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Names | |
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Preferred IUPAC name N1-(4-Methylpentan-2-yl)-N4-phenylbenzene-1,4-diamine | |
Other names N-(1,3-dimethylbutyl)-N'-phenyl-1,4-benzenediamine
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Identifiers | |
3D model (JSmol) | |
ChEMBL | |
ChemSpider | |
ECHA InfoCard | 100.011.222 |
EC Number |
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PubChem CID | |
UNII | |
UN number | 3077 |
CompTox Dashboard (EPA) | |
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Properties | |
C18H24N2 | |
Molar mass | 268.404 g·mol−1 |
Appearance | brown or violet solid powder |
Density | 1.07 |
Melting point | 45 °C (113 °F; 318 K) |
Boiling point | 260 °C (500 °F; 533 K) |
log P | 3.972 |
Hazards | |
GHS labelling: | |
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Danger | |
H302, H317, H360, H410 | |
P201, P202, P261, P264, P270, P272, P273, P280, P281, P301+P312, P302+P352, P308+P313, P321, P330, P333+P313, P363, P391, P405, P501 | |
Flash point | 204 °C (399 °F; 477 K) |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). |
6PPD is an organic chemical widely used as stabilising additive (or antidegradant) in rubbers, such as NR, SBR and BR; all of which are common in vehicle tires. [1] Although it is an effective antioxidant it is primarily used because of its excellent antiozonant performance. It is one of several antiozonants based around p-phenylenediamine. [2]
It has been used in rubber since the late 1970s, [3] but has been the subject of increasing scrutiny since 2021, when it was determined that its oxidation product (6PPD-Q) causes pre-spawn mortality in coho salmon. [4] [5]
6PPD is prepared by reductive amination of methyl isobutyl ketone (which has six carbon atoms, hence the '6' in the name) with phenyl phenylenediamine (PPD). [6] This produces a racemic mixture.
6PPD is a common rubber antiozonant found in vehicle tires. It is mobile within the rubber and slowly migrates to the surface via blooming. On the surface it forms a "scavenger-protective film" that reacts with the ozone more quickly than the ozone can react with the rubber. [7] This process forms aminoxyl radicals [8] [9] and was first thought to degrade only to the quinone diimine, but has since been understood to continue to oxidize to quinones, amongst other products. [10] Despite 6PPD being used in tires since the mid 1970s, its transformation to quinones was first recognized in 2020. [11] [12] The oxidized products are not effective antiozonants, meaning that 6PPD is a sacrificial agent.
The tendency of 6PPD to bloom towards the surface is protective because the surface film of antiozonant is replenished from reserves held within the rubber. However, this same property facilitates the transfer of 6PPD and its oxidation products into the environment as tire-wear debris. The 6PPD-quinone (6PPD-Q, CAS RN: 2754428-18-5) is of particular and increasing concern, due to its toxicity to fish.
6PPD and 6PPD-quinone enter the environment through tire-wear particles and are sufficiently water-soluble to enter river systems via urban runoff. From here they become widely distributed (at decreasing levels) from urban rivers through estuaries, coasts and finally deep-sea areas. [13]
6PPD-quinone is of environmental concern because it is toxic to coho salmon, killing them before they spawn in freshwater streams. [14] [15] [16]
A 2022 study also identified the toxic impact on species like brook trout and rainbow trout. [17] The published lethal concentrations are: [17] [18]
It is not known why the ozone-oxidised 6PPD is toxic to coho salmon, but has been suggested that the large differences in lethal dose between species may relate to their ability to rid themselves of 6PPD-Q via glucuronidation. [19] The Nisqually and nonprofit Long Live the Kings installed a mobile stormwater filter at a bridge in the Ohop Valley in 2022. The Washington Department of Ecology, Washington State University and the US Tire Manufacturer's Association are working on regulation and education. [20]
6PPD itself is deadly to rotifers, especially in combination with sodium chloride, though not at the level generally found in the runoff from road salt. [21] A small-scale biomonitoring study in South China has shown both 6PPD and 6PPDQ to be present in human urine; concentrations were low but the health implications are unknown. [22] A synthetic route to the 6PPD-quinone has been posted on ChemRxiv. [23]
Indoor air quality (IAQ) is the air quality within buildings and structures. Poor indoor air quality due to indoor air pollution is known to affect the health, comfort, and well-being of building occupants. It has also been linked to sick building syndrome, respiratory issues, reduced productivity, and impaired learning in schools. Common pollutants of indoor air include: secondhand tobacco smoke, air pollutants from indoor combustion, radon, molds and other allergens, carbon monoxide, volatile organic compounds, legionella and other bacteria, asbestos fibers, carbon dioxide, ozone and particulates.
