TRICHLOROETHYL PHOSPHATE

TRICHLOROETHYL PHOSPHATE=TCEP

CAS Number: 115-96-8
CAS Name: Tris(2-chloroethyl) phosphate
Molecular Formula: C6H12Cl3O4P

Trichloroethyl Phosphate (TCEP) is a chemical compound used as a flame retardant, plasticizer, and viscosity regulator in various types of polymers including polyurethanes, polyester resins, and polyacrylates.

Article service life
Other release to the environment of Trichloroethyl Phosphate is likely to occur from: outdoor use in long-life materials with low release rate (e.g. metal, wooden and plastic construction and building materials).
Trichloroethyl Phosphate can be found in products with material based on: stone, plaster, cement, glass or ceramic (e.g. dishes, pots/pans, food storage containers, construction and isolation material) and metal (e.g. cutlery, pots, toys, jewellery).

Widespread uses by professional workers for Trichloroethyl Phosphate:
Trichloroethyl Phosphate is used in the following products: coating products.
Trichloroethyl Phosphate is used in the following areas: offshore mining and building & construction work.
Other release to the environment of Trichloroethyl Phosphate is likely to occur from: outdoor use resulting in inclusion into or onto a materials (e.g. binding agent in paints and coatings or adhesives).

Trichloroethyl Phosphate uses at industrial sites
Trichloroethyl Phosphate is used in the following products: coating products.
Trichloroethyl Phosphate is used in the following areas: offshore mining and building & construction work.
Release to the environment of this substance can occur from industrial use: in the production of articles.

Trichloroethyl Phosphate general description
Trichloroethyl Phosphate is used as a flame retardant in plastics, especially inflexible foams used in automobiles and furniture and in rigid foams used for building insulation.

Trichloroethyl Phosphate application
Trichloroethyl Phosphate was used in dynamic air sampling of airborne organophosphate triesters using a solid-phase microextraction device.
Trichloroethyl Phosphate is often used as a reducing agent to break disulfide bonds within and between proteins as a preparatory step for gel electrophoresis.

Compared to the other two most common agents used for this purpose (dithiothreitol and β-mercaptoethanol), Trichloroethyl Phosphate has the advantages of being odorless, a more powerful reducing agent, an irreversible reducing agent (in the sense that Trichloroethyl Phosphate does not regenerate—the end product of Trichloroethyl Phosphate-mediated disulfide cleavage is in fact two free thiols/cysteines), more hydrophilic, and more resistant to oxidation in air.
Trichloroethyl Phosphate also does not reduce metals used in immobilized metal affinity chromatography.

Trichloroethyl Phosphate is particularly useful when labeling cysteine residues with maleimides. Trichloroethyl Phosphate can keep the cysteines from forming di-sulfide bonds and unlike dithiothreitol and β-mercaptoethanol, it will not react as readily with the maleimide.
However, Trichloroethyl Phosphate has been reported to react with maleimide under certain conditions.

Trichloroethyl Phosphate is also used in the tissue homogenization process for RNA isolation.

For Ultraviolet–visible spectroscopy applications, Trichloroethyl Phosphate is useful when it is important to avoid interfering absorbance from 250 to 285 nanometers which can occur with dithiothreitol. Dithiothreitol will slowly over time absorb more and more light in this spectrum as various redox reactions occur.

Uses of Trichloroethyl Phosphate
Trichloroethyl Phosphate is used primarily as an additive plasticiser and viscosity regulator with flame-retarding
properties for the production of unsaturated polyester resins (~ 80 %). Other fields of
application are acrylic resins, adhesives and coatings.
The main industrial branches to use TCEP as a flame-retardant plasticiser are the furniture,
the textile and the building industry (roof insulation); it is also used in the manufacture of
cars, railways and aircrafts.
Other utilisation of Trichloroethyl Phosphate is flame resistant paints and varnishes, e.g. for polyvinyl acetate or
acetyl cellulose and the use as a secondary plasticiser for polyvinyl chloride to suppress the
flammability resulting from plasticisers such as phthalates. It can be assumed that no TCEP is
formulated into consumer paints. 

