The whole truth about phenol and formaldehyde

2024 Author: Seth Attwood | [email protected]. Last modified: 2023-12-16 15:55

The material was created with the aim of eliminating (in a nutshell, you cannot eliminate it, but I would like it) to reduce hygienic illiteracy. There are a couple of substances that accompany modern man, with the persistence of a shadow. These are phenol and formaldehyde.

I wouldn't have bothered writing a note if I hadn't caught my eye:

1. several articles that tell how these compounds are useful in economic activities (but who can argue) and are not at all harmful to humans (TBM, TBM, TBM …). Some authors even argued that the maximum permissible concentration of these substances was taken from the ceiling and one should not be afraid of exceeding the maximum permissible concentration;
2. TV shows about construction and repair in which chipboard and OSB are actively and incorrectly used in decoration;
3. other massive examples of brain dusting about the use of potential sources without taking into account hygiene requirements (furniture, construction and finishing materials)

In general, the soul of a sanitary doctor could not stand such obscurantism and I decided to convey to the community information that, of course, will not save from death (fans of the sarcastic "we will all die !!!" at a later time.

At first I wanted to find a reasonable article, but … from reasonable materials, only educational literature on hygiene, which in general, too much, and supporting information, I often found from manufacturers of various materials. Agree that when a technologist of some linoleum production, taken by the gills, recognizes how the company saves - this is much more convex than a textbook on communal hygiene.

But there are also opposite examples, when manufacturers follow the path of improving quality and safety, and they also contributed to the formation of my view of the problem.

First, a brief description of these substances, taken mainly from Wikipedia, since considered it inappropriate to fill a note with a lot of information from scientific publications.

PHENOL

Application

According to the data for 2006, the world consumption of phenol has the following structure:

44% of phenol is used for the production of bisphenol A, which, in turn, is used for the production of polycarbonates and epoxy resins;

30% of phenol is used for the production of phenol-formaldehyde resins;

12% of phenol is converted by hydrogenation into cyclohexanol, which is used to obtain artificial fibers - nylon and nylon;

In Russia, a large amount of phenol is used in oil refining, in particular for the selective purification of oils in technological units of the 37/1 and A-37/1 types. Phenol exhibits high selectivity and efficiency in the removal of resinous substances, various polycyclic aromatic hydrocarbons with short side chains, as well as compounds containing sulfur from oils [4];

the rest of the phenol is spent on other needs, including the production of antioxidants (ionol), nonionic surfactants - polyoxyethylated alkyl phenols (neonols), other phenols (cresols), drugs (aspirin), antiseptics (xeroform) and pesticides. A solution of 1, 4% phenol is used in medicine (orasept) as an anesthetic and antiseptic.

Phenol and its derivatives are responsible for the preserving properties of smoke smoke. Phenol is also used as a preservative in vaccines. An example of use as an antiseptic is the drug "Orasept" and "Fukortsin". In cosmetology as a chemical peel (toxic).

in cattle breeding: disinfection of animals with solutions of phenol and its derivatives.

in cosmetology for deep peeling.

Toxic properties

Phenol is poisonous … Refers to highly hazardous substances (Hazard class II). Inhalation causes dysfunction of the nervous system … Dust, vapors and phenol solution irritate the mucous membranes of the eyes, respiratory tract, skin, causing chemical burns. There is no evidence that phenol is carcinogenic in humans.

Maximum permissible concentration (MPC) of phenol:

MPCr.z. = 1 mg / m³

MPCr.s = 0.3 mg / m³

MPCm.r. = 0.01 mg / m³

MPCs. = 0, 003 mg / m³

MPCv. = 0, 001 mg / l.

Getting on the skin, phenol is very quickly absorbed even through intact areas and after a few minutes begins to affect the brain tissue. First, there is a short-term excitement, and then paralysis of the respiratory center. Even when exposed to minimal doses of phenol, sneezing, coughing, headache, dizziness, pallor, nausea, and loss of strength are observed. Severe cases of poisoning are characterized by unconsciousness, cyanosis, difficulty breathing, numbness of the cornea, rapid, barely perceptible pulse, cold sweat, and often convulsions. The lethal dose for humans when ingested is 1-10 g, for children 0.05-0.5 g.

Chronic poisoning

In chronic poisoning - weakness, sweating, irritability, fatigue, poor sleep, headaches, dizziness, dyspeptic symptoms, functional disorders of the central nervous system, secretory-motor activity of the stomach, initial symptoms of chronic toxic hepatitis. Dry skin, itchy skin, dermatitis.

