Tert-butyl hydroperoxide = TBHP = Tertiary butyl hydroperoxide= t-Butyl hydroperoxide = 2-Hydroperoxy-2-methylpropane
TBHP is a clear, colorless, stable and aqueous solution of approximately 70 wt% t-butyl hydroperoxide and 30 wt% water.
The active oxygen content is about 12%. TBHP has a characteristic odor.
Chemical Name: 1,1-Dimethyl ethyl hydroperoxide
Chemical Family: Alkyl hydroperoxide
Tert.butyl hydroperoxide.
Tert.butyl hydroperoxide acts as an initiator (radical source) in the polymerization of monomers, e.g. ethylene in combination with other peroxides or oxygen, vinylacetate or (meth-)acrylates with suitable reducing agents (Fe-salts, sulfites, dithionites, rongalite, ascorbinic acid or sugar).
Tert.butyl hydroperoxide also acts as initiator for the copolymerization of styrene butadiene or acrylnitrile / butadiene / styrene in emulsion in combination with redox-systems in order to increase polymerization rate.
Tert.butyl hydroperoxide appears as a colorless mobile liquid which is de-sensitized with water with molecular weight of 90.1 g/mol.
Tert.butyl hydroperoxide is liquid even under high pressure and particularly suitable for reduction of residual monomer.
Product Type
Crosslinking Catalysts / Accelerators / Initiators > Organic Peroxides
Polymerization Initiators / Inhibitors / Catalysts > Polymerization initiators
Synonym: 1,1-Dimethylethyl hydroperoxide, 2-Hydroperoxy-2-methylpropane, tert-Butyl hydroperoxide solution, TBHP
Tert-butyl hydroperoxide is used as a chemical intermediate, a curing agent for polyesters, and a catalyst for polymerization; also used for bleaching and deodorizing; [HSDB] A polymerization initiator used to produce specialty chemicals in closed systems; [ACGIH]
Common Names: Tertiary butyl hydroperoxide
t-Butyl hydroperoxide
2-Hydroperoxy-2-methylpropane
TBHP
CAS Number: 75-91-2
Formula: C4H10O2, 70% in H2O
Tert-Butyl hydroperoxide is used as an initiator in thermal polymerization and photopolymerization reaction when exposed to heat or light.
KEYWORDS:
Tert-butyl hydroperoxide, TBHP, Tertiary butyl hydroperoxide, t-Butyl hydroperoxide, 2-Hydroperoxy-2-methylpropane, Alkyl hydroperoxide, 75-91-2, 200-915-7, Trigonox a-75, Trigonox A-W70
● Polymerization initiator
● Curing agent
● Chemical synthesis
Depending upon application, the key segments of the global tert-butyl hydroperoxide market are polymerization initiator, chemical synthesis, curing agent, etc. Of them, polymerization initiator and chemical synthesis application segments are said to be driving the market. The usage of TBHP in various applications in different region is diversified, with polymerization initiator generally dominating the demand.
Tert.butyl hydroperoxide acts as an initiator (radical source) in the polymerization of monomers, e.g. ethylene in combination with other peroxides or oxygen, vinylacetate or (meth-)acrylates with suitable reducing agents (Fe-salts, sulfites, dithionites, rongalite, ascorbinic acid or sugar).
Tert.butyl hydroperoxide also acts as initiator for the copolymerization of styrene butadiene or acrylnitrile / butadiene / styrene in emulsion in combination with redox-systems in order to increase polymerization rate.
Tert.butyl hydroperoxide appears as a colorless mobile liquid which is de-sensitized with water with molecular weight of 90.1 g/mol.
Tert.butyl hydroperoxide is liquid even under high pressure and particularly suitable for reduction of residual monomer.
Product Type
Crosslinking Catalysts / Accelerators / Initiators > Organic Peroxides
Polymerization Initiators / Inhibitors / Catalysts > Polymerization initiators
TBHP provides a readily available and convenient source of active oxygen suitable for diverse oxidation technologies.
Epoxidation of propylene to propylene oxide is the largest commercial application of TBHP.
Under the polymerization initiation reaction, TBHP is employed to synthesize many perester, dialkyl peroxide, and perketal derivatives, as it serves as a free radical initiator for polymerization, co-polymerization, graft polymerization, and curing of polymers. TBHP is also used in manufacture of specialty chemicals required in fine chemical and performance chemical industries such as pharmaceuticals and agrochemicals. It can selectively oxidize hydrocarbons, olefins, and alcohols. Asymmetric epoxidation and kinetic resolution with TBHP can provide access to complex chiral intermediates.
Commonly used production processes of TBHP include reaction between hydrogen peroxide and tert butanol (TBA) in the presence of sulfuric acid.
The TBHP-based PO production process generates TBA as by-product, along with PO.
The recyclic nature of the process reduces the intensity of grade of TBHP at every pass.
It enables manufacturers to procure TBHP at a lower cost than that of the original production.
This is expected to act as a driver for the global TBHP market.
tert-Butyl hydroperoxide (tBuOOH) is an organic peroxide widely used in a variety of oxidation processes, for example Sharpless epoxidation.
TBHP is normally supplied as a 69–70% aqueous solution.
Tert-butyl hydroperoxide (TBHP) is an organic peroxide that exists as a clear colorless, stable aqueous solution.
The demand for Tert-butyl hydroperoxide is high in various industries such as petrochemical and chemical for the synthesis of fine chemicals, agrochemicals, and pharmaceutical products.
One trend in the market is increasing demand for TBHP as a curing agent. A curing agent is a substance that is mainly used to harden a surface or a layer.
TBHP is an excellent curing agent, and it is applied on a polymeric surface to facilitate higher bonding of the molecular components of a material.
One driver in the market is increased demand for TBHP as polymerization initiator. TBHP is mainly used as a polymerization initiator in chemicals synthesis and processes that yield large chemical compounds. TBHP is an initiator that is used in chain-growth polymerization such as radical polymerization.
Identification of the substance
CAS-No.: 75-91-2
EINECS-No.: 200-915-7
IUPAC name: tert-Butyl hydroperoxide
Synonyms: TBHP, 2-Hydroxyperoxy-2-methylpropane, (1,1-)Dimethylethyl
hydroperoxide, tert-Butyl hydrogen peroxide,
Trade names: TBHP-70 (T-Hydro), Cadox TBH, Trigonox AW70, Perbutyl H
TBHP is used for the emulsion polymerization of Styrene, Acrylates and Metacrylates and the curing of polyester resins.
Tert-butyl hydroperoxide (TBHP) is suitable to be used as active peroxide in high pressure polymerization or as initiator in oxygen combination of Ethylene.
Common applications of Tert-butyl hydroperoxide (TBHP) are acrylate, vinylacetate, styrene - butadiene production, curing of styrene - polyester resins, oxidizing agent for hydrocarbons.
Application
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.
Tert-butyl hydroperoxide is an alkyl hydroperoxide in which the alkyl group is tert-butyl. It is widely used in a variety of oxidation processes. It has a role as an antibacterial agent and an oxidising agent.
Tert-butyl hydroperoxide is a catalyst in polymerization reactions to introduce peroxy group into organic molecules, in radical substitution reactions.
Uses : 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 (70 % or 80%, stabilized with water and phosphoric acid) is suitable for curing polyester resins and for the emulsion polymerization of styrene -butadiene rubbers.
TBHP is an intermediate in the production of propylene oxide and t-butyl alcohol from isobutane and propylene
Tert-Butyl hydroperoxide is used as an initiator and finishing catalyst in the solution and emulsion polymerization methods for polystyrene and polyacrylates
Tert-Butyl hydroperoxide is used in the polymerization of vinyl chloride and vinyl acetate
Tert-Butyl hydroperoxide is an oxidation and sulfonation catalyst in bleaching and deodorizing operations
TBHP an anti-slime agent in cooling systems and as a settling agent in aqueous slurries of various mineral tailings.
