M in nonane (over molecular sieve 4 ??)

Physical Description
Watery odorless colorless liquid. Floats on and dissolves slowly in water.

IDENTIFICATION: tert-Butyl hydroperoxide is a water-white liquid. It moderately soluble in water. 

USE: tert-Butyl hydroperoxide is an important commercial chemical. It is used in many chemical manufacturing processes and is used in bleaching and deodorizing. 

The general population is not likely to be exposed to tert-butyl hydroperoxide. If tert-butyl hydroperoxide is released to the environment, it will be broken down in air. tert-Butyl hydroperoxide is expected to be broken down by sunlight. It will not move into air from moist soil and water surfaces. tert-Butyl hydroperoxide is unstable and breaks down rapidly to oxygen. 

Application Areas
Industrially, tert-butyl hydroperoxide is used as a radical polymerization initiator. For example, its reaction with propene yields propylene oxide and the byproduct t-butanol which can dehydrate to isobutene and convert to MTBE.

Synthesis and production
Many synthetic routes are available, including:

The reaction of hydrogen peroxide with isobutylene or tert-butyl alcohol in the presence of sulfuric acid
Auto-oxidation of isobutane with oxygen

Formulation or re-packing
tert-Butyl hydroperoxide is used in the following products: polymers.
Release to the environment of tert-Butyl hydroperoxide can occur from industrial use: formulation of mixtures and formulation in materials.
Uses at industrial sites
tert-Butyl hydroperoxide is used in the following products: polymers.
tert-Butyl hydroperoxide is used in the following areas: formulation of mixtures and/or re-packaging.
Release to the environment of tert-Butyl hydroperoxide can occur from industrial use: as an intermediate step in further manufacturing of another substance (use of intermediates), as a processing aid and as a processing aid.

USE AREAS 
-General adhesives and binding agents for a variety of uses    
-Relating to agricultural, including the raising and farming of animals and growing of crops    
-Products used to care for apparel (e.g., she polish, products to repair footwear or leather, waterproofing sprays, etc.)    
-Related to the building or construction process for buildings or boats (includes activities such as plumbing and electrical work, bricklaying, etc)    
-Materials used in the building process, such as flooring, insulation, caulk, tile, wood, glass, etc.    
-Flooring materials (carpets, wood, vinyl flooring), or related to flooring such as wax or polish for floors    
-Wall construction materials, or wall coverings    
-Catalyst
-Drug product, or related to the manufacturing of drugs, veterinary, animal, or pet.
- pharmaceutical
-Related to computers or the manufacturing of computers    
-Related to the activity of fishing    
-Includes antifoaming agents, coagulating agents, dispersion agents, emulsifiers, flotation agents, foaming agents, viscosity adjusters, etc    
-Includes food packaging, paper plates, cutlery, small appliances such as roasters, etc.; does not include facilities that manufacture food    
-Related to forestry    
-Related to the activity of hunting    
-Related to all forms of cleaning/washing, including cleaning products used in the home, laundry detergents, soaps, de-greasers, spot removers, etc; modifiers included when specific information is known, such as dry cleaning, laundry, soap, window/floor, etc 
-Materials used in the building process, such as flooring, insulation, caulk, tile, wood, glass, etc.
-Wood used as a building material, wood preservatives
- related to the manufacturing of chemicals, or laboratory chemicals.
-Related to manufacturing for export.
-Furniture, or the manufacturing of furniture 
-Manufacturing of or related to machinery, for production of cement or food, air/spacecraft machinery, electrical machinery, etc
-Related to metals - manufacturing of metals, casting of metals, production of metals, surface treatment of metals, etc
-Crude oil, crude petroleum, refined oil products, fuel oils, drilling oils    
-Various types of paint for various uses, modifiers included when more information is known
-Plastic products, industry for plastics, manufacturing of plastics, plastic additives (modifiers included when known)
-Raw materials used in a variety of products and industries (e.g. in cosmetics, chemical manufacturing, production of metals, etc); modifiers included when known to indicate what the raw materials are used for.
- Rubber products (e.g. tires) and their manufacture    
- Various types of paint for various uses.
- Modifier included when source indicates the product is water-based    
- Related to the manufacturing of pulp or paper products, or paper products in general    
- Substances used for preventing, destroying or mitigating pests    
- Additive for products to promote hardening, used in paints and varnishes, plastics, etc.
- Accelerators, activators, oxidation agents, reducing agents, etc    
- General antioxidants, application indicated if known    
- Oxidizing/reducing agents
- Related to fracking, natural gas, industrial gases    
- Crude oil, crude petroleum, refined oil products, fuel oils, drilling oils    
- Surface treatments for metals, hardening agents, corrosion inhibitors, polishing agents, rust inhibitors, water repellants, etc (surfaces to be applied to often not indicated in source description)     
- chairs and seats    

-Catalyst in polymerization reactions. To introduce peroxy group into organic molecules, in radical substitution reactions.
-Polymerization, oxidation, sulfonation catalyst, bleaching, deodorizing
- tert-Butyl hydroperoxide is used as an oxidant in the Halcon process for the production of propylene oxide. The standard commercial product (80%, stabilized with water and phosphoric acid) is suitable for curing polyester resins and for the emulsion polymerization of styrene-butadiene rubbers.

