T-Hydro® Solutiont-Butyl Hydroperoxide

T-Hydro® Solution

SUMMARYT-HYDRO® TBHP Solution is a highly

versatile product, containing 69-70% ter-

tiary-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 cus-

tomers 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.

ADVANTAGESMany 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

T-HYDRO's thermal stability provides for

safer handling than other commonly used

oxidizing agents. It has a high self-

accelerating decomposition temperature

(190°F/88°C).

Little to no decomposition occurs up to

moderate temperatures (~100°F/38°C). 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 chemoselec-

tivity. 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.

Product Overview

TBHP, wt.% 69-70

TBA, wt.% max 0.5

Ketones, wt.% max. 0.2

DTBP/Dialkyl Peroxides, wt.% max 0.1

Other Organics, wt.% max. 0.4

Other Hydroperoxides, wt.% max. 1.0

Water phase, free, wt.% max 0.7

Water, wt.% by difference balance

Active Oxygen, wt.% 12

Density, lb/gal @ 25°C 7.8

Specific Gravity @ 25°C 0.935

Refractive Index 1.3246

Flash Point °F/°C) 109/43

Boiling Point °F/°C) 205/96

Storage Temperature Range (°F) 50-100

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.

Table ITYPICAL COMPOSITION AND PROPERTIESCOST

EFFECTIVE

MANUFACTURING EXCELLENCE

T-Hydro® Solution

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 pres-

sure is slightly higher than water's and sig-

nificantly 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.

Worldwide Sourcing

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

Free Radical PolymerizationInitiatorEmulsion, 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 tem-

perature 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 -20°C. In addition, T-HYDRO’s high

thermal stability relative to other peroxides

makes it ideal in high temperature process-

es. 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

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.

Applications

T-HYDRO serves many

diverse applications

because of its

versatility. Its cost

effectiveness gives it

commercial value.

SAFER

HANDLING

T-Hydro® Solution

EpoxidationEpoxidation with TBHP provides excellent

reactivity control under mild reaction

conditions with proper catalyst choice.

Epoxidation of long chain α-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 reac-

tivity to minimize side reactions and achieve

high yields and chemo-, regio-, and stereo-

selectivity. These catalysts include molyb-

denum, tungsten, and vanadium complexes.

Lyondell Chemical Company's epoxidation

of propylene to propylene oxide is a multi-

billion pound a year commercial application

for TBHP. For further discussion, consult

the epoxidation technical bulletin.

OxidationT-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 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, alco-

hols, ethers, and other organic compounds.

In addition, volatile tertiary butyl alcohol

byproduct can be removed easily from the

reaction mixture to give the desired prod-

ucts high purity. Pharmaceutical, agrochem-

ical, fragrance, and other chemical industries

find TBHP to be an excellent alternative to

other oxidants.

TBHP gives excellent reactivitycontrol with proper

catalyst choice.

Miscellaneous ApplicationsTBHP, 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 paraf-

fin 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 reduc-

ing the wear of one or more metal and/or

ceramic surfaces in contact with an advanced

ceramic surface.

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 C12–C18 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 fordiverse applications

because of its solventcompatibility.

T-Hydro® Solution

T-HYDRO's three enemies are ignition

sources, heat, and contamination. To mini-

mize 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 flare-

burning effect. During combustion thermal

decomposition may occur as well.

Flammability limits depend upon tempera-

ture, pressure, volume of sample tested,

shape of container, and type of ignition

source. When measured at 80°C (176°F),

the lower flammability limit of T-HYDRO

vapors in air is 5.75 vol% TBHP.

Because TBHP decomposes at elevated tem-

peratures 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

(100°F or 38°C), 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 monox-

ide. The thermal decomposition rate and

half-life of TBHP depends on surface-to-vol-

ume effects, container material, and contam-

ination.

Potential Hazards

Self-accelerating decomposition becomes sig-

nificant (i.e., greater than 1% per hour) at a

temperature of approximately 88°C (190°F).

Using an Accelerating Rate Calorimeter

(ARC™) with a passivated stainless steel

bomb, the 10-hour half-life of TBHP in T-

HYDRO was approximately 118°C (244°F).

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, espe-

cially, 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

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, irre-

versible skin and eye damage. Exposure to

vapor can cause severe skin, eye, and respira-

tory 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.

Toxicology

T-Hydro® Solution

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 estimat-

ing the percent conversion in a typical

waste water stream. Studies indicate that

tertiary butyl alcohol is treatable in accli-

mated, 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 infor-

mation 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.

Environment

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 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

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 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

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

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 customer’s 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 customer’s 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