TBHP is PRINCIPALLY CHEMICAL INTERMEDIATE FOR PROPYLENE OXIDE & T-BUTYL ALCOHOL;
Tert-butyl hydroperoxide (TBHP)is an organic peroxide that exists as a clear colorless, stable aqueous solution. The demand for the product is high in various industries such as petrochemical and chemical for the synthesis of fine chemicals, agrochemicals, and pharmaceutical products.
TBHP is INITIATOR FOR VINYL CHLORIDE POLYMERIZATION & COPOLYMERIZATION;
CHEMICAL INTERMEDIATE FOR ADHESIVES, PLASTICS, RUBBER & ELASTOMERS
Applications TBHP provides a readily available and convenient source of active oxygen suitable for diverse oxidation technologies.
Epoxidation of propylene to propylene oxide accounts for the largest commercial application for TBHP.
Producers of initiators use TBHP solution to synthesize many perester, dialkyl peroxide and perketal derivatives.
The product itself serves as a free radical initiator for polymerizations, copolymerizations, graft polymerizations and curing of polymers.
TBHP offers advantages of versatility, regioselectivity, stereoselectivity, chemoselectivity and reactivity control with catalyst choice, mild reaction conditions and bulk availability.
TBHP finds use in preparing specialty chemicals required by fine chemical and performance chemical industries such as pharmaceuticals and agrochemicals.
TBHP can selectively oxidize hydrocarbons, olefins and alcohols. Asymmetric epoxidation and kinetic resolution with TBHP can provide access to complex chiral intermediates.
TBHP is primarily used in the chemical industry as starting material (or intermediate) and as a reactive ingredient (catalyst, initiator or curing agent).
Applications of TBHP are:
• the epoxidation of propylene to propylene oxide (intermediate);
• free radical initiator for polymerisations, copolymerisations, graft polymerisations and curing of polymers (plastic industry);
• free radical initiator to polymerise unsaturated monomers, usually to high polymers. Mainly used by manufacturers of synthetic lattices or water borne dispersions. Also used as a component of catalysts systems for unsaturated polyester resins (resin industry);
• the synthesis of other organic peroxy molecules (as a precursor of initiators) such as perester, persulphate, dialkyl peroxide and perketal derivatives;
• the preparation of speciality chemicals required by fine chemical and performance chemical industries, such as pharmaceuticals and agrochemicals (fungicide).
• the use as an ingredient of hardeners for plastics. These products contain 5 - 20 % TBHP. Hardeners for plastics are also used in the plastic industry.
Tert-Butyl hydroperoxide is an organic peroxide widely used in a variety of oxidation processes, for example Sharpless epoxidation.
Tert-Butyl hydroperoxide is normally supplied as a 69- 70% aqueous solution.
TBHP is mainly used as a polymerization initiator in chemical synthesis and processes that yield large chemical compounds.
TBHP is an initiator that is used in chain-growth polymerization such as radical polymerization.
TBHP is used as an initiator in thermal polymerization and photopolymerization reaction when exposed to heat or light.
TBHP, when used in thermal polymerization mechanism, generates radicals or cations.
TBHP acts as a photopolymerization initiator when exposed to UV radiations, and it has applications in photocurable composites.
tert-Butyl hydroperoxide is used as an initiator for radical polymerization and in various oxidation process such as sharpless epoxidation.
tert-Butyl hydroperoxide is involved in osmium catalyzed vicinal hydroxylation of olefins under alkaline conditions.
Furthermore, tert-Butyl hydroperoxide is used in catalytic asymmetric oxidation of sulfides to sulfoxides using binaphthol as a chiral auxiliary and in the oxidation of dibenzothiophenes.
tert-Butyl hydroperoxide plays an important role for the introduction of peroxy groups in organic synthesis.
Notes
Light sensitive. Store in cool place. Incompatible with powdered metals, strong oxidizing agents, reducing agents, acids, alkalis and heavy metals.
Tert-butyl Hydroperoxide (TBHP) is a clear, colorless, stable and aqueous solution which belongs to the alkyl hydroperoxide chemical family. It is highly reactive, inflammable, and decomposes due to contamination.
Tert-butyl hydroperoxide (TBHP) is an easily available and convenient source of active oxygen suitable for diverse oxidation technologies. Epoxidation of propylene to propylene oxide is the largest commercial application of TBHP. TBHP is also used in production of specialty chemicals needed in fine chemical and performance chemical industries such as pharmaceuticals and agrochemicals. It can selectively oxidize hydrocarbons, olefins, and alcohols. Asymmetric epoxidation and kinetic resolution with TBHP can provide access to complex chiral intermediates.
The main drawback of the market is that usage of tert-butyl hydroperoxide-based process is limited, while that of other processes is growing. Many companies have come up with proprietary technologies for the production of PO that do not involve the use of TBHP. Companies are also collaborating with each other by examining their PO production processes and developing joint-innovative processes. These factors are likely to act as restraints of the global TBHP market.
Synonyms
1,1-Dimethylethyl hydroperoxide; 1,1-Dimethylethylhydroperoxide; 2-Hydroperoxy-2-methylpropane; Cadox TBH; DE 488; DE-488; Hydroperoxide, 1,1-dimethylethyl; Hydroperoxide, tert-butyl; Hydroperoxyde de butyle tertiaire [French]; Perbutyl H; Slimicide; Slimicide DE-488; T-Butyl hydroperoxide; TBHP-70; Tertiary butyl hydroperoxide; Trigonox A-75 [Czech]; Trigonox A-W70; t-Butylhydroperoxide; terc. Butylhydroperoxid [Czech]; terc.Butylhydroperoxid [Czech]; tert-Butyl hydrogen peroxide; tert-Butylhydroperoxide; [ChemIDplus] UN3109
Category: Peroxides, Organic
Physical Hazards
TBHP is a highly reactive product. The three types of significant physical hazards are flammability, thermal and decomposition due to contamination.
To minimize these hazards, avoid exposure to heat, fire or any condition that will concentrate the liquid material.
Store away from heat, sparks, open flames, foreign contaminants, combustibles and reducing agents. Inspect containers frequently to identify bulges or leaks.
1.3.1 Flammability Hazards TBHP is highly combustible with a flash point of 38°C (100°F).
Once ignited, the material burns with a flare-burning effect.
During combustion, thermal decomposition may occur as well.
As a peroxide, TBHP vapors can burn in the absence of oxygen.
Determination of flammability limits are affected by temperature, pressure, the volume of sample tested and type of ignition source.
The lower flammability limit of solution vapors in air is 5.75 vol% TBHP at 80°C (176°F). The upper flammability limit is 100 vol% TBHP.
Because TBHP is capable of decomposing at elevated temperatures with the generation of oxygen, the flammability limits in nitrogen were also measured under the above conditions.
The lower flammability limit in pure nitrogen is 42.8 mol% and the upper limit is 100%.
The lower flammability limit will decrease as decomposition occurs and oxygen is generated, depending on temperature and time.
Similarly, the flash point of TBHP in pure nitrogen is 74°C (165°F) and will decrease as decomposition occurs.
Product identifier
Product name : TBHP-70-AQ
Chemical name : tert-butyl hydroperoxide
CAS-No. : 75-91-2
Recommended use of the chemical and restrictions on use
Recommended use : polymerisation initiators
Oxidizing agents
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
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
Consumer Uses:
Electrical and electronic products
Fuels and related products
Paints and coatings
Plastic and rubber products not covered elsewhere
Water treatment products
Synthesis and production
Many synthetic routes are available, including:
Reaction of hydrogen peroxide with isobutylene or tert-butyl alcohol in the presence of sulfuric acid
Auto-oxidation of isobutane with oxygen
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%.
Safety
tert-butyl hydroperoxide is an exceptionally dangerous chemical that is highly reactive, flammable and toxic.
TBHP is corrosive to skin and mucous membranes and causes respiratory distress when inhaled.
A solution of tert-butyl hydroperoxide and water with a concentration of greater than 90% is forbidden to be shipped according to US Department of Transportation Hazardous Materials Table 49 CFR 172.101.