Molecular Mass: 285.49
Boiling Point: 330 °C @ Press: 800 Torr
Melting Point: -55 °C
Odor: Low Odor
Color: Clear, transparent liquid
Form: Low viscosity liquid
Density: 1.425 g/cm3 @ Temp: 20 °C
InChI: 1S/C6H12Cl3O4P/c7-1-4-11-14(10,12-5-2-8)13-6-3-9/h1-6H2
InChIKey: HQUQLFOMPYWACS-UHFFFAOYSA-N
SMILES: P(OCCCl)(OCCCl)(OCCCl)=O
Canonical SMILES: O=P(OCCCl)(OCCCl)OCCCl
XLogP3-AA: 1.3
Hydrogen Bond Donor Count: 0
Hydrogen Bond Acceptor Count: 4
Rotatable Bond Count: 9
Exact Mass: 283.953879
Monoisotopic Mass: 283.953879
Topological Polar Surface Area: 44.8 Ų
Heavy Atom Count: 14
Formal Charge: 0
Complexity: 152
Isotope Atom Count: 0
Defined Atom Stereocenter Count: 0
Undefined Atom Stereocenter Count: 0
Defined Bond Stereocenter Count: 0
Undefined Bond Stereocenter Count: 0
Covalently-Bonded Unit Count: 1
Compound Is Canonicalized: Yes

Environmental releases
On the local scale releases of Trichloroethyl Phosphate are expected during the industrial use of the polymer
components as well as the formulation and industrial use (processing) of paints and varnishes.
The less relevant use of Trichloroethyl Phosphate as an intermediate should be considered additionally. Although
there is no production in Europe a generic scenario for production is performed. The flame
retardant Trichloroethyl Phosphate is physically combined with the polymer matrix. Therefore, Trichloroethyl Phosphate could
migrate to the surface. Releases might be expected during service life and disposal of products
containing Trichloroethyl Phosphate.

Environmental fate
Trichloroethyl Phosphate is considered as non biodegradable. Trichloroethyl Phosphate is not expected to hydrolyse under
environmental conditions. Direct photolysis in water does not play an important role either.
An estimation of the half life for the atmospheric reaction of Trichloroethyl Phosphate with hydroxyl radicals
with the programme AOP 1.65 results in a half-life of 17.5 h (24-h day, 5x105 OH/cm3).
With a Henry’s law constant of 4.155 x 10-5 Pa·m3
·mol-1, Trichloroethyl Phosphate has a low volatility.
There are no experimental results on the adsorption of Trichloroethyl Phosphate to soil available. A KOC of
110.2 l/kg was calculated using a log Kow of 1.78. The adsorption of Trichloroethyl Phosphate is classified as
being ‘low’. Trichloroethyl Phosphate does not meet the PBT criteria.

According to Mackay model (level 1) the hydrosphere is the target compartment of Trichloroethyl Phosphate
(94.8 %), followed by terrestrial compartment (5.06 %).
The log KOW of 1.78 indicates a low bioaccumulation potential. The highest measured BCF in
fish are <1.2-5.1.
Based on the physical chemical properties as well as the biodegradation rate of 0 h-1 in the
WWTP, it can be estimated that 98.6 % of Trichloroethyl Phosphate remain in the water and 1.4 % is adsorbed to
sludge.

As a flame retardant in paint and coating manufacturing, polymers, and articles;
In industrial and commercial aircraft interiors and aerospace products;
For laboratory chemicals; and
In commercial and consumer products, including paints and coatings, fabric and textile, products, foam seating, and construction materials.
The above listed conditions of use are ways that a person or the environment could be potentially exposed to this chemical. However, when conducting a risk evaluation, EPA also considers the hazards (i.e. health effects or environmental impacts) that could occur from coming in contact with a chemical.

