T-Hydro Solution

t-Butyl Hydroperoxide

T-Hydro Solution Product Overview

SUMMARY ADVANTAGES

T-HYDRO TBHP Solution is a highly versatile product, containing 69-70% tertiary-butyl hydroperoxide (TBHP) in water, produced by Lyondell Chemical Company. T-HYDRO is one of the safest organic peroxides and one of only two organic peroxides that the Department of Transportation certifies for tank truck shipment. We maintain an oversized fleet of dedicated trucks and iso-containers equipped with the necessary safety features to provide on-time deliveries worldwide. We produce T-HYDRO at four commercial plants located in Texas and the Netherlands. Worldwide capacity totals 62 million pounds. Because of our responsibility to our customers and the marketplace, we continually incorporate safety, process, mechanical, and environmental improvements. These upgrades represent a significant investment in order to maintain reliable, uninterrupted product supply. We call this commitment Manufacturing Excellence.

Many industries including polymers and specialty chemicals use T-HYDRO as an initiator and/or oxidant because of its many advantages over competitive products: Safer Handling Broad Solvent Compatibility High Selectivity Excellent Reactivity Control Mild Reaction Conditions Volatile, Stable Byproduct Cost Effectiveness

Little to no decomposition occurs up to moderate temperatures (~100F/38C). As a result, storage and handling do not present the difficulties associated with many other organic peroxides. T-HYDRO provides versatility and convenience in many applications because of solvent compatibility. TBHP'S solubility in water is about 15 wt.%. TBHP is also miscible with most organic solvents. T-HYDRO provides excellent reactivity control with catalyst choice and often mild reaction conditions. Selectivity advantages include regioselectivity, stereoselectivity, and chemoselectivity. When reacted, the byproduct tertiary butyl alcohol is stable. Simple distillation easily reduces the alcohol to low residual levels. T-HYDRO is also more cost effective than competitive organic peroxides due to its low price and high efficiency.

T-HYDRO's thermal stability provides for safer handling than other commonly used oxidizing agents. It has a high selfaccelerating decomposition temperature (190F/88C).

T-Hydro Solution General Properties

T-HYDRO IS AN IDEAL SOURCE OF TBHP. ITS CONSISTENT QUALITY AND LOW LEVEL OF IMPURITIES MAKE IT A REAGENT OF CHOICE. TABLE I SHOWS THE TYPICAL COMPOSITION AND PROPERTIES OF T-HYDRO.

ST VE I O T CFFEC
E

Table I TYPICAL COMPOSITION AND PROPERTIES

TBHP, wt.% TBA, wt.% max Ketones, wt.% max. DTBP/Dialkyl Peroxides, wt.% max Other Organics, wt.% max. Other Hydroperoxides, wt.% max. Water phase, free, wt.% max Water, wt.% by difference 69-70 0.5 0.2 0.1 0.4 1.0 0.7 balance

Active Oxygen, wt.% Density, lb/gal @ 25C Specific Gravity @ 25C Refractive Index Flash Point F/C) Boiling Point F/C) Storage Temperature Range (F)

12 7.8 0.935 1.3246 109/43 205/96 50-100

MANUFACTURING EXCELLENCE

T-Hydro Solution Worldwide Sourcing

Figure I shows the solubility characteristics of the TBHP and water system. At ambient temperatures, dilution of the single phase T-HYDRO solution results in the formation of two liquid phases. Dilution to about 15% TBHP in water gives a new single liquid phase again. The solubility of water in TBHP depends on temperature as well as other factors. Small changes in temperature may create a separate water phase. A unique characteristic of TBHP is its high thermal stability compared with other organic peroxides. The Self Accelerating Decomposition Temperature (SADT) in Table II of the Applications Section illustrates the stability. This characteristic makes TBHP an effective high-temperature polymerization initiator.

Figure II shows that T-HYDRO's vapor pressure is slightly higher than water's and significantly higher than that of neat TBHP for temperatures that range from freezing to boiling. Dilution of T-HYDRO with water raises the relative volatility of TBHP with respect to water, as presented in Figure III.

TBHP is soluble in most solvents. Typical solvents include methanol, ethanol, isopropanol, acetone, tertiary butyl alcohol, methy tert- butyl ether, dimethyl formamide, and propylene glycol as well as hydrocarbon solvents. Table II (see Applications Section) compares TBHP's solvent compatibility versus other peroxides.

Liquid-liquid extraction of T-HYDRO with organic solvents such as n-heptane, toluene, iso-octane and methyl tert-butyl ether produces non-aqueous forms of TBHP. Figure IV provides the ternary phase diagram for TBHP, water, and various solvents. This capability of T-HYDRO makes it a versatile oxidation agent for selective aqueous or non-aqueous oxidations.