In some sources TBHP also has an NFPA 704 rating of 4 for health, 4 for flammability, 4 for reactivity and is a potent oxidant, however other sources claim lower ratings of 3-2-2 or 1-4-4.
See also
Di-tert-butyl peroxide
Preferred IUPAC name: 2-Methylpropane-2-peroxol
Systematic IUPAC name: tert-Butyl hydroperoxide
CAS Number: 75-91-2
EC Number: 200-915-7
Properties
Chemical formula: C4H10O2
Molar mass: 90.122 g·mol−1
Appearance: Colorless liquid
Density: 0.935 g/mL
Melting point: −3 °C (27 °F; 270 K)
Boiling point: 37 °C (99 °F; 310 K) at 2.0 kPa
Solubility in water: miscible
log P: 1.23
Acidity (pKa): 12.69
Basicity (pKb): 1.31
Refractive index (nD): 1.3870
Thermochemistry
Std enthalpy of formation (ΔfH⦵298): −294±5 kJ/mol
Std enthalpy of combustion (ΔcH⦵298): 2.710±0.005 MJ/mol
Type:Organic Peroxides
Applications Include:Thermoplastics , Coatings, Dispersions & Speciality Polymers , Beyond Polymers
Chemical Name:tert.Butyl hydroperoxide
CAS Number:75-91-2
Chemical Formula:C4H10O2
Delivery Form:70 %, aqueous solution
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
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
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 ??)
IDENTIFICATION:
tert-Butyl hydroperoxide is a water-white liquid.
TBHP is moderately soluble in water.
USE: tert-Butyl hydroperoxide is an important commercial chemical.
TBHP is used in many chemical manufacturing processes and is used in bleaching and deodorizing.
EXPOSURE: Workers that use tert-butyl hydroperoxide may breathe in vapors or have direct skin contact.
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.
RISK: Specific data on tert-butyl hydroperoxide to cause toxic effects in humans are not available.
However, related chemicals (hydroperoxides) are known to causes severe irritation of the skin, eyes and mucous membranes.
Skin or eye contact for a long time or in large amounts may cause serious injury.
Exposure to hydroperoxide vapor may cause coughing, wheezing and/or shortness of breath, headache, fluid build-up in the lungs, labored breathing, lack of coordination, weakness and dizziness.
Stomach cramps, burning sensation and weakness has been reported following ingestion of hydroperoxides.
Hazard statements : H226 Flammable liquid and vapour.
H242 Heating may cause a fire.
H302 Harmful if swallowed.
H311 Toxic in contact with skin.
H314 Causes severe skin burns and eye damage.
H317 May cause an allergic skin reaction.
H330 Fatal if inhaled.
H341 Suspected of causing genetic defects.
H411 Toxic to aquatic life with long lasting effects.
Precautionary statements :
Prevention:
P210 Keep away from heat/ sparks/ open flames/ hot surfaces. No smoking.
P220 Keep/Store away from clothing/ strong acids, bases, heavy metal salts and other reducing substances /combustible materials.
P234 Keep only in original container.
P260 Do not breathe dust/ fume/ gas/ mist/ vapours/ spray.
P264 Wash skin thoroughly after handling.
P273 Avoid release to the environment.
P280 Wear protective gloves/ protective clothing/ eye protection/ face protection.
P281 Use personal protective equipment as required.
Response:
P303 + P361 + P353 IF ON SKIN (or hair): Remove/ Take off immediately all contaminated clothing. Rinse skin with water/ shower.
P304 + P340 + P310 IF INHALED: Remove victim to fresh air and keep at rest in a position comfortable for breathing. Immediately call a POISON CENTER or doctor/ physician.
P305 + P351 + P338 + P310 IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. Immediately call a POISON CENTER or doctor/ physician.
P370 + P378 In case of fire: Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide for extinction.
P391 Collect spillage.
Storage:
P403 + P233 Store in a well-ventilated place. Keep container tightly closed.
P411 + P235 Store at temperatures not exceeding 35 °C/ 95°F. Keep cool.
Appearance : liquid
Colour : colourless, clear
Odour : characteristic
Odour Threshold : not determined
pH : ca. 4.3
Melting point/range : < 0 °C
Boiling point/boiling range : 96 °C(1,013 hPa)
Decomposition: yes
Flash point : 38 °C
Method: closed cup
Evaporation rate : No data available
Flammability (solid, gas) : Not applicable
Upper explosion limit / Upper
flammability limit: ca. 99.99 %(V)
Lower explosion limit / Lower
flammability limit: ca. 5.7 %(V)
Vapour pressure : 50.78 hPa (25 °C)
Relative vapour density : ca. 3.1 (15 - 20 °C )(Air = 1.0)
Density : ca. 0.93 g/cm3 (20 °C)
Solubility(ies)
Water solubility : > 691 g/l soluble (20 °C)
Partition coefficient: noctanol/water: log Pow: 0.85 (20 °C)
Self-Accelerating decomposition temperature (SADT): 80 °C
Method: UN-Test H.4
SADT-Self Accelerating Decomposition Temperature. Lowest temperature at which the tested package size will undergo a self-accelerating decomposition reaction.
Thermal Hazards
Compared with most other hydroperoxides, T-Hydro TBHP has high thermal stability.
The material is stable at temperatures below approximately 38°C (100°F), and unadulterated material may keep for several months without a significant loss of activity.
However, at increased temperatures T-Hydro solution will deflagrate rather than detonate with a concurrent generation of oxygen, highly flammable isobutylene and incomplete combustion products such as carbon monoxide.
The thermal decomposition rate and half-life of TBHP will change dramatically depending upon specific conditions.
Surface-tovolume effects as well as container material and trace contamination may change rate and temperature relationships for decomposition.
Using an accelerating rate calorimeter in which the stainless steel bomb was first passivated, the 10-hour half-life of contaminate-free T-Hydro TBHP is approximately 118°C (244°F).
Self-accelerating decomposition becomes significant (i.e., the self-heat rate greater than 0.02°C per minute) at a temperature of approximately 110°C (230°F).
Decomposition proceeds at a faster rate in an untreated stainless steel bomb.
The estimated SADT for a standard 55-gallon carbon steel, polyethylene-lined drum is 77°C (171°F).
The SADT for a 5-gallon steel container is estimated at 88°C.
TBHP is considered a Volatile Organic Compound (VOC) under the Clean Air Act (CAA) of 1990.
It is not a Hazardous Air Pollutant (HAP) and therefore not subject to control under Title III of the Act.
As a VOC, TBHP is subject to the new regulations for ozone non-attainment areas.
These regulations, which vary by area depending on the severity of nonattainment, require emission controls on industrial sources of VOCs.
Any facility with the potential to emit TBHP may be subject to emission control requirements.
Consult with federal, state and local officials to determine regulation requirements for the facility.
The discharge of wastewater containing TBHP (as with most pollutants) to waters of the United States is regulated under the National Pollutant Discharge Elimination System (NPDES) permit program of the Clean Water Act.
TBHP is not listed as a priority pollutant under this Act, and Federal Water Quality Criteria for the protection of human health and/or aquatic organisms have not been developed for this material.
TBHP is not specifically regulated under the EPA pretreatment standards.
TBHP may be subject to case-by-case determination of NPDES
In spite of the safety of T-Hydro solution relative to other peroxides, testing has shown that under conditions where TBHP is concentrated in the liquid, explosions are possible.
ATAMAN recommends taking one of these two precautions to lower this risk:
1) provide for water dilution or 2) add a combustion modifier. Water injection acts as a diluent to prevent TBHP from concentrating during a fire.
To allow for safe dilution without overfilling, the liquid level should be limited to approximately 70-80% of the full tank volume.
Water dilution or combustion modifiers do not prevent flammability in the vapor phase.
Addition of a combustion modifier entails installing polyethylene INTALOX saddles which capture free radicals.
These saddles are three inch, low density polyethylene having a melt index (ASTM D 1238-82 Condition E) above 0.2 grams per 10 minutes.
