p-Phenylenediamine (PPD) is a derivative of aniline used in kevlar, hair dye and henna substitutions among other things, the derivatives of which are used in antiozonants among other horrors

January 5, 2024
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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.

Production

PPD is produced via three routes. Most commonly, 4-nitrochlorobenzene is treated with ammonia and the resulting 4-nitroaniline is then hydrogenated:

In the DuPont route, aniline is converted to diphenyltriazine, which is then converted by acid-catalysis to 4-aminoazobenzene. Hydrogenation of the latter affords PPD.

4-Nitroaniline, p-nitroaniline or 1-amino-4-nitrobenzene is an organic compound with the formula C6H6N2O2. A yellow solid, it is one of three isomers of nitroaniline. It is an intermediate in the production of dyes, antioxidants, pharmaceuticals, gasoline, gum inhibitors, poultry medicines, and as a corrosion inhibitor. 4-Nitroaniline is produced industrially via the amination of 4-nitrochlorobenzene:

ClC6H4NO2 + 2 NH3 → H2NC6H4NO2 + NH4Cl

Below is a laboratory synthesis of 4-nitroaniline from aniline. The key step in this reaction sequence is an electrophilic aromatic substitution to install the nitro group para to the amino group. The amino group can be easily protonated and become a meta director. Therefore, a protection of the acetyl group is required. After this reaction, a separation must be performed to remove 2-nitroaniline, which is also formed in a small amount during the reaction.

Applications

4-Nitroaniline is mainly consumed industrially as a precursor to p-phenylenediamine, an important dye component. The reduction is effected using iron metal and by catalytic hydrogenation.

It is a starting material for the synthesis of Para Red, the first azo dye:

Synthesis of Para Red

Laboratory use

Nitroaniline undergoes diazotization, which allows access to 1,4-dinitrobenzene and nitrophenylarsonic acid. With phosgene, it converts to 4-nitrophenylisocyanate.

Carbon snake demonstration

When heated with sulfuric acid, it dehydrates and polymerizes explosively into a rigid foam.

Carbon snake local links

In Carbon snake demo, paranitroaniline can be used instead of sugar, if the experiment is allowed to proceed under an obligatory fumehood. With this method the reaction phase prior to the black snake’s appearance is longer, but once complete, the black snake itself rises from the container very rapidly. This reaction may cause an explosion if too much sulfuric acid is used.

Toxicity

The compound is toxic by way of inhalation, ingestion, and absorption, and should be handled with care. Its LD50 in rats is 750.0 mg/kg when administered orally. 4-Nitroaniline is particularly harmful to all aquatic organisms, and can cause long-term damage to the environment if released as a pollutant.

See also

Uses

Precursor to polymers

PPD is a precursor to aramid plastics and fibers such as Kevlar and Twaron. These applications exploit PPD’s difunctionality, i.e. the presence of two amines which allow the molecules to be strung together. This polymer arises from the reaction of PPD and terephthaloyl chloride. The reaction of PPD with phosgene gives the diisocyanate, a precursor to urethane polymers.

Molecular structure of Kevlar: the monomer subunit is bolded, dashed lines indicate hydrogen bonds.

Dyeing

This compound is a common hair dye. Its use is being supplanted by other aniline analogues and derivatives such as 2,5-diamino(hydroxyethylbenzene and 2,5-diaminotoluene). Other popular derivatives include tetraaminopyrimidine and indoanilines and indophenols. Derivatives of diaminopyrazole give both red and violet colours. In these applications, the nearly colourless dye precursor oxidizes to the dye.

  • Thomas Clausen et al. “Hair Preparations” in Ullmann’s Encyclopedia of Industrial Chemistry, 2007, Wiley-VCH, Weinheim. doi:10.1002/14356007.a12_571.pub2

Rubber antioxidant

A vehicle tire showing signs of ozone cracking

PPD is easily oxidized, and for this reason, derivatives of PPD are used as antiozonants in the production of rubber products (e.g., IPPD). The substituents (naphthyl, isopropyl, etc.) affect the effectiveness of their antioxidant roles as well as their properties as skin irritants.