T-Hydro Solution Worldwide Sourcing

T-Hydro Solution Applications

Free Radical Polymerization Initiator

Emulsion, solution, bulk and suspension polymerization processes utilize TBHP as a free radical initiator or curing agent. The polymer industry uses straight T-HYDRO as a free radical initiator over a broad temperature range under thermal or appropriate redox initiation. Redox agents/promoters such as sulfur dioxide, sulfide salts, and transition metal salts readily activate TBHP. Polymerization temperatures can be as low as -20C. In addition, T-HYDROs high thermal stability relative to other peroxides makes it ideal in high temperature processes. However, T-HYDRO is a highly reactive product and should never be premixed with promoters. Use special caution when using T-HYDRO with redox agent, systems. For a more detailed discussion, refer to the polymerization technical bulletin.
Synthesis of Peroxy Derivatives

T-HYDRO serves many diverse applications because of its versatility. Its cost effectiveness gives it commercial value.

The largest application for T-HYDRO is the production of tertiary-butyl derivatives, particularly peresters, perketals, and dialkyl peroxides. T-HYDRO is an excellent source of the tertiary-butyl peroxy group because of its thermal stability, handling advantages, and few byproducts.

R E F G N A I S ANDL
H

T-Hydro Solution

Epoxidation

Miscellaneous Applications

Epoxidation with TBHP provides excellent reactivity control under mild reaction conditions with proper catalyst choice. Epoxidation of long chain -olefins or their derivatives with TBHP and transition metal catalyst systems produces epoxides with or in high selectivity and yields. Such products include polyol modifiers for surfactants, epoxy reactive diluents, intermediates for tube and fuel additives, and scavengers for H2S and other acids. Epoxidation with TBHP offers many advantages over chlorohydrin and peracid technologies. Careful choice of transition metal catalysts allows good control of reactivity to minimize side reactions and achieve high yields and chemo-, regio-, and stereoselectivity. These catalysts include molybdenum, tungsten, and vanadium complexes. Lyondell Chemical Company's epoxidation of propylene to propylene oxide is a multibillion pound a year commercial application for TBHP. For further discussion, consult the epoxidation technical bulletin.

TBHP gives excellent reactivity control with proper catalyst choice.

Oxidation

T-HYDRO is a readily available source of active oxygen. Although most oxidations using hydroperoxides require anhydrous conditions, some reactions can be carried out with aqueous TBHP. In addition, simple extractive distillation of T-HYDRO readily provides anhydrous TBHP solutions.

TBHP, when used with transition metals, effectively removes sulfur from petroleum. It scavenges volatile sulfur compounds and oxidizes them to soluble derivatives. Adding TBHP to lubricants such as sulfurized paraffin oil can improve load carrying antiwear and extreme pressure properties for metal cutting. Adding TBHP to lubricating oil also has been found to be effective in reducing the wear of one or more metal and/or ceramic surfaces in contact with an advanced ceramic surface.

TBHP and metal catalyst systems give high selectivity compared to other oxidizing agents such as hydrogen peroxide and peracetic acid. TBHP with transition metal catalysts can selectively oxidize olefins, alcohols, ethers, and other organic compounds. In addition, volatile tertiary butyl alcohol byproduct can be removed easily from the reaction mixture to give the desired products high purity. Pharmaceutical, agrochemical, fragrance, and other chemical industries find TBHP to be an excellent alternative to other oxidants.

TBHP also finds use as a flocculent for borine-containing solutions in ores, coal, or industrial slurry processing. Mixtures of TBHP and di-t-butyl peroxide help prepare epoxidized surfactants from a methylated ethylene oxide polyol and a C12C18 olefin. TBHP with various catalyst systems can degrade thermoplastics, oils, and fats to low molecular weight hydrocarbons for recycling and waste treatment.

T-HYDRO is convenient to use for diverse applications because of its solvent compatibility.

T-Hydro Solution Potential Hazards

T-HYDRO's three enemies are ignition sources, heat, and contamination. To minimize the resulting hazards, avoid prolonged 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 for bulges or leaks. T-HYDRO is highly combustible. Once ignited, the material burns with a flareburning effect. During combustion thermal decomposition may occur as well. Flammability limits depend upon temperature, pressure, volume of sample tested, shape of container, and type of ignition source. When measured at 80C (176F), the lower flammability limit of T-HYDRO vapors in air is 5.75 vol% TBHP. Because TBHP decomposes 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 nitrogen is 42.8 mol%, and the upper limit is 100%. Compared with most other hydroperoxides, T-HYDRO has high thermal stability. The material is stable at ambient temperatures (100F or 38C), and unadulterated material may be kept for several months without a significant loss of activity. However, at increased temperatures T-HYDRO will rapidly decompose with flame propagation at velocities between a few decimeters and meters per second. In addition, TBHP decomposition generates oxygen, highly flammable isobutylene, and incomplete combustion products such as carbon monoxide. The thermal decomposition rate and half-life of TBHP depends on surface-to-volume effects, container material, and contamination. Self-accelerating decomposition becomes significant (i.e., greater than 1% per hour) at a temperature of approximately 88C (190F). Using an Accelerating Rate Calorimeter (ARC) with a passivated stainless steel bomb, the 10-hour half-life of TBHP in THYDRO was approximately 118C (244F). Decomposition proceeded at a faster rate in an untreated stainless steel bomb. Figure V provides half-life data for T-HYDRO by the ARC method. Contamination with acids, bases, and, especially, polyvalent metal ions such as those from iron can accelerate the decomposition rate. Spontaneous combustion may occur if mixed with readily oxidizable organic or flammable material. For example, addition of caustic material leads to exothermic decomposition and the generation of oxygen.