The quantity of PE saddles to T-Hydro TBHP ratio should be greater than 0.0123 by weight.
Visually inspect and check the melt index of the saddles on a regular basis, at a minimum of once every year.
Replace them when discoloration, fracture, severe deformation, low melt index or other indication of change is noticed.
Solubility characteristics of TBHP and water are somewhat unusual
To maintain solution strength near the desired level with minimal loss to the water layer or thermal decomposition, keep the temperature in the range from 10°C to 38°C (50°F to 100°F).
At the standard 69 to 70 percent concentration, the solubility of water in TBHP decreases with temperature.
Heating or cooling can result in a second phase (about 85 percent water and 15 percent TBHP) settling to the bottom of the storage tank.
Because this phase is denser, it will accumulate at the low points.
To maintain the product quality, periodically draw down any accumulated second phase water to preclude the inadvertent transfer of the water phase along with the solution phase.
The solution begins to freeze at about -3°C (27°F) with the appearance of ice crystals.
As the temperature drops, the concentration changes until a second solid phase appears at about -11°C (12°F).
Upon remelting and remixing, the resultant solution has essentially the same composition as the original material. Neither the solution nor the solidified product has been found to be impact or shock sensitive.
The need for insulation or a temperature control system depends on local temperature conditions.
Other names: Hydroperoxide, 1,1-dimethylethyl; Cadox TBH; Perbutyl H; 2-Hydroperoxy-2-methylpropane; 1,1-Dimethylethyl hydroperoxide; tert-C4H9OOH; tert-Butyl hydrogen peroxide; Hydroperoxide, tert-butyl; Hydroperoxyde de butyle tertiaire; Slimicide DE-488; Terc. butylhydroperoxid; Trigonox A-75; TBHP-70; Trigonox A-W70; t-Butylhydroperoxide; Aztec t-butyl Hydroperoxide-70, Aq; Dimethylethyl hydroperoxide; T-Hydro; TBHP; Tertiary-butyl hydroperoxide; NSC 672
1,1-Dimethylethyl hydroperoxide
200-915-7 [EINECS]
2-Hydroperoxy-2-methylpropane
2-Methyl-2-propanyl hydroperoxide [ACD/IUPAC Name]
2-Methyl-2-propanylhydroperoxid [German] [ACD/IUPAC Name]
75-91-2 [RN]
Hydroperoxide, 1,1-dimethylethyl [ACD/Index Name]
Hydroperoxide, 1,1-dimethylethyl (9CI)
Hydroperoxyde de 2-méthyl-2-propanyle [French] [ACD/IUPAC Name]
Kayabutyl H
MFCD00002130 [MDL number]
Perbutyl H 69T
Perbutyl H 80
tbhp
tBuOOH
t-butyl hydroperoxide
t-butylhydroperoxide
t-butyl-hydroperoxide
tert-Butyl hydroperoxide [Wiki]
tert-butylhydrogenperoxide
tert-Butyl-hydroperoxide
TERT-BUTYLHYDROPEROXIDE
Trigonox A-W 70
[540-80-7]
1,1-Dimethylethyl hydroperoxide; 2-Hydroperoxy-2-methylpropane; tert-Butyl hydroperoxide solution; TBHP
1,1-Dimethylethylhydroperoxide
1209339
208-757-0 [EINECS]
2-hydroperoxy-2-methyl-propane
2-Methyl-prop-2-yl-hydroperoxide
4-01-00-01616 (Beilstein Handbook Reference) [Beilstein]
540-80-7 [RN]
70% aqueous solution
79-91-2
Aztec t-butyl Hydroperoxide-70, Aq
Cadox TBH
D020122
Dimethylethyl hydroperoxide
EINECS 200-915-7
https://www.ebi.ac.uk/chebi/searchId.do?chebiId=CHEBI:64090
Hydroperoxide, 1,1-dimethylethyl-
hydroperoxide, t-butyl
Hydroperoxide, tert-Butyl
Hydroperoxyde de butyle tertiaire
Hydroperoxyde de butyle tertiaire [French]
Luperox TBH 70X
Luperox(R) TBH70X, tert-Butyl hydroperoxide solution
MFCD00002055 [MDL number]
Perbutyl H
Perbutyl H 69
RA0802000
Slimicide [Trade name]
Slimicide DE-488
t Butyl Hydroperoxide
t Butylhydroperoxide
TBHP;tert-Butyl hydroperoxide
Terc. butylhydroperoxid
terc. Butylhydroperoxid [Czech]
terc.Butylhydroperoxid [Czech]
terc.Butylhydroperoxid [Czech]
tert Butyl Hydroperoxide
tert Butylhydroperoxide
tert.-Butyl hydroperoxide
tert-Butyl hydrogen peroxide
tert-Butyl Hydroperoxide (70per cent in Water)
Tert-Butyl hydroperoxide, 70% solution in water
TERT-BUTYL HYDROPEROXIDE|2-METHYLPROPANE-2-PEROXOL
tert-C4H9OOH
Tertiary butyl hydroperoxide
tertiary Butylhydroperoxide
Tertiary-butyl hydroperoxide
tertiary-Butylhydroperoxide
T-Hydro
Trigonox a-75
Trigonox A-75 [Czech]
Trigonox A-80 (Salt/Mix)
Trigonox A-W70
UN 2093 (Salt/Mix)
UN 2094 (Salt/Mix)
USP -800 (Salt/Mix)
WLN: QOX1&1&1
过氧化叔丁醇 [Chinese]
Tert-butyl hydroperoxide (TBHP) as a diesel additive
Abstract
The present invention relates to the use of TBHP as a fuel additive and in particular as an additive to diesel fuel.
This application is a National Phase application of International Application No. PCT/EP2012/072877, filed Nov. 16, 2012, which claims priority to European Patent Application No. 11189416.8, filed Nov. 16, 2011, each of which is incorporated herein by reference in its entirety.
The present invention relates to the use of tert-butyl hydroperoxide (TBHP) and blends thereof as a fuel additive and in particular as an additive to diesel fuels.
The cetane number is a characteristic parameter for the combustion quality of diesel fuel.
The cetane number is a measure of the ease of ignition or the ignition delay, that is to say the time between the start of fuel injection and the start of combustion.
Rapid ignition followed by combustion that is uniform and as complete as possible is advantageous. The higher the cetane number, the shorter the ignition delay and the better the combustion quality.
Various additives are used to increase the cetane number.
On a commercial scale, 2-EHN (2-ethylhexyl nitrate) is currently used almost exclusively.
Problems with this additive are its high toxicity, its poor storage stability, safety-critical properties, and considerable additional costs. The use of 2-EHN is problematic on account of its explosiveness in particular.
Furthermore, the nitrogen content can lead to high, undesirable NOX emissions.
Additives that increase the cetane number are also described in U.S. Pat. No. 2,763,537, for example, including alkyl nitrates, nitrites, nitroso compounds, diazo compounds and organic peroxides. With the exception of small amounts of DTBP (di-tert-butyl peroxide), organic peroxides are currently not used commercially as diesel additives. This is for reasons of cost, safety and compatibility.
Commercially available peroxide preparations often contain large amounts of water as phlegmatiser, have insufficient thermal or chemical stability, cannot be used commercially as a fuel additive on account of the raw materials or production processes used, or contain aromatic radicals which adversely affect pollutant emission. Peroxides phlegmatised with water are unsuitable as a propellant additive, however, because water does not mix with the propellant but forms a two-phase system.
Organic peroxides are thermally unstable compounds which decompose exothermally with cleavage of the peroxidic oxygen-oxygen bond.
Therefore, for the safe handling or safe transport of organic peroxides, they must, for safety considerations, often be phlegmatised or are produced industrially already in dilution.
In that respect, some anhydrous peroxides are not obtainable or are obtainable only with a high technical outlay.
It was an object of the present invention to provide an improved fuel additive, in particular with regard to pollutant emission, effectiveness, handling ability and costs.