Trichloroethyl phosphate uses and applications include: Flame retardant plasticizer for plastics including rigid PU and polyisocyanurate foams, PVC, carpet backing, flame-laminated and rebonded flexible foam, coatings, most thermosets, adhesives, cast acrylic sheet, wood-resin composites (particle board); fire-resistant cellulose ester plasticizer; in food packaging adhesives

Trichloroethyl Phosphate uses 
General adhesives and binding agents for a variety of uses
Materials used in the building process, such as flooring, insulation, caulk, tile, wood, glass, etc.
Insulating materials to protect from noise, cold, etc (such as used in homes or buildings), insulating materials related to electricity
Related to products specifically designed for children (e.g. toys, children's cosmetics, etc)
Insulating materials to protect from noise, cold, etc (such as used in homes or buildings), insulating materials related to electricity
Fire prevention materials, or additives/coatings to prevent flammability in paints, textiles, plastics, etc
Plastic products, industry for plastics, manufacturing of plastics, plastic additives (modifiers included when known)
Fragrances or odor agents, can be used in home products (cleaners, laundry products, air fresheners) or similar industrial products; usage indicated when known; more specific modifiers included when known.
Related to electrical work (such as wiring of a building), electric current insulation materials, or other electrical components    
Furniture, or the manufacturing of furniture (can include chairs and tables, and more general furniture such as mattresses, patio furniture, etc.)

Manufacturing of or related to machinery, for production of cement or food, air/spacescraft machinery, electrical machinery, etc
Various types of paint for various uses, modifiers included when more information is known
Plastic products, industry for plastics, manufacturing of plastics, plastic additives (modifiers included when known)
Relating to the disposal and/or treatment of sewage
Textiles used for clothing or furniture upholstery processes related to textiles (e.g. softeners, antiwrinkle agents), or the processing/manufacturing of textiles 
Toys (e.g. dress-up clothes, dolls, playground equipment, bath toys, etc); pet toys; includes additional modifiers when appropriate
Used primarily as an additive plasticiser and viscosity regulator with flame-retarding properties for polyurethane, polyesters, polyvinyl chloride and other polymers.

Trichloroethyl Phosphate is Used in rigid polyurethane and polyisocyanurate foams, carpet backing, flame-laminated and rebonded flexible foam, flame-retardant coatings, most classes of thermosets, adhesives (gv), cast acrylic sheet, and wood-resin composites such as particle board.
Emulsions of tris(2-chloroethyl) phosphate, blended with a binder such as a vinyl or acrylic emulsion, can be used for applications such as the backcoating of upholstery. It can be used as a secondary plasticizer in polyvinyl chloride to suppress the flammability resulting from plasticizers such as phthalates. Where a particularly high degree of flame retardancy is required, it can be used in combination with the aromatic phosphate plasticizers. Such formulations can serve as an alternative to the use of antimony oxide in plasticized vinyl polymers.
Trichloroethyl Phosphate is Used with melamine in flexible urethane foam cushions and institutional mattresses.
Tris(beta-chloroethyl) phosphate is used as versatile flame retardant for flexible as well as rigid polyurethane foams. Even though tris(beta-chloroethyl) phosphate is an additive type of flame retardant, that is, not incorporated as a part of the substrate by chemical bonding, it still offers good retention except under very hot and humid conditions.
Flame retardant in plastics, especially in flexible foams used in automobiles and furniture, and in rigid foams used for building insulation.

What is Trichloroethyl Phosphate?
Trichloroethyl Phosphate is a flame retardant.
Trichloroethyl Phosphate has been added to polyurethane foams and plastics in:
Certain children’s products with foam padding, such as some crib bumpers, sleep mats, changing table pads, and portable mattresses.
Some motor vehicles, furniture, building insulation, back-coatings of carpets and upholstery, and electronic and electrical devices.

Summary
Chemical flame retardant use developed in response to an increase in fire safety regulations in the 1970's. Trichloroethyl Phosphate is a human-made, phosphate-based chemical added to certain plastics, fabrics, and foams, to slow their capacity to ignite and burn.