T-Hydro Solution Toxicology

Lyondell Chemical has conducted extensive toxicity testing on T-HYDRO as shown by Table III. The primary routes of entry are through inhalation and dermal exposures. Single exposures can lead to severe, irreversible skin and eye damage. Exposure to vapor can cause severe skin, eye, and respiratory tract irritation. T-HYDRO is not expected to present a dermal sensitization hazard. It should be considered moderately toxic for short-term exposures. Repeated dose studies have also resulted in local irritation effects following oral and inhalation exposures. Oral exposures have caused severe irritation and edema of the stomach. Male rats exposed to repeated oral doses of T-HYDRO have developed specific kidney effects commonly found in that species. Rats exposed to T-HYDRO aerosol have shown increased eye and nasal secretions from its irritant properties. T-HYDRO has not been shown to produce any harmful reproductive or developmental effects in tests conducted with laboratory animals. Like other reactive peroxides, T-HYDRO is active in cell mutation studies. However, T-HYDRO does not produce mutagenic effects in whole animal studies. Some studies designed to evaluate cancer mechanisms have shown that T-HYDRO produces tumors indirectly; however, additional studies have not identified any cancer producing capability. Based on the available information, T-HYDRO is not expected to be carcinogenic.

T-Hydro Solution Environment

The biotreatability of aqueous TBHP streams has not been identified. Reducing agents as well as acids and transition metal ions which may be available in waste water streams can convert TBHP to tertiary butyl alcohol. No data exists at this time estimating the percent conversion in a typical waste water stream. Studies indicate that tertiary butyl alcohol is treatable in acclimated, well-operated biological treatment systems. However, the conditions and/or retention time required may exceed typical conditions. The primary pathways for TBHP removal from soils probably are biodegradation and transport to groundwater. Available information indicates that T-HYDRO should not bioaccumulate in plants and animals. Lyondell Chemical Company's Material Safety Data Sheet and Product Safety Bulletin contain detailed information pertinent to the safe handling of T-HYDRO TBHP.

T-Hydro Solution
___________________________________________________________ Quality Commitment
It is the policy of Lyondell Chemical Company to provide products and services that meet the requirements of all our customers, as well as to select suppliers who meet our requirements for consistent products and services.

To Accomplish This We Will:

Involve all employees as active participants in a team effort to continuously improve the quality of our products and services. Regard management of quality improvement as a critical element for our business success and hold managers accountable for managing the process. Continually measure the progress made by each of our units in meeting customer requirements. Provide a specific means by which all employees are comfortable in frankly identifying and eliminating obstacles that get in the way of improving the quality of their work. Train all employees in the principles and methods of total quality improvement. Recognize employees individually and in groups for quality improvement achievements.

Visit us at our Web site: www.lyondell.com

World Headquarters Lyondell Chemical Company 1221 McKinney Street Houston, TX 77010 USA Telephone: (713) 652-7200 Facsimile: (713) 309-4944 MSDS Hotline: (800) 700-0946 European Headquarters Lyondell Chemical Europe, Inc. P. O. Box 2416 3000 CK Rotterdam The Netherlands Telephone: (31) (10) 275-5500 Facsimile: (31) (10) 275-5599 Asian Headquarters Lyondell Asia Pacific, Ltd. 41st Floor, The Lee Gardens 33 Hysan Avenue Causeway Bay Hong Kong Telephone: (852) 28822-668 Facsimile: (852) 28401-690

Newtown Square Technology Center Lyondell Chemical Company 3801 West Chester Pike Newtown Square, PA 19073-2387 USA Telephone: (610) 359-2000 Facsimile (610) 359-2841

Lyondell South America Av Roque Petroni Jr, 999, cj 123 Sao Paulo, SP 04707-910 Brazil Telephone: (55) 11-5185-9300 Facsimile: (55) 11-5185-9333

Telephone toll-free in the U.S. and Canada 1-888-777-0232

For assistance in Europe and Asia telephone 33 3 44 24 92 05 For assistance in Brazil telephone 55-11-5185-9321 For assistance in other countries in South America telephone 55-11-5185-9303

_________________________________________________________________________________
This information is believed to be accurate as of the date of publication. It is the sole responsibility of the customer to determine whether the product is appropriate and suitable for the customers specific use. Specific end uses may require approval by appropriate regulatory agencies. Lyondell Chemical Company makes no warranties, express or implied, regarding the product or information contained therein. The applicable Material Data Sheet should be reviewed by customer before handling the Lyondell Chemical product. Lyondell Chemical Company disclaims any liability for infringement of any patent by reason of customers use of any Lyondell Chemical Company products in combination with other materials or in any process. 2004 Lyondell Chemical Company 2644-V2-0204 supersedes OP167-1294