The invention therefore relates to a fuel comprising tert-butyl hydroperoxide (TBHP) as an additive.
In a preferred embodiment, the invention relates to a fuel comprising tert-butyl hydroperoxide (TBHP) as an additive component in a mixture of TBHP with other organic peroxides, in particular other organic anhydrous peroxides such as, for example, di-tert-butyl peroxide (DTBP).
Surprisingly, it has been found that tert-butyl hydroperoxide, in particular in anhydrous form, is suitable as a fuel additive.
By using TBHP as an additive, in particular the cetane number of the fuel is increased and is preferably raised, compared with the base fuel, by a value of at least 2, more preferably at least 3, yet more preferably at least 4 and most preferably at least 5. The cetane number can be determined according to ASTM 0613, for example.
An increase in the cetane number is a measure of the improvement of the ease of ignition of the fuel.
It has further been found that, with the same consumption, the pollutant emissions, in particular the hydrocarbon emission and/or the carbon monoxide emission, can be reduced significantly, whereby at the same time the NOx emission is not raised considerably.
These advantages are obtained in vehicles without a catalyst, but surprisingly also in vehicles with a catalyst.
Surprisingly, it has been possible to determine reduced pollutant emissions both before a downstream catalytic converter and after a downstream catalytic converter. A reduction in the pollutant emissions after the catalyst has been found especially in phase 1 (cycles 1 to 4) of the NEDC driving cycle, in which low speeds of up to 50 km/h are driven and in which the catalyst does not yet reach the full operating temperature. In that respect, TBHP, in particular anhydrous TBHP, and blends thereof are of very great interest also in regions in which the catalyst density in existing vehicle fleets is already very high, such as, for example, Europe, because a large number of journeys are made with vehicles in which the catalyst does not reach the full operating temperature. TBHP, in particular anhydrous TBHP, and blends thereof as a fuel additive consequently also reduce pollutant emission, in particular the emission of hydrocarbons and carbon monoxide, irrespectively of the prevalence of catalytic converters.
Even in vehicles that are operated without a catalyst, pollutant emission in phase 1 (cycles 1 to 4) of the NEDC driving cycle is higher than in phase 2 (cycle 5). In phase 1, the reduction of hydrocarbon and carbon monoxide emissions with fuels that comprise TBHP, in particular anhydrous TBHP, as an additive is particularly high. This is the desired effect, especially for short journeys. In principle, the pollutant emissions of, for example, hydrocarbons and carbon monoxide are higher in the case of the combustion of lower-quality propellant grades than in the case of higher-quality propellant grades.
It has now been found, surprisingly, that TBHP as an additive reduces the pollutant emissions of, for example, hydrocarbons and carbon monoxide to a greater extent when using higher-quality diesel grades, such as, for example, a commercial Euro4 diesel, than when using lower-quality diesel grades, such as, for example, a commercial US diesel. In that respect, TBHP is also suitable, for example, especially as a propellant additive for regions in which higher-quality propellant grades are typically used.
Anhydrous TBHP is preferably used according to the invention as a fuel additive.
Anhydrous means that the content of water in the TBHP composition is <5 wt. %, in particular <1 wt. %, yet more preferably <0.3 wt. %.
By using anhydrous TBHP, which is miscible with fuel and in particular with diesel propellant, the formation of an undesirable, second aqueous phase is avoided.
TBHP is preferably used as an additive in an anhydrous organic solvent.
Polar and non-polar solvents can be used.
Examples of suitable non-polar solvents are alkyls and in particular aliphatic hydrocarbons, in particular isododecane, isooctane, decane, nonane or/and n-octane or mixtures of different aliphatic compounds. Examples of polar solvents are in particular oxygen-containing solvents, such as, for example, alcohols or/and ethers. Alkyl alcohols are preferably used as solvents, in particular C1-C8-alkyl alcohols, more preferably C2-C6-alkyl alcohols, yet more preferably butanol and most preferably tert-butanol. By using alcohols and in particular tert-butanol, the oxygen content in the fuel additive is increased further, which is desirable and contributes to improving combustion, as a result of the oxygen enrichment, and accordingly to reducing pollutant emission.
Specifically when using a fuel additive comprising TBHP in tert-butanol (TBA), a significant reduction in soot and pollutant emission has been observed.
The amount of TBHP in the additive is preferably at least 10 wt. %, more preferably at least 30 wt. %, yet more preferably at least 40 wt. % and most preferably at least 50 wt. %.
Pure TBHP is not preferred for safety considerations. The amount of TBHP in the additive is therefore preferably up to 90 wt. %, more preferably up to 75 wt. % and most preferably up to 60 wt. %. The amount of anhydrous organic solvents, in particular of alcohols and preferably of tert-butanol, is accordingly at least 10 wt. %, more preferably at least 25 wt. % and most preferably at least 40 wt. %, and up to 90 wt. %, more preferably up to 70 wt. % and most preferably up to 50 wt. %.
An additive that comprises from 30 to 70 wt. % TBHP in from 70 to 30 wt. % tert-butanol has been shown to be particularly suitable and accordingly most preferred.
An additive that comprises from 50 to 60 wt. % TBHP in from 50 to 40 wt. % tert-butanol is yet more preferred.
An additive that comprises 55 wt. % TBHP and 45 wt. % TBA is most preferred.
By the phlegmatisation of TBHP in an oxygen-containing solvent, preferably in an alcohol and in particular in tert-butanol, safety during industrial TBHP production, transport and further handling is improved.
Further particularly preferred solvents are ethers and polyethers, particularly preferably aliphatic or cyclic ethers and/or polyethers.
As well as reducing pollutants in the exhaust, phlegmatisation with an oxygen-containing solvent, preferably an alcohol and in particular tert-butyl alcohol, also leads to an increase in the oxygen content of the additive.
For example, a mixture of 55 wt. % TBHP and 45 wt. % TBA has an oxygen content of about 29.3 wt. % oxygen, of which about 9.8 wt. % is active oxygen.
The fuel according to the invention can comprise known fuels or propellants as the base fuel, such as, for example, petrol, in particular regular petrol, super grade petrol, etc., diesel fuels such as, for example, diesel, biodiesel or the like, but also very low diesel grades, such as, for example, various marine diesel grades, rape methyl ester, oxymethylene ethers, kerosine or rocket propellant. The fuel, in particular a diesel fuel or kerosine, can be provided, for example, for diesel generators in, for example, motor vehicles, ships or for stationary diesel engines for power generation or also for aircraft or rocket engines.
By means of the additive according to the invention, the ease of ignition of the fuel in particular is increased.
Furthermore, the emission of soot and hydrocarbons and carbon monoxide in the combustion engine is reduced significantly, in particular with unchanged or virtually unchanged NOx emission.
Particularly preferably, the fuel according to the invention comprises as the base fuel a high-quality diesel which meets Euro4 diesel requirements.
The TBHP used as additive according to the invention is also significantly better to handle from a safety point of view as compared with the additives conventionally used, such as, for example, 2-EHN.
By using TBHP in anhydrous form, in particular in an aqueous organic solvent, the formation of two separate phases is avoided and the use of TBHP as a fuel additive is thereby made possible for the first time.
As compared with conventionally used 2-EHN, the combustion is improved by the use according to the invention of TBHP as additive (in particular lower hydrocarbon, carbon monoxide and soot emission). Furthermore, TBHP does not contain nitrogen, so that the problems associated therewith, and in particular the problem of the formation of nitric oxides, are reduced according to the invention.
TBHP is furthermore significantly safer than 2-EHN in terms of safety, in particular in relation to decomposition.
A measure of the rate of decomposition and the build up of pressure during the decomposition of a product is the Koenen test. The greater the Koenen value, the more violent the decomposition.
Thus, the Koenen for 2-EHN is 1.0, while the Koenen for a TBHP phlegmatised with TBA is <1.
The energy released in the decomposition of 2-EHN, with ΔH=2210 J/g, is also significantly higher than that of a TBHP/TBA mixture, with ΔH=729 J/g.