Trichloroethyl Phosphate can enter the environment through wastewater, manufacturing processes, and leaching from disposed materials containing the chemical, among other means. Studies have found Trichloroethyl Phosphate persists in water and soil, but has low potential to build up within the tissues of organisms (i.e., bioaccumulate) and is a low- to moderate-toxicant to certain species. There is limited data regarding human health effects but adverse effects linked to Trichloroethyl Phosphate in laboratory animal studies include carcinogenicity, reproductive toxicity, and neurotoxicity.

During the 2011 legislative session, New York became the first state to prohibit the sale or offer for sale of certain child care products containing Trichloroethyl Phosphate. The ban begins December 1, 2013, and violators are subject to civil penalties.

This report cites information resources from a number of jurisdictions that have reviewed scientific studies on Trichloroethyl Phosphate's effects. For the reader's convenience, we numbered and listed the studies in Attachment 1 and cite the reference number in the text.

Trichloroethyl Phosphate (TCEP)

Trichloroethyl Phosphate is part of a chemical class of fire retardants called “phosphate esters,” and is produced by reacting phosphorus oxychloride (a chemical derived from white phosphorus) with an alcohol.Trichloroethyl Phosphate is added to many consumer products such as textiles, carpeting, furniture foams, and electronics, to reduce flammability.

Trichloroethyl Phosphate is one of several types of phosphorus-based retardants referred to as “tris” chemicals (“tris” applies to chemical compounds with three parts of equal structure). Other forms of “tris” flame retardants include tris(1,3-dichloro-2-propyl)phosphate (TDCP or TDCPP), tris(1-chloro-2-propyl)phosphate (TCPP), and tris(2,3-dibromopropyl)phosphate (tris-BP), which have similar properties but different structures.

Abstract
Organophosphate flame retardants (PFRs) are a new class of flame retardants. The health risks of PFRs have received attention recently. However, little is known about the potential toxicity of PFRs on the nervous system. Herein, we evaluated the neurotoxic effects of two typical PFRs, tris(2-chloroethyl) phosphate (TCEP) and tris(2-chloropropyl) phosphate (TCPP), using Caenorhabditis elegans. Median lethal concentrations of chronic exposure (3 d) were 1578 and 857 mg L−1 for TCEP and TCPP, respectively. The sublethal dose of TCEP or TCPP significantly inhibited the body length and reduced the lifespans of nematodes. 500 mg L−1 and above of TCEP/TCPP led to a significant decline in the locomotor frequency of body bending and head thrashing.

Furthermore, their exposure reduced the crawling speed and the frequency of bending oscillation of nematodes. This indicates that TCEP/TCPP induces locomotor deficits, along with Parkinsonian-like movement impairment including bradykinesia and hypokinesia. Using transgenic worms, we found that TCEP/TCPP could induce down-expression of Pdat-1 and resulted in the degeneration of dopaminergic neurons, especially PDE neurons. Moreover, TCEP/TCPP induced over-expression of unc-54, which indicates the aggregation of α-synuclein in the process of degeneration. These findings suggest the neurotoxicity risks of organophosphorus flame retardants, which are associated with the locomotor deficits and dopaminergic degeneration.

The effective removal of organophosphorus compounds (OPs) effectively from water environment remains an important but challenging task. In this study, a resin-based nanocomposite of hydrated iron oxide (HD1) was used as Fenton-like catalyst for effectively catalyzing the decomposition of hydrogen peroxide to degrade tris(2-chloroethyl) phosphate (TCEP).

The results showed that HD1 was successfully prepared, which had great versatility, catalytic performance and adsorption capacity. Besides, HD1/H2O2 was capable of degrading TCEP completely with less than 0.2 mg/L of inorganic phosphorus (IP) in the effluent at the initial TCEP of 38 mg/L, pH = 4, H2O2 dosage of 20 mM, and the Kobs could result in about 1.0530 min−1 under identical conditions. More attractively, inorganic ions (i.e., Clˉ, CO32ˉ, SO42ˉ, NO3ˉ, HCO3ˉ, Ca2+, and Mg2+) exhibited moderate effect on TCEP degradation.