Carcinogenicity

Carcinogens are “incorporated” into the structure of DNA or cause breaks in its strands, thereby leading to changes in its coding properties. These defects in DNA structure are partially eliminated by the cell's repair systems. The end effect is the formation of a tumor- thus depends on many interrelated factors, unequally studied and insufficiently controlled, which greatly complicates the task of managing this process.

The plurality of stages of carcinogenesis makes it possible to intervene in it in different ways and with different results. In particular, the suppression of the function of the cell's regenerative systems undoubtedly makes the work of carcinogens more efficient. Therefore, substances that do not have their own carcinogenic activity can enhance the effect of other carcinogens, acting as "assistants", "assistants". This action is called co-carcinogenic. A co-carcinogenic effect is also achieved if the “assistant” substance facilitates the penetration of the carcinogen into the tissues, promotes its transformation into the final carcinogen and binding to DNA, or “pushes” the cell already transformed by the carcinogen to multiply.

And here a wide field of activity opens up for other, non-carcinogenic compounds, including phenolic ones. One of the most convenient and visual models for studying the co-carcinogenic effect of a wide variety of substances, including phenols, is the model for obtaining skin cancers. One of the carcinogens (benzo (a) pyrene, methylcholanthrene, or another classical compound) is applied to the intact skin of mice or rats, previously deprived of hair, at a dose that is insufficient to cause cancer, but causes the transformation of some of the skin cells. Tumors in such animals practically do not occur. But if, after some time, the same area of the skin is influenced (once or repeatedly) with other substances, then under the influence of some of them, tumors develop. These substances themselves do not have their own carcinogenic effect, but in combination with a true carcinogen, they enhance and manifest its effect. Such substances are referred to as co-carcinogens.

FORMALDEHYDE

Application

An aqueous solution of formaldehyde (methanediol) stabilized with methanol - formalin - causes denaturation of proteins, therefore it is used as a tanning agent in tanning and gelatin tanning in film production. Due to the strong tanning effect, formaldehyde is also a strong antiseptic, this property of formalin is used in medicine (formidron, Formagel and similar drugs) and for the preservation of biological materials (the creation of anatomical and other drugs).

Formaldehyde is used as a fumigation agent, in particular during storage and transportation of grain.

An aqueous solution of formaldehyde (methanediol) stabilized with urea - UFC - is one of the most important sources of formaldehyde and urea in the production of urea formaldehyde, melamine urea formaldehyde resins and for the treatment of urea against caking; used in the woodworking and furniture industries for the production of plywood, chipboard, etc.

The main part of formaldehyde is used for the manufacture of thermosetting polymers (phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins); it is also widely used in industrial organic synthesis (pentaerythritol, trimethylolpropane, etc.).

During storage (at temperatures below 9 ° C), the formaldehyde solution becomes cloudy, a white precipitate (paraformaldehyde) precipitates.

Registered in the food industry under the code E240.

The use of formaldehyde in cosmetics

Directive 76/768 EEC allows the use of formaldehyde as a preservative in an amount of up to 0.1% in cosmetics intended for oral hygiene, and up to 0.2% in other cosmetic preparations.

In pharmacology, preparations containing up to 0.5% formaldehyde are used to reduce sweating without any restrictions, and only when using an ointment containing 5% of this substance, it is recommended not to apply it to the skin of the face. It is forbidden to use for the preservation of products in aerosols, sprays. Products must have a warning “contains formaldehyde” if the formaldehyde content in finished products exceeds 0.05%. In terms of the spectrum of antimicrobial activity, formaldehyde is active against gram-positive, gram-negative bacteria, yeast-like and mold fungi. At the same time, formaldehyde and parabens reduce antimicrobial properties in the presence of proteins. Along with this, an improvement in the physical and mechanical properties of the hair after its treatment with formalin was established. Keratin can interact with formaldehyde in different ways. Formaldehyde can react with - S - H groups, forming bonds - S - CH2 - S - C - NH2 with side chain groups, etc. arginine groups.

There is practically no information in the literature on the effect of dilute formaldehyde solutions on human skin. It is known that if a rabbit's ear is kept in formalin (37% formaldehyde solution) for 30 minutes, then it will turn red and peel off, and then fully recover (regenerate).