Chloromethane, also called methyl chloride, Refrigerant-40, R-40 or HCC 40, is an organic compound with the chemical formula CH3Cl. One of the haloalkanes, it is a colorless, sweet-smelling, flammable gas. Methyl chloride is a crucial reagent in industrial chemistry, although it is rarely present in consumer products, and was formerly utilized as a refrigerant. Most chloromethane is biogenic.
p-Phenylenediamine (PPD) is an organic compound with the formula C6H4(NH2)2. This derivative of aniline is a white solid, but samples can darken due to air oxidation. It is mainly used as a component of engineering polymers and composites like kevlar. It is also an ingredient in hair dyes and is occasionally used as a substitute for henna.
In organic chemistry, organophosphates are a class of organophosphorus compounds with the general structure O=P(OR)3, a central phosphate molecule with alkyl or aromatic substituents. They can be considered as esters of phosphoric acid. Organophosphates are best known for their use as pesticides.
In organic chemistry, ozonolysis is an organic reaction where the unsaturated bonds are cleaved with ozone. Multiple carbon–carbon bond are replaced by carbonyl groups, such as aldehydes, ketones, and carboxylic acids. The reaction is predominantly applied to alkenes, but alkynes and azo compounds are also susceptible to cleavage. The outcome of the reaction depends on the type of multiple bond being oxidized and the work-up conditions.
In organic chemistry, peroxyacyl nitrates are powerful respiratory and eye irritants present in photochemical smog. They are nitrates produced in the thermal equilibrium between organic peroxy radicals by the gas-phase oxidation of a variety of volatile organic compounds (VOCs), or by aldehydes and other oxygenated VOCs oxidizing in the presence of NO2.
Chlorinated paraffins (CPs) are complex mixtures of polychlorinated n-alkanes. The chlorination degree of CPs can vary between 30 and 70 wt%. CPs are subdivided according to their carbon chain length into short-chain CPs, medium-chain CPs and long-chain CPs. Depending on chain length and chlorine content, CPs are colorless or yellowish liquids or solids.
Menachem Elimelech is the Nancy and Clint Carlson Professor at Rice University, with joint appointments in the Department of Civil & Environmental Engineering and the Department of Chemical & Biomolecular Engineering. Prior to his appointment at Rice University, he was the Sterling Professor of Chemical and Environmental Engineering at Yale University. Elimelech moved from the University of California, Los Angeles (UCLA) to Yale University in 1998 and founded Yale's Environmental Engineering program.
Polymer stabilizers are chemical additives which may be added to polymeric materials to inhibit or retard their degradation. Mainly they protect plastic and rubber products against heat, oxidation, and UV light. The biggest quantity of stabilizers is used for polyvinyl chloride (PVC), as the production and processing of this type of plastic would not be possible without stabilizing chemicals. Common polymer degradation processes include oxidation, UV-damage, thermal degradation, ozonolysis, combinations thereof such as photo-oxidation, as well as reactions with catalyst residues, dyes, or impurities. All of these degrade the polymer at a chemical level, via chain scission, uncontrolled recombination and cross-linking, which adversely affects many key properties such as strength, malleability, appearance and colour.
An antiozonant, also known as anti-ozonant, is an organic compound that prevents or retards damage caused by ozone. The most important antiozonants are those which prevent degradation of elastomers like rubber. A number of research projects study the application of another type of antiozonants to protect plants as well as salmonids that are affected by the chemicals.