  • Hans-Wilhelm Engels et al., “Rubber, 4. Chemicals and Additives” in Ullmann’s Encyclopedia of Industrial Chemistry, 2007, Wiley-VCH, Weinheim. doi:10.1002/14356007.a23_365.pub2

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.

Effect of ozone

Main article: Ozone cracking

Many elastomers are rich in unsaturated double bonds, which can react with ozone present in the air in process known as ozonolysis. This reaction breaks the polymer chains, degrading the mechanical properties of the material. The most obvious effect of this is cracking of the elastomer (ozone cracking), which is exacerbated by mechanical stress. The rate of degradation is effected both by the chemical structure of the elastomer and the amount of ozone in the environment. Elastomers which are rich in double bonds, such as natural rubber, polybutadiene, styrene-butadiene rubber and nitrile rubber are the most sensitive to degradation, whereas butyl rubber, polychloroprene, EPDM and Viton are more resistant. Ground-level ozone is naturally present, but it is also a product of smog and thus degradation is faster in areas of high air pollution. All of these factors make vehicle tires particularly vulnerable, as they contain a high level of unsaturated groups, operate in areas prone to air pollution and are subjected to significant mechanical stresses.

The distribution of atmospheric ozone

Protection of elastomers

Antiozonants are used as additives in tire manufacturing to retard the effects of ozone.

  • Hans-Wilhelm Engels et al., “Rubber, 4. Chemicals and Additives” in Ullmann’s Encyclopedia of Industrial Chemistry, 2007, Wiley-VCH, Weinheim. doi:10.1002/14356007.a23_365.pub2.

The most common antiozonants for elastomers are N,N′-substituted p-phenylenediamines (PPD) which can be categorized in three types:

Other classes include:

Protection of plants

For the protection of plants like winter wheat[citation needed] or maize.  

Ethylene diurea (EDU) has been used successfully as antiozonant.

Other uses

A substituted form of PPD sold under the name CD-4 is also used as a developing agent in the C-41 color photographic film development process, reacting with the silver grains in the film and creating the colored dyes that form the image.

  • The C-41 process is the same for all C-41 films, although different manufacturers’ processing chemistries vary slightly. After exposure, the film is developed in a “color developer”. The developing ingredient is a paraphenylene diamine-based chemical known as CD-4. The developer develops the silver in the emulsion layers. As the silver is developing, oxidized developer reacts with the dye couplers, resulting in formation of dyes. The control of temperature and agitation of the film in the developer is critical in obtaining consistent, accurate results. Incorrect temperature can result in severe color shifts or significant under- or overdevelopment of the film. After the developer, a bleach converts the metallic silver generated by development to silver halide, which is soluble in fixer. After the bleach, a fixer removes the silver halide. This is followed by a wash, and a final stabilizer and rinse to complete the process. There are simplified versions of the process that use a combined bleach-fix (EDTA) that dissolves the silver generated by development and removes undeveloped silver halide. These are not used by commercial C-41 processors, and are marketed for home or field use.
  • The fourth in the series of color developing agents used in developing color films, commonly known as CD-4, is chemically known as 4-(N-Ethyl-N-2-hydroxyethyl)-2-methylphenylenediamine sulfate. In color development, after reducing a silver atom in a silver halide crystal, the oxidized developing agent combines with a color coupler to form a color dye molecule.
  • See Also

PPD is also used as a Henna surrogate for temporary tattoos. Its usage can lead to severe contact dermatitis. Oh…they forget the side effect of death. The internet suggests young people, primarily girls, are committing suicide with this stuff. Not sure I believe the deaths are suicides.

“Suicide by self-poisoning is a common cause of death, especially in the younger population. More specifically, hair-dye poisoning is being increasingly used for suicide. Paraphenylenediamine (PPD), also known as “Kala pathar”, is a highly toxic ingredient present in hair-dye that can cause death.”

  • Omer Sultan M, Inam Khan M, Ali R, Farooque U, Hassan SA, Karimi S, Cheema O, Pillai B, Asghar F, Javed R. Paraphenylenediamine (Kala Pathar) Poisoning at the National Poison Control Center in Karachi: A Prospective Study. Cureus. 2020 May 29;12(5):e8352. doi: 10.7759/cureus.8352. PMID: 32617225; PMCID: PMC7325408.