Since formaldehyde in developed countries is used exclusively in the composition of cosmetic preparations that do not remain on the skin, the likelihood of a skin reaction was calculated for cases of using a shampoo containing 0.1% formaldehyde as a preservative. The calculation showed that an undesirable skin reaction when using this shampoo will occur only in 1 person out of 75,000 … First, the calculation was based on baseline data on formaldehyde content directly on human skin. When washing hair, only a small part of the formaldehyde in the shampoo is in direct contact with the skin. Secondly, due to the low stability of formaldehyde in aqueous solutions (evaporation), its concentration decreases over time.

Safety and toxic properties

Explosion category IIB according to GOST R 51330.11-99, explosion group T2 according to GOST R 51330.5-99. Concentration limits of ignition 7-73% vol.; Hazard class II (highly hazardous); auto-ignition temperature - 435 ° C.

Formaldehyde is formed in the body through the oxidation of methanol.

Possesses toxicity, negatively affects genetic material, reproductive organs, respiratory tract, eyes, skin. It has a strong effect on the central nervous system.

Maximum permissible concentration (MPC) of formaldehyde:

MPCr.z. = 0.5 mg / m³

MPCm.r. = 0.05 mg / m³

MPCs. = 0.01 mg / m³

MPCv. = 0.05 mg / l

On May 25, 2014, the Resolution of the Chief State Sanitary Doctor of the Russian Federation came into force, according to which the following values of MPCm.r. were established. = 0.05 mg / m³, MPCs.with. = 0.01 mg / m³^[8]

The lethal dose of a 40% aqueous solution of formaldehyde (formalin) is 10-50 g.

Effects on the body and symptoms of chronic poisoning

Formaldehyde is toxic: ingestion of 60-90 ml is fatal. Symptoms of poisoning: pallor, loss of strength, unconsciousness, depression, shortness of breath, headache, often convulsions.

In acute inhalation poisoning: conjunctivitis, acute bronchitis, up to pulmonary edema. Gradually, signs of damage to the central nervous system (dizziness, fear, unsteady gait, convulsions) increase. In case of poisoning through the mouth: burns of the mucous membranes of the digestive tract (burning, pain in the pharynx, along the esophagus, in the stomach, vomiting of bloody masses, diarrhea), hemorrhagic nephritis, anuria. Edema of the larynx, reflex cessation of breathing are possible.

Chronic poisoning in those working with technical formalin is manifested by weight loss, dyspeptic symptoms, damage to the central nervous system (mental agitation, trembling, ataxia, visual disturbances, persistent headaches, poor sleep). Organic diseases of the nervous system (thalamic syndrome), sweating disorders, and temperature asymmetry are described. Cases of bronchial asthma have been reported.

Under conditions of exposure to formalin vapors (for example, among workers engaged in the manufacture of artificial resins), as well as in direct contact with formalin or its solutions, pronounced dermatitis of the face, forearms and hands, nail damage (fragility, softening). Dermatitis and eczema of an allergic nature are possible. After the postponed poisoning, the sensitivity to formalin increases. There is evidence of an adverse effect on the specific functions of the female body.

Carcinogenicity

Formaldehyde is included in the list of carcinogenic substances GN 1.1.725-98 in the section “probably carcinogenic to humans”, while its carcinogenicity to animals has been proven.

(here Wikipedia is outdated - GN is no longer valid, but formaldehyde is in SanPiN 1.2.2353-08 Carcinogenic factors and basic requirements for the prevention of carcinogenic hazards)

I noticed that most people think the main sources of phenol and formaldehyde are finishing materials, but in the first (by deceit) place - furniture! And not just furniture. And having all the necessary certificates. One firm is especially vividly remembered, the main feature of which was the use of everything "environmentally friendly", "green", well, etc. So, in the office they had such a smell, of the aforementioned couple, that the question arose in full measure, how to sniff out “environmental friendliness” to customers in such a chemical stench. The measurements showed an excess (I do not remember how many, but many, many) times. Additional conditions of the problem - all furniture and all finishing materials have passports and are "environmentally friendly" to nimagu on paper; the ventilation system is REALLY maintained and cleaned; the premise itself is a large hall with office enclosures, an aquarium - a meeting room in the center and two isolated rooms - a bathroom and a director's office. So, all the furniture is tested and has certificates, but only tests are carried out in a climatic chamber.