Industry Uses    
Fillers
Fuels and fuel additives
Intermediates
Paint additives and coating additives not described by other categories
Plasticizers
Plating agents and surface treating agents
Process regulators
Processing aids, not otherwise listed

Consumer Uses
Electrical and electronic products
Fuels and related products
Paints and coatings
Plastic and rubber products not covered elsewhere
Water treatment products

Methods of Manufacturing
The oxidation of isobutane with oxygen in the gas phase at 160 °C and a residence time of ca. 3 min leads to a 70% yield of tert-butyl hydroperoxide with a conversion of 80%. Hydrogen bromide is used as the initiator. Byproducts include di-tert-butyl peroxide, tert-butanol, and various alkyl bromides. Another process operates in the liquid phase at 130 °C and 3.5 MPa without a catalyst. The hydroperoxide is obtained in a yield of ca. 60% with an isobutane conversion of < 25%.

Industry Processing Sectors
Adhesive manufacturing
All other basic organic chemical manufacturing
All other chemical product and preparation manufacturing
Electrical equipment, appliance, and component manufacturing
Oil and gas drilling, extraction, and support activities
Paint and coating manufacturing
Petrochemical manufacturing
Plastic material and resin manufacturing
Plastics product manufacturing
Rubber product manufacturing
Services

Chemical Properties    
tert-Butyl hydroperoxide (TBHP) is a water-white liquid commonly commercially available as a 70% solution in water; 80% solutions are also available. It is used to initiate polymerization reactions and in organic syntheses to introduce peroxy groups into the molecule. Tert-Butyl Hydroperoxide vapour can burn in the absence of air and maybe flammable at either elevated temperature or at reduced pressure. Fine mist/spray may be combustible at temperatures below the normal flashpoint. When evaporated, the residual liquid will concentrate Tert-Butyl Hydroperoxide content and may reach an explosive concentration (＞90%). Closed containers may generate internal pressure through the degradation of Tert-Butyl Hydroperoxide to oxygen. Tert-Butyl Hydroperoxide is a highly reactive product. The three types of significant physical hazards are flammability, thermal, and decomposition due to contamination. 

Uses    
It is used to initiate polymerization reactions and in organic syntheses to introduce peroxy groups into the molecule.

Catalyst in polymerization reactions. To introduce peroxy group into org molecules, in radical substitution reactions.

Definition
An alkyl hydroperoxide in which the alkyl group is tert-butyl. It is widely used in a variety of oxidation processes.
Production Methods    Tert-Butyl Hydroperoxide is produced by the liquid-phase reaction of isobutane and molecular oxygen or by mixing equimolar amounts of t-butyl alcohol and 30–50% hydrogen peroxide. Tert-Butyl Hydroperoxide can also be prepared from t-butyl alcohol and 30% hydrogen peroxide in the presence of sulfuric acid or by oxidation of tert-butylmagnesium chloride. The manufacturing process of Tert-Butyl Hydroperoxide is in a closed system.

Purification Methods    
Care should be taken when handling this peroxide because of the possibility of EXPLOSION. It explodes when heated over an open flame. Alcoholic and volatile impurities can be removed by prolonged refluxing at 40o under reduced pressure, or by steam distillation. For example, Bartlett, Benzing and Pincock refluxed at 30mm pressure in an azeotropic separation apparatus until two phases no longer separated, and then distilled at 41o/23mm. The pure material is stored under N2, in the dark at 0o. Crude commercial material has been added to 25% NaOH below 30o, and the crystals of the sodium salt have been collected, washed twice with *benzene and dissolved in distilled water. After adjusting the pH of the solution to 7.5 by adding solid CO2, the peroxide is extracted into pet ether, from which, after drying with K2CO3, it is recovered by distilling off the solvent under reduced pressure at room temperature. The temperatures should be kept below 75o. It has also been distilled through a-helices packed column (ca 15 plates) and the material with b 34-35o/20mm was collected. Similarly, a solution in pet ether has been extracted with cold aqueous NaOH, and the hydroperoxide has been regenerated by adding at 0o, KHSO4 at a pH not higher than 4.5, then extracted into diethyl ether, dried with MgSO4, filtered and the ether evaporated in a rotary evaporator under reduced pressure. A 3M solution of Tert-Butyl Hydroperoxide in CH2Cl2 is prepared by swirling 85mL (0.61mol) of commercial Tert-Butyl Hydroperoxide (70% TBHP-30% H2O, d 0.935 ca 7.2mmol/mL) with 140mL of CH2Cl2 in a separating funnel. The milky mixture is allowed to stand until the phases separate (ca 30minutes). The organic (lower) layer (ca 200mL) containing 0.60mole of Tert-Butyl Hydroperoxide is separated from the aqueous layer (ca 21mL) and used without further drying.