The negative effect of natural organic matters (NOM) (i.e., HA) on the degradation of TCEP was responsible for competition for the active oxygen species. Combined with electron paramagnetic resonance (EPR) spectra, X-ray photoelectron spectroscopy (XPS) and other analytical methods and radical quenching experiments, the possible removal process of TCEP was discussed, including two processes of oxidative degradation and immobilization of IP. Besides, hydroxyl radicals (•OH) was the key active species that contributed to TCEP degradation through hydroxylation-oxidation and C–O bond cracking, and specificity adsorption of HFO on IP was revealed. Furthermore, the results showed that HD1 had desirable acid and alkali resistance. In the continuous running fixed bed column experiment, HD1 showed a satisfactory performance in cycle operations. This work proposed a new enhanced process for removing TCEP in water environment by HD1/H2O2, and the multi-functional material, HD1 was promising in treatment of water containing organic phosphorus pollutants.

Trichloroethyl Phosphate will be believed that this study will provide new ideas and new materials for the treatment of organic phosphorus-based organic pollutants, and lay the foundation for further deepening and expanding the application of adsorption resins in the field of water pollution control.

Regulations and the voluntary activities of manufacturers have led to a market shift in the use of flame retardants (FRs). Accordingly, organophosphate ester flame retardants (OPFRs) have emerged as a replacement for polybrominated diphenyl ethers (PBDEs). One of the widely used OPFRs is tris(2-chloroethyl) phosphate (TCEP), the considerable usage of which has reached 1.0 Mt globally. High concentrations of TCEP in indoor dust (∼2.0 × 105 ng g−1), Trichloroethyl Phosphates detection in nearly all foodstuffs (max. concentration of ∼30–300 ng g−1 or ng L−1), human body burden, and toxicological properties as revealed by meta-analysis make TCEP hard to distinguish from traditional FRs, and this situation requires researchers to rethink whether or not TCEP is an appropriate choice as a new FR. However, there are many unresolved issues, which may impede global health agencies in framing stringent regulations and manufacturers considering the meticulous use of TCEP.

Therefore, the aim of the present review is to highlight the factors that influence TCEP emissions from its sources, its bioaccessibility, threat of trophic transfer, and toxicogenomics in order to provide better insight into its emergence as an FR. Finally, remediation strategies for dealing with TCEP emissions, and future research directions are addressed.

The spontaneous hydrolysis of 2,2,2-trichloroethyl phosphate was investigated at 90°C in aqueous media with an ionic strength of 0.10 (KNO3) over pH 3–5. The reaction followed apparent first-order kinetics with respect to the phosphate species. Trichloroethanol once produced during the reaction was further hydrolyzed with the liberation of hydrochloric acid. However, the liberation of hydrochloric acid has never been detected unless the phosphate was hydrolyzed. No significant participation of the neighboring β-chlorine atom was observed in the phosphate hydrolysis.

Other Names for TRICHLOROETHYL PHOSPHATE
Ethanol, 2-chloro-, 1,1′,1′′-phosphate
Ethanol, 2-chloro-, phosphate (3:1)
Celluflex CEF
Tris(β-chloroethyl) phosphate
Tris(2-chloroethyl) phosphate
Tris(chloroethyl) phosphate
Tri(β-chloroethyl) phosphate
Tri(2-chloroethyl) phosphate
Tris(2-chloroethyl) orthophosphate
Niax Flame Retardant 3CF
3CF
Niax 3CF
Disflamoll TCA
Fyrol CEF
Genomoll P
TCEP
Tri(chloroethyl) phosphate
Fyrol CF
CLP
Amgard TCEP
CEF
NSC 3213
Phosphoric acid tris(2-chloroethyl) ester
Roflam E