Climate chamber … on your fingers

GOST 30255-95 Furniture, wood and polymer materials. Method for determining the release of formaldehyde and other harmful volatile chemicals in climatic chambers

From there:

4.1 To test furniture products, samples are taken in an amount that creates a given saturation of the chamber volume:

- for cabinet furniture, tables, beds - 1 m of the sample surface area per 1 m of the volume of the climatic chamber;

- for furniture items for sitting and lying - 0.3 m of the sample surface area per 1 m of the volume of the climatic chamber.

The surface area of the samples is calculated with an error of ± 3%. It includes the total area on 2 sides of all furniture parts (surfaces of the rear walls, the bottom of drawers, shelves, surfaces behind mirrors, plugs in furniture for sitting and lying, etc.).

3.1.3 In the working volume of the chamber during the tests, the following parameters must be maintained:

air temperature - (23 ± 2) ° С;

relative air humidity - (45 ± 5)%;

air exchange per hour - 1 ± 0, 1.

Testing of parquet products is carried out with air exchange (0.5 ± 0.05) per hour.

6.7 The evaluation of the test results is carried out by comparing them with the maximum permissible concentrations of harmful substances in the atmospheric air, approved in the prescribed manner by the bodies of the State Sanitary and Epidemiological Surveillance.

So, let's take, for example, a room, and in it there is a wardrobe, a bed, a table, and a chair.

cabinet width - 1.2m, height -2.4m, depth -0.6m with 2 shelves. Its surface area is 21.6m²… Because a cabinet made of chipboard and plywood, but with coatings and claddings, then suppose that he gave in the chamber, for simplicity and clarity, the result of 1 MPC. Thus, for the concentration in the room with this cabinet to be 1 MPC, the required volume of the room should be 21.6 m³… With a ceiling height of 2.5m (frequent standard), 8.64m will be required² area of the room.

Desk (writing - laminated chipboard is the simplest) - 8, 54m³ and 3, 4m² respectively.

A wooden bed with a mattress will require - 29.3 m³ and 11, 7m².

Chair 2, 5 m³ and 1m².

Total: 24.3 m² must be in the room so that it does not exceed the MPC with a single air exchange. And yet, there is nothing in the room, no finishing materials, no sources of phenol and formaldehyde - bare concrete on the walls, floor and ceiling (although in some cases, they are also sources).

It's hard to find a room at 24.3 m², so other ways are needed.

improving the quality of furniture (under capitalism, this is not the # 1 path, but the last one, since it leads to costs)

an increase in the frequency of air exchange (natural ventilation can only give a 4-fold air exchange - then the microclimate parameters are violated).

Air filtration (well, this is absolutely fantastic)

Now answer yourself - what method is used in your home?

Although the furniture is not all that bad. There are manufacturers who are trying to make a quality product, but … As soon as capitalism once again tightens the stranglehold - the quality decreases.

Let's move on to building materials. Actually, it was some kind of repair and mowing gear that made me take up the keyboard, they showed me how to stuff more OSB and chipboard into a living room.

Chipboard must comply with the same GOST, but … Do you know why chipboard is pasted over with foil? And one of my acquaintances now knows for sure. And after all, which is typical, I explained to him why and explained the importance of ventilation, but ventilation by 50tyr increases the cost of construction, and chipboard is cheaper than other materials on the floor. So, he is a film, which, as they said in TV publisher glued so as not to stain chipboard before painting, tore it off in a room without ventilation, etc. lost consciousness, how bad he was then he painted. So, he vomited, oklemalsya and finished the floors. But even such a vivid experience did not make him reconsider his views on "convenient and cheap" building materials and lack of ventilation.

Well, chipboard needs to be insulated, but where is it written about (except for special literature), and on telebrainer do not tell. But the true masterpiece is GOST on OSB: GOST 32567-2013 "Wood boards with oriented shavings. Specifications"

Actually, everything becomes clear from the information of this standard:

"1 DEVELOPED by the Autonomous Non-Commercial Organization Center for Certification of Forest Products" LESSERTIKA "(ANO TsSL" LESSERTIKA "), Closed Joint Stock Company" Consulting Firm "Design, Investments, Consulting" (CJSC "Consulting Firm" PIK "), Limited Liability Company" Kronospan "(LLC" Kronospan "), Limited Liability Company" Kronostar "(LLC" Kronostar "), Limited Liability Company" ORIS "(LLC" ORIS ") and Limited Liability Company" DOK "Kalevala" (LLC "DOK" Kalevala ")"