In comparison with di-tert-butyl peroxide (DTBP), which is already being used as a fuel additive, TBHP advantageously has a higher flashpoint of 21° C.
The flashpoint of DTBP is, for example, significantly lower than that of TBHP and below room temperature at <0° C.
Furthermore, the conductivity of DTBP, at <3 pS/m, is extremely low, so that operations of siphoning DTBP are very critical in terms of safety on account of possible charge separations, because such charge separations can generate sufficient ignition energy to ignite DTBP, because DTBP requires only a very small amount of ignition energy of <0.1 mJ.
The energy released in the decomposition of DTBP, with ΔH=1370 J/g, is also significantly higher than that of TBHP phlegmatised with TBA, with ΔH 729 J/g.
In contrast to non-polar DTBP, polar TBHP is conductive (>1000 pS/m) and accordingly such charge separations do not occur, so that TBHP can be handled significantly more safely than DTBP.
According to the invention, the fuel comprises preferably from 0.001 wt. % to 10 wt. %, more preferably from 0.005 wt. % to 5 wt. % and most preferably from 0.01 wt. % to 2 wt. %, TBHP.
According to the invention it has been found that a reduction in the pollutant emission can be achieved even with small amounts of additive.
Particularly preferably, the fuel according to the invention therefore comprises up to 0.5 wt. % TBHP, yet more preferably up to 0.25 wt. % TBHP and most preferably up to 0.15 wt. %.
It is also possible according to the invention to combine the TBHP-containing additive according to the invention with other additives.
Preference is given, for example, to combination with other peroxides, in particular with other organic peroxides and preferably with other anhydrous organic peroxides, and in particular with di-tert-butyl peroxide (DTBP).
Particular preference is given to an additive that comprises TBHP and DTBP. An additive comprising TBHP, DTBP and TBA is most preferred.
Synergistic effects have surprisingly been found for the combination of anhydrous TBHP with DTBP as additive, so that the combination according to the invention of anhydrous TBHP with DTBP leads to a greater reduction of pollutants than can be achieved by comparable amounts of TBHP or DTBP alone.
The weight ratio of TBHP and DTBP is preferably from 10:90 to 90:10, in particular from 20:80 to 80:20 and yet more preferably from 30:70 to 70:30.
The amount of TBHP and DTBP in the additive is preferably at least 10 wt. %, more preferably at least 30 wt. %, yet more preferably at least 40 wt. % and most preferably at least 50 wt. %. Furthermore, the amount of TBHP and DTBP in the additive is preferably up to 90 wt. %, more preferably up to 75 wt. % and most preferably up to 60 wt. %.
The amount of anhydrous organic solvents, in particular of alcohols and preferably of tert-butanol, is accordingly at least 10 wt. %, more preferably at least 25 wt. % and most preferably at least 40 wt. %, and up to 90 wt. %, more preferably up to 70 wt. % and most preferably up to 50 wt. %.
The production of TBHP can be carried out by known production processes.
The fuel additive according to the invention comprises in particular anhydrous TBHP and preferably TBHP in an organic solvent.
The organic solvent is preferably an alcohol, in particular tert-butanol.
Particular preference is given to an additive comprising from 30 to 70 wt. % TBHP in from 70 to 30 wt. % organic solvent, in particular TBA, more preferably from 50 to 60 wt. % TBHP in from 50 to 40 wt. % organic solvent, in particular TBA.
Particular preference is further given to a fuel additive which, as well as comprising TBHP, comprises a further organic peroxide, in particular a further anhydrous organic peroxide. An additive comprising TBHP and DTBP is most preferred. In a particularly preferred embodiment, the peroxides are present in the additive in an alcohol, in particular in TBA.
Preference is further given to a fuel additive which, as well as comprising TBHP, comprises another known fuel additive, such as, for example, 2-EHN.
In a particularly preferred embodiment, the TBHP is present in an alcohol, in particular in TBA.
The preferred relative proportions of TBHP, optional further organic peroxide such as, for example, DTBP and organic solvent, in particular TBA, are as described hereinbefore.
It has further been found according to the invention that the pollutant emission can be reduced using the fuel additive according to the invention or a fuel comprising the fuel additive according to the invention.
The invention therefore relates also to the use of TBHP for pollutant reduction, in particular for reducing the hydrocarbon emission and/or the carbon monoxide emission.
The invention relates particularly preferably to the use of TBHP for reducing pollutant emission in vehicles with a catalyst. The use of an additive comprising TBHP, DTBP and TBA for pollutant emission is most preferred.
The invention relates further to a fuel additive comprising TBHP, in particular as described hereinbefore, and to the use of TBHP or of the fuel additives described herein for increasing the cetane number.
The invention relates further to a fuel additive comprising TBHP, in particular as described hereinbefore, and to the use of TBHP or of the fuel additives described herein for pollutant reduction, in particular for reducing the emission of hydrocarbons or/and carbon monoxide.
BUTYL HYDROPEROXIDE (TERTIARY)
CADOX TBH
1,1-DIMETHYLETHYL HYDROPEROXIDE
1,1-DIMETHYLETHYLHYDROPEROXIDE
ETHYLDIETHYLPEROXIDE
2-HYDROPEROXY-2-METHYLPROPANE
KAYABUTYL H
PERBUTYL H
PERBUTYL H 69T
PERBUTYL H 80
T-BUTYL HYDROPEROXIDE
T-BUTYLHYDROPEROXIDE
TERT-BUTYL HYDROPEROXIDE
TRIGONOX
TRIGONOX A-75
TRIGONOX A-W 70
Tert-Butyl hydroperoxide 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.TBHP is mainly used as a polymerization initiator in chemical synthesis and processes that yield large chemical compounds. TBHP is an initiator that is used in chain-growth polymerization such as radical polymerization. It is used as an initiator in thermal polymerization and photopolymerization reaction when exposed to heat or light. TBHP, when used in thermal polymerization mechanism, generates radicals or cations. TBHP acts as a photopolymerization initiator when exposed to UV radiations, and it has applications in photocurable composites.
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.
TBHP vapor can burn in the absence of air and may be flammable at either elevated temperature or at reduced pressure.
Fine mist/spray may be combustible at temperatures below the normal flash point.
When evaporated, the residual liquid will concentrate TBHP content and may reach an explosive concentration (＞90%). Closed containers may generate internal pressure through the degradation of TBHP to oxygen . TBHP is a highly reactive product. The three types of significant physical hazards are flammability, thermal, and decomposition due to contamination. To minimize these hazards, avoid exposure to heat, fire, or any condition that will concentrate the liquid material. Store away from heat, sparks, open flames, foreign contaminants, combustibles, and reducing agents. Inspect containers frequently to identify bulges or leaks (7a, 125).
Uses: tert-Butyl hydroperoxide (TBHP) is used to initiate polymerization reactionsand in organic syntheses to introduce peroxygroups into the molecule.
Uses:tert-Butyl hydroperoxide (TBHP) is Catalyst in polymerization reactions.
To introduce peroxy group into org molecules, in radical substitution reactions: Kharasch, Fono, J. organic. Chem. 23, 325 (1948); see also Kharasch, Sosnovsky, Tetrahedron 3, 97, 105 (1958).
Definition
ChEBI: An alkyl hydroperoxide in which the alkyl group is tert-butyl.
It is widely used in a variety of oxidation processes.
Production Methods: TBHP 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. TBHP 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 TBHP is in a closed system.
General Description: Watery odorless colorless liquid. Floats and mixes slowly with water.
Air & Water Reactions: Water soluble.
Reactivity Profile: Most alkyl monohydroperoxides are liquid.
The explosivity of the lower members (e.g., methyl hydroperoxide, or possibly, traces of the dialkyl peroxides) decreasing with increasing chain length and branching [Bretherick 2nd ed. 1979 p. 10]. Though relatively stable, explosions have been caused by distillation to dryness [Milas, JACS 1946, 68, 205] or attempted distillation at atmospheric pressure [Castrantas 1965 p. 15].