Microplastics are fragments of any type of plastic less than 5 mm (0.20 in) in length, according to the U.S. National Oceanic and Atmospheric Administration (NOAA) and the European Chemicals Agency. US EPA researchers define microplastics, or MPs, as plastic particles ranging in size from 5 millimeters (mm), which is about the size of a pencil eraser, to 1 nanometer (nm). For comparison, a strand of human hair is about 80,000 nanometers wide.
Ethylene diurea (EDU) is an organic compound with the formula (CH2NHCONH2)2. It is a white solid.
Pre-spawn mortality is a phenomenon where adult coho salmon, Oncorhynchus kisutch, die before spawning when returning to freshwater streams to spawn. It is also known as Urban Runoff Mortality Syndrome in more recent studies. This occurrence has been observed in much of the Puget Sound region of the Pacific Northwest. During fall migration, salmonids pass through urban watersheds which are contaminated with stormwater runoff. As the coho salmon pass through these waters, many will show symptoms of lethargy, loss of equilibrium and disorientation, and die within a few hours of showing these symptoms. These symptoms and behaviors are prevalent after rain events. Mortality often occurs before salmon have the opportunity to spawn, which is determined by cutting open female carcasses and observing for unfertilized eggs. Rates of pre-spawn mortality could impact the local salmon populations. Based on model projections, if rates continue, populations of coho salmon could become extinct within the next few decades.
Aminoxyl denotes a radical functional group with general structure R2N–O•. It is commonly known as a nitroxyl radical or a nitroxide, however IUPAC discourages the use of these terms, as they erroneously suggest the presence of a nitro group. Aminoxyls are structurally related to hydroxylamines and N-oxoammonium salts, with which they can interconvert via a series of redox steps.
N-Isopropyl-N′-phenyl-1,4-phenylenediamine (often abbreviated IPPD) is an organic compound commonly used as an antiozonant in rubbers. Like other p-phenylenediamine-based antiozonants it works by virtue of its low ionization energy, which allows it to react with ozone faster than ozone will react with rubber. This reaction converts it to the corresponding aminoxyl radical (R2N–O•), with the ozone being converted to a hydroperoxyl radical (HOO•), these species can then be scavenged by other antioxidant polymer stabilizers.
Rubber pollution, similar to plastic pollution, occurs in various environments, and originates from a variety of sources, ranging from the food industry processing chain to tire wear. Synthetic and natural rubber dust and fragments now occur in food, airborne as particulates in air pollution, hidden in the earth as soil pollution, and in waterways, lakes and the sea.
4-Aminodiphenylamine is a diphenylamine with an additional amine substituent. This dimer of aniline has various industrial uses, including as a hair dye ingredient, but also has raised concerns about toxicity by skin contact. It is also a starting material for the synthesis of 6PPD, an antiozonant for various rubber products. A colorimetric test for the quantitative analysis of nitrite, at levels below 100 nanograms per milliliter, is based on nitrite-catalyzed coupling of 4-aminodiphenylamine with N,N-dimethylaniline.
Hexa(methoxymethyl)melamine (HMMM) is a hemiaminal ether commonly used as a crosslinking agent in the production of coatings and rubber items. It is produced via the reaction of melamine with formaldehyde and excess methanol, with the later also acting as a solvent for the reaction. It can be considered as a monomeric intermediate in the formation of melamine resin.
The TOP Assay is a laboratory method developed in 2012 that oxidatively converts (unknown) precursor compounds of perfluorocarboxylic acids (PFCAs) into the latter. This makes quantification possible. Potassium peroxodisulfate is used. This sum parameter can be used to determine the concentration of precursor compounds present by comparing the sample before and after the application of the TOP Assay.
... existing TWP [tire wear particle] loading, leaching, and toxicity assessments are clearly incomplete. ... Accordingly, the human health effects of such exposures merit evaluation. ... It is unlikely that coho salmon are uniquely sensitive ... ( in print 8 Jan 2021)