Those. The standard was developed by OSB manufacturers. And everything would be nothing if it were not for:

6.2 The content of chemicals in the boards except formaldehyde (see 5.12) should not exceed the maximum permissible standards for their release into the air for this product, established by the regulatory documents of the national sanitary and epidemiological surveillance authorities

5.12 The maximum permissible norms for the content of formaldehyde in the plate, the release of formaldehyde from the plate into the air, for plates of formaldehyde emission classes E0.5, E1 and E2 should not exceed the values indicated in Table 8. Plates made without formaldehyde-containing materials are classified as class E0.5 without testing. To determine the formaldehyde emission class, the manufacturer uses one of the methods.

Again the climatic chamber. Now let's estimate what area a room with OSB should have - walls with an emission class E0, 5 in order for the air in the room to meet the requirements.

Let's look at the standard in GN 2.1.6.3492-17 "Maximum permissible concentrations (MPC) of pollutants in the atmospheric air of urban and rural settlements"

It is worth noting here what the maximum one-time (maximum one-time) and average daily MPC are.

Maximum one-time MPC - MPC, which is established to prevent reflex reactions in humans (smelling, changes in the bioelectric activity of the brain, light sensitivity of the eyes, etc.) under short-term exposure to atmospheric pollution (up to 20 minutes).

Average daily MPC - MPC, which is established in order to prevent the general toxic, carcinogenic and mutagenic effect of a substance on the human body.

Thus, the GOST has already provided for the possibility of exceeding the MPC by 8 times for OSB with emission class E0.5.

It is not difficult to guess that all MPCs will be exceeded, which directly indicates that the contact of the OSB with the living environment is unacceptable.

For those who doubt and believe that once the limiting sign of harm is reflex-resorptive, i.e. The worst thing is that maybe it is a person who is calming down, and that's all. For them, I will add that in SanPiN 1.2.2353-08 Carcinogenic factors and basic requirements for the prevention of carcinogenic hazards, the following are separately highlighted:

Hygienic standards for the air of residential and non-industrial premises

2.1.1.74. Formaldehyde - 0.01 mg / m³»

And even in the GOST on OSB, the use and need for material isolation are not stipulated in any way.

Let's estimate what the area of a room with 2.5 m ceilings should be, upholstered from the inside with an OSB made according to GOST and even emitting Formaldehyde - 0.01 mg / m³, i.e. 1 MPC (which I can't believe). Here the limit of my mathematical knowledge happened, but provided that the room is square, here is the formula: 2.5x²= 2 (2.5x + 2.5x + x²) maybe I'm mistaken, the room should be as much as 400m².

Such wild numbers indicate that the OSB must be isolated from the air of the living quarters. Lamination and painting do a good job of this.

Actually, for these purposes, chipboard furniture is laminated. And the integrity of these coatings will be the most important safety criterion for both furniture and other materials made using phenol-formaldehyde and urea-formaldehyde resins.

It should be noted that insulating paints such as oil paints, after drying, get rid of unpolymerized residues and are a safe coating. But again, oil paints are safe only when applied in a not too thick layer, otherwise unreacted residues of any chemistry will be released into the room air for a long time.

Well, for sweetness, for those who like to argue that mineral wool is an "ecological" product

Mineral wool manufacturing steps

Melting of raw materials (dolomite, basalt, diabase, slags from other industries). The pre-prepared mixture is loaded into special ovens, vats or cupolas. The working temperature reaches 1400-1500 degrees.

Fibering. The finished melt moves into the centrifuge, where the rollers rotating at a speed of 7000 rpm turn the composition into many separate and independent fibers.

Treatment of fibers with anti-caking and synthetic-based binder components, for which various resins are most often used (phenol-formaldehyde and cyan-formaldehyde). Due to the powerful flow of air, the fibers move into the cooling chamber, forming something resembling a carpet;

Special equipment gives the cloth the required volume and length, after which the carpet enters the heat chamber. Under the influence of high temperature, the composition polymerizes and acquires its final volume.

Then the mineral wool is cut into blocks and packed.

P. S. We live in the environment that is, we use the materials that are available. So let's use materials according to their properties, not fairy tales. greedy managers, do not give up modern materials, but take into account their danger.

PS.2 As you know, most intestinal poisoning begins with the words: "Why will he have something in the refrigerator" (This is the second extreme - ignoring reality).