Hazard Moderate fire risk. Oxidizer.
Health Hazard: tert-Butyl hydroperoxide is a strong irritant.
Floyd and Stockinger (1958) observed thatdirect cutaneous application in rats did notcause immediate discomfort, but the delayedaction was severe.
The symptoms were erythemaand edema within 2–3 days.
Exposureto 500 mg in 24 hours produced asevere effect on rabbit skin, while a rinse of150 mg/min was severe to eyes.
It is moderately toxic; the effects aresomewhat similar to those of MEK peroxide.Symptoms from oral administration in ratswere weakness, shivering, and prostration.
LD50 value, intraperitoneal (rats): 87 mg/kg
LD50 value, oral (rats): 406 mg/kg.
Health Hazard
Moderately toxic by inhalation and ingestion and severely irritating to the eyes an skin.
t-Butyl hydroperoxide has not been found to be carcinogenic or to show reproductive or developmental toxicity in huma
Fire Hazard
tert-Butyl hydroperoxide is a flammable liquid and a highly reactive oxidizing agent. Pure TBHP is shock sensitive and may explode on heating.
Carbon dioxide or dry chemical extinguishers should be used for fires involving tert-butyl hydroperoxide.
Flammability and Explosibility tert-Butyl hydroperoxide is a flammable liquid and a highly reactive oxidizing agent. Pure TBHP is shock sensitive and may explode on heating.
Carbon dioxide or dry chemical extinguishers should be used for fires involving tert-butyl hydroperoxide.
Safety Profile
Moderately toxic by ingestion and inhalation. A severe skin and eye irritant.
Mutation data reported.
At highest dosage levels, symptoms noted were severe depression, incoordmation, and cyanosis.
Death was due to respiratory arrest. Very dangerous fire hazard when exposed to heat or flame, or by spontaneous chemical reaction such as with reducing materials. Moderately explosive; may explode during distillation. Violent reaction with traces of acid. Concentrated solutions may ignite spontaneously on contact with molecular sieve.
Mixtures with transition metal salts may react vigorously and release oxygen. Forms an unstable solution with 1,2-dichloroethane.
To fight fire, use alcohol foam, CO2, dry chemical.
When heated to decomposition it emits acrid smoke and fumes.
See also PEROXIDES, ORGANIC.
Carcinogenicity
A study performed to evaluate the carcinogenicity of TBHP found it was not carcinogenic when applied to the skin of mice at 16.6% of the peroxide 6 times a week for 45 weeks.
However, if its application was preceded by 0.05 mg of 4-nitroquinoline-1-oxide as a 0.25% solution in benzene applied 20 times over 7 weeks followed by TBHP (16.6% in benzene), then malignant skin tumors appeared between days 390 and 405 of the experiment . This supports the theory that peroxides are not complete carcinogens, but may act as promoters .
The effects of TBHP on promotable and nonpromotable mouse epidermal cell culture lines were reported by Muehlematter et al. .
storage tert-butyl hydroperoxide should be stored in the dark at room temperature (do not refrigerate) separately from oxidizable compounds, flammable substances, and acids.
Reactions involving this substance should be carried out behind a safety shield.
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 [J Am Chem Soc 82 1762 1960] refluxed at 30mm pressure in an azeotropic separation apparatus until two phases no longer separated, and then distilled at 41o/23mm. 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 [O'Brien et al. J Am Chem Soc 79 6238 1957].
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 [Milac & Djokic J Am Chem Soc 84 3098 1962].
A 3M solution of TBHP in CH2Cl2 is prepared by swirling 85mL (0.61mol) of commercial TBHP (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 TBHP is separated from the aqueous layer (ca 21mL) and used without further drying.
TBHP is assayed by iodometric titration. With 90% grade TBHP (w/w, d 0.90, ca 9.0mmole/mL) no separation of layers occurs, i.e. when TBHP (66.67mL, 0.60mole) is added to CH2Cl2 (140mL) the resulting solution (ca 200mL) should be clear. [Walling & Buckler J Am Chem Soc 77 6032 1955, Rogers & Campbell J Am Chem Soc 74 4742 1952, Akashi et al. J Org Chem 43 2063 1978 state the quality of available grades, handling and compatibility for reactions, Beilstein 1 IV 1616.]
Incompatibilities
tert-Butyl hydroperoxide and concentrated aqueous solutions of TBHP 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. TBHP can initiate polymerization of certain olefins.
Waste Disposal
Excess tert-butyl hydroperoxide and waste material containing this substance should be placed in an appropriate container, clearly labeled, and handled according to your institution's waste disposal guidelines.
tert-Butyl hydroperoxide Preparation Products And Raw materials
Raw materials Hydrogen peroxide-->tert-Butanol-->4-NITRO-2-SULFOANILINE-->Sulfuric acid hydrogen tert-butyl ester-->TERT-BUTYLMAGNESIUM CHLORIDE-->Vitamin D3-->L(+)-Ascorbic acid-->1,1-DICHLOROETHANE-->Isobutyric acid
Preparation Products
Propylene oxide-->(+)-DISPARLURE-->1-FLUORO-4-(TRIFLUOROMETHYLTHIO)BENZENE-->2-Quinolinecarboxaldehyde-->Cinmethylin-->2-QUINOXALINECARBALDEHYDE-->5-NITRO-2-HYDROXY-4-METHOXYPYRIDINE-->2,4-DICHLORO-5-NITROPYRIDINE-->tetrahydro-2-furyl acetate-->Di-tert-butyl peroxide-->Methyl 2-bromobenzoate-->tert-Butyl peroxypivalate-->4-(METHYLSULFINYL)PHENOL-->tert-Butyl peroxyacetate-->Dimethyl Furan-2,5-dicarboxylate
By clocking a maximum CAGR of 1.4% from 2017 to 2025, the global tert-butyl hydroperoxide market is expected to grow its revenue share to 46.61% by 2025. Curing agents follow in the second position in terms of revenue share. Vis-à-vis growth rate, chemical synthesis is also expected to register the same CAGR as polymerization initiator.
Global Tert-Butyl Hydroperoxide Market to Observe Growth as the Solution is a Convenient Source of Oxygen
The global tert-butyl hydroperoxide market is likely to witness considerable in the years to come. Tert-butyl Hydroperoxide or TBHP refers to a clear, aqueous, stable, and colorless solution that is commonly found at a concentration of 30wt% water and 70wt% TBHP. The chemical family of alkyl hydroperoxide chemical comes with TBHP. This solution is a highly reactive substance with three major physical hazards: contamination-related decomposition, thermal, and flammability.
Tert-butyl hydroperoxide is a convenient and a hassle-free source of active oxygen that can be used in a variety of oxidation processes. The most common commercial application of tert-butyl hydroperoxide is the epoxidation of propylene to propylene oxide. As a free radical initiator for curing of polymers, graft polymerization,co-polymerization, and polymerization, this solution is used to synthesize a variety of perketal, dialkyl peroxide, and perester derivatives in the polymerization initiation reaction. TBHP also finds utilization in the making of specialty chemicals for different industries like agrochemicals and pharmaceuticals that require performance chemicals and fine chemicals. It can oxidize alcohols, olefins, and hydrocarbons selectively.
Increased Demand in the Making of Specialty Chemicals to Spur Market Growth
Tert-butyl hydroperoxide is a convenient and cheap source of active oxygen that can be used in a variety of oxidation processes. The most common commercial usage of tert-butyl hydroperoxide is the epoxidation of propylene to propylene oxide. This product is also utilized in the making of specialty chemicals for various industries like agrochemicals and pharmaceuticals. Access to complicated chiral intermediates can be obtained through and kinetic resolution and asymmetric epoxidation.
The main flaw of the global tert-butyl hydroperoxide market is that the use of these solution-based processes is restricted, whilst the use of other processes is increasing. Many businesses have developed proprietary technologies that are meant for making PO not requiring the use of TBHP. Companies are also working together to examine their processes of PO manufacturing and coming up with joint-innovative processes.