There are three pages of results when I type the search criteria into PMC. These are from page 1.

Para-phenylenediamine (shown here) is chemically very different from the lawsone found in henna.
  • Black henna powder may be derived from indigo (from the plant Indigofera tinctoria). It may also contain unlisted dyes and chemicals such as para-phenylenediamine (PPD), which can stain skin black quickly, but can cause severe allergic reactions and permanent scarring if left on for more than 2–3 days. The FDA specifically forbids PPD to be used for this purpose, and may prosecute those who produce black henna. Artists who injure clients with black henna in the U.S. may be sued for damages.
  • The name arose from imports of plant-based hair dyes into the West in the late 19th century. Partly fermented, dried indigo was called black henna because it could be used in combination with henna to dye hair black. This gave rise to the belief that there was such a thing as black henna which could dye skin black. Indigo will not dye skin black. Pictures of indigenous people with black body art (either alkalized henna or from some other source) also fed the belief that there was such a thing as black henna.[citation needed]
  • In the 1990s, henna artists in Africa, India, Bali, the Arabian Peninsula and the West began to experiment with PPD-based black hair dye, applying it as a thick paste as they would apply henna, in an effort to find something that would quickly make jet-black temporary body art. PPD can cause severe allergic reactions, with blistering, intense itching, permanent scarring, and permanent chemical sensitivities. Estimates of allergic reactions range between 3% and 15%. Henna does not cause these injuries. Black henna made with PPD can cause lifelong sensitization to coal tar derivatives while black henna made with gasoline, kerosene, lighter fluid, paint thinner, and benzene has been linked to adult acute leukemia.
    • Van den Keybus, C.; Morren, M.-A.; Goossens, A. (September 2005). “Walking difficulties due to an allergic reaction to a temporary tattoo”. Contact Dermatitis. 53 (3): 180–181. doi:10.1111/j.0105-1873.2005.0407m.x. PMID 16128770. S2CID 28624688.
    • Stante, M; Giorgini, S; Lotti, T (April 2006). “Allergic contact dermatitis from henna temporary tattoo”. Journal of the European Academy of Dermatology and Venereology. 20 (4): 484–486. doi:10.1111/j.1468-3083.2006.01483.x. PMID 16643167. S2CID 43067542.
    • Jung, Peter; Sesztak-Greinecker, Gabriele; Wantke, Felix; Gotz, Manfred; Jarisch, Reinhart; Hemmer, Wolfgang (April 2006). “A painful experience: black henna tattoo causing severe, bullous contact dermatitis”. Contact Dermatitis. 54 (4): 219–220. doi:10.1111/j.0105-1873.2006.0775g.x. PMID 16650103. S2CID 43613761.
    • Hassan, Inaam Bashir; Islam, Sherief I. A. M.; Alizadeh, Hussain; Kristensen, Jorgen; Kambal, Amr; Sonday, Shanaaz; Bernseen, Roos M. D. (21 July 2009). “Acute leukemia among the adult population of United Arab Emirates: an epidemiological study”. Leukemia & Lymphoma. 50 (7): 1138–1147. doi:10.1080/10428190902919184. PMID 19557635. S2CID 205701235.
  • The most frequent serious health consequence of having a black henna temporary tattoo is sensitization to hair dye and related chemicals. If a person has had a black henna tattoo and later dyes their hair with chemical hair dye, the allergic reaction may be life-threatening and require hospitalization. Because of the epidemic of PPD allergic reactions, chemical hair dye products now post warnings on the labels: “Temporary black henna tattoos may increase your risk of allergy. Do not colour your hair if: … – you have experienced a reaction to a temporary black henna tattoo in the past.”
    • Sosted, Heidi; Johansen, Jeanne Duus; Andersen, Klaus Ejner; Menne, Torkil (February 2006). “Severe allergic hair dye reactions in 8 children”. Contact Dermatitis. 54 (2): 87–91. doi:10.1111/j.0105-1873.2006.00746.x. PMID 16487280. S2CID 39281376.
    • Commission Directive 2009/134/EC of 28 October 2009 amending Council Directive 76/768/EEC concerning cosmetic products for the purposes of adapting Annex III thereto to technical progress
  • PPD is illegal for use on skin in western countries, though enforcement is difficult. Physicians have urged governments to legislate against black henna because of the frequency and severity of injuries, especially to children. To assist the prosecution of vendors, government agencies encourage citizens to report injuries and illegal use of PPD black henna. When used in hair dye, the PPD amount must be below 6%, and application instructions warn that the dye must not touch the scalp and must be quickly rinsed away. Black henna pastes have PPD percentages from 10% to 80%, and are left on the skin for half an hour.
  • PPD black henna use is widespread, particularly in tourist areas. Because the blistering reaction appears 3 to 12 days after the application, most tourists have left and do not return to show how much damage the artist has done. This permits the artists to continue injuring others, unaware they are causing severe injuries. The high-profit margins of black henna and the demand for body art that emulates “tribal tattoos” further encourage artists to deny the dangers.
  • It is not difficult to recognize and avoid PPD black henna:
    • if a paste stains skin on the torso black in less than ½ hour, it has PPD in it.
    • if the paste is mixed with peroxide, or if peroxide is wiped over the design to bring out the color, it has PPD in it.
  • PPD sensitivity is lifelong. A person who has become sensitized through black henna tattoos may have future allergic reactions to perfumes, printer ink, chemical hair dyes, textile dye, photographic developer, sunscreen and some medications. A person who has had a black henna tattoo should consult their physician about the health consequences of PPD sensitization.