Incompatibilities    
tert-Butyl hydroperoxide and concentrated aqueous solutions of Tert-Butyl Hydroperoxide react violently with traces of acid and the salts of certain metals, including, in particular, manganese, iron, and cobalt. Mixing anhydrous tert-butyl hydroperoxide with organic and readily oxidized substances can cause ignition and explosion. Tert-Butyl Hydroperoxide can initiate the polymerization of certain olefins.

Environmental Fate and Behavior of Tert butyl hydroperoxide
 Tert-butyl hydroperoxide is expected to have high mobility in soil. If released to air, Tert-butyl hydroperoxide will exist solely as a vapor in the ambient atmosphere. In aqueous environments, Tert-butyl hydroperoxide is not expected to adsorb to sediment or suspended solids, and volatilization is expected to be the primary fate process. The half-lives for this compound in a variety of media allow for some moderate long-range transport, but not incredible distances.
An estimated bioconcentration factor (BCF) of 3 was calculated for Tert-butyl hydroperoxide Syracuse Research Corporation (SRC), using an estimated log Kow of 0.94 and a regression-derived equation. According to a classification scheme, this BCF suggests the potential for bioconcentration in aquatic organisms is low.

Tert-butyl hydroperoxide (TBHP)'s production and use as a chemical intermediate may result in its release to the environment through various waste streams(SRC).
Based on a classification scheme, an estimated Koc value of 86(SRC), determined from a structure estimation method, indicates that Tert-butyl hydroperoxide (TBHP) is expected to have high mobility in soil(SRC). However, hydroperoxides react with a variety of compounds and are reduced readily to the corresponding alcohols. They are decomposed readily by multivalent metal ions, are photo- and thermally sensitive and undergo initial oxygen-oxygen bond homolysis, and are attacked readily by free radicals, undergoing induced and self-induced decomposition. Chemical degradation is expected to be the dominant fate process in soil(SRC). The pKa of Tert-butyl hydroperoxide (TBHP) is 12.80, indicating that this compound will exist in the unionized form in the environment. Volatilization of Tert-butyl hydroperoxide (TBHP) from moist soil surfaces is expected to be an important fate process(SRC) given an estimated Henry's Law constant of 1.6X10-5 atm-cu m/mole(SRC), using a fragment constant estimation method. Tert-butyl hydroperoxide (TBHP) is expected to volatilize from dry soil surfaces(SRC) based upon a vapour pressure of 5.46 mm Hg at 25 °C. Utilizing the Japanese MITI test, 0% of the Theoretical BOD was reached in 4 weeks indicating that biodegradation is not an important environmental fate process in soil(SRC).

Based on a classification scheme, an estimated Koc value of 86(SRC), determined from a structure estimation method, indicates that tert-butyl hydroperoxide is not expected to adsorb to suspended solids and sediment(SRC). However, hydroperoxides react with a variety of compounds and are reduced readily to the corresponding alcohols. They are decomposed readily by multivalent metal ions, are photo- and thermally sensitive and undergo initial oxygen-oxygen bond homolysis, and they are attacked readily by free radicals, undergoing induced and self-induced decompositions. Chemical degradation is expected to be the dominant fate process in water(SRC). Volatilization from water surfaces is expected based upon an estimated Henry's Law constant of 1.6X10-5 atm-cu m/mole(SRC), developed using a fragment constant estimation method. Using this Henry's Law constant and an estimation method, volatilization half-lives for a model river and model lake are 2 and 20 days, respectively(SRC). A pKa of 12.8 indicates tert-butyl hydroperoxide will exist in the unionized form at pH values of 5 to 9(SRC). According to a classification scheme, an estimated BCF of 3(SRC), from an estimated log Kow of 0.94 and a regression-derived equation, suggests the potential for bioconcentration in aquatic organisms is low(SRC). Utilizing the Japanese MITI test, 0% of the Theoretical BOD was reached in 4 weeks indicating that biodegradation is not an important environmental fate process in water(SRC).