Tert-butyl hydroperoxide
Other names: 1,1-Dimethylethyl hydroperoxide;
2-Hydroperoxy-2-methylpropane; Aztec t-butyl Hydroperoxide-70, Aq;
Cadox TBH; Dimethylethyl hydroperoxide; Hydroperoxide,
1,1-dimethylethyl; Hydroperoxide, tert-butyl; Hydroperoxyde de butyle
tertiaire; NSC 672; Perbutyl H; Slimicide DE-488; T-Hydro; TBHP;
TBHP-70; Terc. butylhydroperoxid; Tertiary-butyl hydroperoxide; Trigonox
A-75; Trigonox A-W70; t-Butylhydroperoxide; tert-Butyl hydrogen
peroxide; tert-C4H9OOH.
InChI: InChI=1S/C4H10O2/c1-4(2,3)6-5/h5H,1-3H3
InChI Key: CIHOLLKRGTVIJN-UHFFFAOYSA-N
Formula: C4H10O2
SMILES: CC(C)(C)OO
Molecular Weight: 90.12
CAS: 75-91-2
Application of Tert-Butyl hydroperoxide:
Industrially, tert-butyl hydroperoxide is used as a radical polymerization initiator.
Tert-Butyl hydroperoxide Synthesis and production
Many synthetic routes are available, including:
Reaction of hydrogen peroxide with isobutylene or tert-butyl alcohol in the presence of sulfuric acid
Reaction between tert-butyl alcohol and peroxymonosulfuric acid (however, an explosive intermediate is formed in this reaction)
Auto-oxidation of isobutylene with oxygen
Safety
Tert-Butyl hydroperoxide tertButyl hydroperoxide C4H10O2
tert-butyl hydroperoxide is an exceptionally dangerous chemical that is highly reactive, flammable and toxic.
Tert-butyl hydroperoxide is corrosive to skin and mucous membranes and causes respiratory distress when inhaled.
TBHP is commercially available and used mostly as TBHP-70 (T-Hydro), an aqueous solution of approximately 70 weight percent TBHP and 30 weight percent water .
The physicochemical properties listed in Table 1 include some values for the pure substance.
TBHP-70 is a highly reactive peroxide with an active oxygen content of about 12%.
Experimental data on explosive properties and oxidising properties were not submitted by industry.
In view of theoretical and structural considerations, however, experimental determination of these properties is considered to be not necessary (TBHP is a hydroperoxide with a reactive oxygenoxygen bond (–O-O-) resulting in significant physical hazards, viz. flammability, thermal decomposition and decomposition due to contamination). All other required physico-chemical data were submitted by industry. Most of these data are based on information from databases, material safety data sheets (ARCO, 1994; MSDS, 1994, 1996) or general published information summarizing experimental or estimated physico-chemical properties. Only the vapour pressure of 2700 kPa at 20 oC and the log Kow of 0.7 at 25 oC are based on full test reports (Hooidonk, 1992). Nevertheless, the available data on the physico-chemical properties of TBHP and TBHP-70 are considered to meet the Annex VIIA requirements. The substance is flammable, but does not need to be classified as flammable according to the criteria. However, the flashpoint indicates labelling with R10. The substance should be classified as oxidising (symbol O) and labelled with the R-sentence R7, because it is an organic peroxide. Furthermore, the following S-sentences are applicable based on the physicochemical properties: S3, S7, S14, S43.
Production process The production of TBHP takes place in a closed batch or closed continuous process.
The main types of production of TBHP are:
• Direct reaction of isobutane and liquid oxygen. (Used by one of the three EU producers. Overall reaction: (CH3)3CH + O2 → (CH3)3COOH. This reaction produces numerous minor by-products such as t-butyl alcohol and dibutyl peroxide which are removed during the purification by distillation which involves a TBHP-water azeotrope. Decanting of the aqueous phase of the distillation process leaves an organic phase containing around 70% TBHP and 30% water.).
• Preparation from tertiary-butyl alcohol and 30% hydrogen peroxide in presence of sulphuric acid (Used by one of the three producers.
Overall reaction: (CH3)C-OH + H2O2 → (CH3)COOH.)
• Oxidising of tertiary-butylmagnesium chloride.
• Epoxidation of propylene catalysed by a molybdenum complex.
• Oxidation of t-butyl alcohol in a 50% hydrogen peroxide solution with a reaction catalyst of silicotungstic acid.
USE PATTERN
Tert-butyl hydroperoxide (TBHP) is primarily used in the chemical industry.
TBHP is used as starting material (or intermediate) and as a reactive ingredient (catalyst, initiator or curing agent).
Applications of Tert-butyl hydroperoxide (TBHP) are as follows :
• Tert-butyl hydroperoxide (TBHP) finds application as an intermediate in the the epoxidation of propylene to propylene oxide.
• Tert-butyl hydroperoxide (TBHP) is free radical initiator for polymerisations, copolymerisations, graft polymerisations and curing of polymers (plastic industry)
• Tert-butyl hydroperoxide (TBHP) is free radical initiator to polymerise unsaturated monomers, usually to high polymers. Tert-butyl hydroperoxide (TBHP) is mainly used by manufacturers of synthetic lattices or water borne dispersions.
Tert-butyl hydroperoxide is also used as a component of catalysts systems for unsaturated polyester resins (use of TBHP in the resin industry)
• Tert-butyl hydroperoxide is employed in the synthesis of other organic peroxy molecules (as a precursor of initiators) such as perester, persulphate, dialkyl peroxide and perketal derivatives;
• Tert-butyl hydroperoxide is used in the preparation of speciality chemicals required by fine chemical and performance chemical industries, such as pharmaceuticals and agrochemicals (fungicide).
• Tert-butyl hydroperoxide is used as an ingredient of hardeners for plastics.
These products contain 5 - 20 % TBHP.
Hardeners for plastics are also used in the plastic industry.
According to the Danish product register TBHP is used in several products.
Only the most important product types and industry groups are listed in descending order according to substance quantity. Product types are paint, lacquer and varnishes, adhesives and binding agents
The increasing demand for TBHP as a curing agent is one of the major trends being witnessed in the global tert-butyl hydroperoxide (TBHP) market.
A curing agent is a substance that is mainly used to harden a surface or a layer.
TBHP is an excellent curing agent, and it is applied on a polymeric surface to facilitate higher bonding of the molecular components of a material.
The stronger the molecular bonds, the higher the strength and hardness of the material.
TBHP is highly used as a curing agent for thermoset resins, coatings, and specialty monomers, and these substances are effectively used in end-use industries such as automotive, aviation, and building and construction.
TBHP is mainly used as a polymerization initiator in chemical synthesis and processes that yield large chemical compounds.
TBHP is an initiator that is used in chain-growth polymerization such as radical polymerization.
TBHP is used as an initiator in thermal polymerization and photopolymerization reaction when exposed to heat or light.
TBHP, when used in thermal polymerization mechanism, generates radicals or cations.
TBHP acts as a photopolymerization initiator when exposed to UV radiations, and it has applications in photocurable composites.
TBHP initiators are extensively used in chemical synthesis to produce chemical-based substance such as acrylic resins, dispersions, and acrylic coatings.
Therefore, the increased demand for TBHP as a polymerization initiator is expected to drive the global TBHP market during the forecast period.
Global tert-butyl hydroperoxide market - Polymerization initiator segment leads the market
This market research report segments the global tert-butyl hydroperoxide market into the following applications (polymerization initiator, curing agent, and chemical synthesis) and key regions (the Americas, APAC, and EMEA). It provides an in-depth analysis of the prominent factors influencing the market, including drivers, opportunities, trends, and industry-specific challenges.
Of the three major applications, the polymerization initiator segment held the largest market share in 2017, contributing to nearly 48% of the market.
The market share occupied by this segment is expected to increase by 2022.
However, this application segment will dominate the global market throughout the forecast period.