PPD is also used as a histological stain for lipids such as myelin.

PPD is used by lichenologists in the PD test to aid identification of Lichens. PPD is used extensively as a cross-linking agent in the formation of COFs (covalent organic frameworks), which have a number of applications in dyes and aromatic compounds adsorption.

P test

This is also known as the PD test. It uses a 1–5% ethanolic solution of para-phenylenediamine (PD), made by placing a drop of ethanol (70–95%) over a few crystals of the chemical; this yields an unstable, light sensitive solution that lasts for about a day. An alternative form of this solution, called Steiner’s solution, is much longer lasting although it produces less intense colour reactions. It is typically prepared by dissolving 1 gram of PD, 10 grams of sodium sulfite, and 0.5 millilitres of detergent in 100 millilitres of water; initially pink in colour, the solution becomes purple with age. Steiner’s solution will last for months. The phenylenediamine reacts with aldehydes to yield Schiff bases according to the following reaction:[8]R−CHO + H2N−C6H4−NH2 → R−CH=N−C6H4−NH2 + H2O Products of this reaction are yellow to red in colour. Most β-orcinol depsidones and some β-orcinol depsides will react positively. PD is poisonous both as a powder and a solution, and surfaces that come in contact with it (including skin) will discolour.

Safety

The aquatic LD50 of PPD is 0.028 mg/L. The U.S. Environmental Protection Agency reported that in rats and mice chronically exposed to PPD in their diet, it simply depressed body weights, and no other clinical signs of toxicity were observed in several studies. One review of 31 English-language articles published between January 1992 and February 2005 that investigated the association between personal hair dye use and cancer as identified through the PubMed search engine found “at least one well-designed study with detailed exposure assessment” that observed associations between personal hair dye use and non-Hodgkin’s lymphoma, multiple myeloma, acute leukemia, and bladder cancer, but those associations were not consistently observed across studies. A formal meta-analysis was not possible due to the heterogeneity of the exposure assessment across the studies.

Patch test

In 2005–06, it was the tenth-most-prevalent allergen in patch tests (5.0%).

The CDC lists PPD as being a contact allergen. Exposure routes are through inhalation, skin absorption, ingestion, and skin and/or eye contact. Symptoms of exposure to PPD include throat irritation (pharynx and larynx), bronchial asthma, and sensitization dermatitis. Sensitization is a lifelong issue, which may lead to active sensitization to products, including but not limited to black clothing, various inks, hair dye, dyed fur, dyed leather, and certain photographic products. It was voted Allergen of the Year in 2006 by the American Contact Dermatitis Society.

Poisoning by PPD is rare in Western countries.In contrast, poisoning by PPD has occurred in Eastern countries, such as Pakistan, where people have committed suicide by consuming it.

See also

References

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