Tert-butyl hydroperoxide (TBHP) provides a readily available and convenient source of active oxygen suitable for diverse oxidation technologies. Producers of initiators use T-Hydro solution to synthesize many perester, dialkyl peroxide and perketal derivatives. The product itself serves as a free radical initiator for polymerization, copolymerizations, graft polymerizations and curing of polymers. Tert-butyl hydroperoxide (TBHP) offers advantages of versatility, regioselectivity, stereoselectivity, chemoselectivity and reactivity control with catalyst choice, mild reaction conditions and bulk availability. Tert-butyl hydroperoxide (TBHP) finds use in preparing speciality chemicals required by fine chemical and performance chemical industries such as pharmaceuticals and agrochemicals. Tert-butyl hydroperoxide (TBHP) can selectively oxidize hydrocarbons, olefins and alcohols. Asymmetric epoxidation and kinetic resolution with Tert-butyl hydroperoxide (TBHP) can provide access to complex chiral intermediates.

tert-Butyl hydroperoxide is used as an initiator for radical polymerization and in various oxidation process such as Sharpless epoxidation. It is involved in the osmium catalyzed vicinal hydroxylation of olefins under alkaline conditions. Furthermore, it is used in catalytic asymmetric oxidation of sulfides to sulfoxides using binaphthol as a chiral auxiliary and in the oxidation of dibenzothiophenes. It plays an important role in the introduction of peroxy groups in organic synthesis.

Tert-Butyl Hydroperoxide Solution is used for the emulsion polymerization of Styrene, Acrylates and Methacrylates and the curing of polyester resins. Suitable to be used as active peroxide in high-pressure polymerization or as an initiator in oxygen combination of Ethylene. Common applications are acrylate, vinyl acetate, styrene-butadiene production, curing of styrene - polyester resins, oxidizing agent for hydrocarbons. Recommended storage temperature is between 0 °C and +30 °C. Keep pails tightly closed. Store and handle in a dry, well-ventilated place. Keep away from sources of heat, ignition and direct sunlight in original packaging. Provide grounding and venting in order to prevent static electricity build-up. Avoid any contact with Amine and Cobalt Accelerators, acids, alkalis and heavy metal compounds such as driers and metal soaps.

Tert-butyl hydroperoxide (TBHP)39’s the production and use as a chemical intermediate may result in its release to the environment through various waste streams. If released to air, a vapour pressure of 5.46 mm Hg at 25 C indicates Tert-butyl hydroperoxide (TBHP) will exist solely as a vapour in the ambient atmosphere. Vapour-phase Tert-butyl hydroperoxide (TBHP) will be degraded in the atmosphere by reaction with photochemically produced hydroxyl radicals; the half-life for this reaction in air is estimated to be 5 days. Tert-butyl hydroperoxide (TBHP) will directly photolyze with breakage of the peroxide bond. If released to soil, Tert-butyl hydroperoxide (TBHP) is expected to have high mobility based upon an estimated Koc of 86. Volatilization from moist soil surfaces may be an important fate process based upon an estimated Henry 39’s Law constant of 1.6X10-5 atm-cu m/mole. The pKa of Tert-butyl hydroperoxide (TBHP) is 12.8, indicating that this compound will exist in the un-ionized form in the environment. Tert-butyl hydroperoxide (TBHP) may volatilize from dry soil surfaces based upon its vapour pressure. Utilizing the Japanese MITI test, 0% of the Theoretical BOD was reached in 4 weeks, indicating that biodegradation is not an important environmental fate process in soil or water. Tert butyl hydroperoxide is expected to react rapidly with organic matter in soil and water and be decomposed rapidly by metal ions, which will attenuate all transport processes. Hydroperoxides would be converted to the corresponding alcohols. If released into water, Tert-butyl hydroperoxide (TBHP) is not expected to adsorb to suspended solids and sediment based upon the estimated Koc. Volatilization from water surfaces is expected to be an important fate process based upon this compound39;s estimated Henry39’s Law constant. Estimated volatilization half-lives for a model river and model lake are 2 and 20 days, respectively. However, hydroperoxides react with a variety of compounds and are reduced readily to the corresponding alcohols. An estimated BCF of 3 suggests the potential for bioconcentration in aquatic organisms is low. Occupational exposure to Tert-butyl hydroperoxide (TBHP) may occur through inhalation and dermal contact with this compound at workplaces where Tert-butyl hydroperoxide (TBHP) is produced or used. The general public is not likely to be exposed to tert-butyl hydroperoxide.