BE497634A - - Google Patents

Description

       

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  FLAME RESISTANT COMPOSITIONS.



   The invention relates to improving the fire and heat resistance of materials, and especially relates to nitrogen-containing compositions having flame retardant and potentially heat insulating properties. The invention also relates to methods for employing said compositions and for treating materials to make them resistant to fire and heat.



   The invention also relates to the products obtained by means of such a treatment.



   The already known anti-retardant compositions can be divided into two classes, of which: one comprises compositions in which at least one of the components indispensable for providing the flame-retardant properties is soluble in water, while the second class consists of the water-insoluble compositions. The first class comprises compositions based on alkali metal silicates and also compositions containing certain inorganic flame-retardant substances soluble in water;

  , such as acids and inorganic salts, particularly phosphates, sulfates, sulfamtes, borates, halides etc. alkali metals and ammonium
The second class consists of compositions containing inorganic flame retardant compounds insoluble in water such as antimony oxide and heavy metal stannates. as well as compositions containing organic materials, such as chlorinated rubber, chlorinated paraffins and other chlorinated organic materials.



   Known effective flame retardant compositions contain inorganic flame retardant compounds which in some cases can be mixed with other materials, but which do not undergo any chemical change whereby the disadvantages inherent in physical and chemical characteristics are reduced or eliminated. poe. acidity, alkalinity or tendency to crystallize o Phosphoric acids and their salts have excellent flame retardant properties, but they do not dry out satisfactorily, or the compositions of which they are a part - are fragile and produce a surface covered with crystals.

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     The object of the invention is to impart flame retardant properties to wood or other combustible materials by coating or impregnating them with improved chemical compositions, which compositions will be referred to below as foam-forming compositions and which; when exposed to heat, are converted into a swollen carbon layer which acts as an insulating agent against heat, which prevents the admission of air and which itself is substantially non-combustible.



   Another object of the invention is to provide compositions comprising flame-retardant inorganic acids in combined form, in which they no longer possess their inherent disadvantageous properties.
Another object of the invention is to provide improved flame retardant resin compositions which do not possess any of the disadvantageous physical and chemical characteristics inherent in inorganic flame retardant compounds. but which at the same time have flame retardant and potentially heat insulating properties.



   Another object of the invention is to provide improved methods of treating materials to give them the properties of fire or heat resistance.



   Another object of the invention is the manufacture of coated or impregnated products having improved resistance to fire and heat:
The invention relates to a flame retardant composition comprising a salt of a basic anion exchange resin containing nitrogen and an inorganic, non-oxidizing acid. Salts of anion exchange resins will be referred to below as "resin salts".

   Resin salts are much less combustible than basic resins and urea itself, and they are capable of forming at high temperatures, such as, for example, wood, wallboard and wallboard temperature. other similar hot materials, a carbonaceous mass which reduces the combustibility of the object and which functions as an insulating agent against heat.



   By "non-oxidizing acids" is meant according to the invention phosphoric acids, sulfuric acid, sulfaminic acid, boric acid, hydrohalogenic acids and the like. Said designation excludes acids such as nitric acid, chloric acid and perchloric acid, which themselves are strong oxidants, and which therefore increase rather than reduce the combustibility of the basic resin.



   In order to form resin salts which are stable with respect to lye, preferably strong non-oxidizing inorganic acids having a dissociation constant of 10-3 or more are used according to the invention. In the present description, the term "acid" also includes acid salts. It has been found that bivalent acids form more stable resin salts than monovalent acids and that trivalent and tetravalent acids form salts. resin with a stability which is even greater than that of bivalent acids.

   While hydrochloric acid, as well as hydrobromic acid, by way of example, together with the basic resin, form resin salts of reduced flammability, which constitute more or less effective flame retardants, and that the Sulfuric acid forms somewhat better resin salts in this respect, it has been found that phosphoric acids together with basic resins provide much higher resin salts. Said salts are non-flammable at flame temperatures of about 705 ° C or less and have excellent flame retardant and potentially heat insulating properties. When exposed to flame temperatures they produce a carbonaceous mass which is resistant to combustion.

   These salts are extremely stable. In some cases they are not only resistant to leaching by water and mono- or bivalent acids, but they are also resistant to alkaline solutions and organic solvents.



   The effectiveness of the product increases as the amount of acid added per gram of basic resin is increased. It has thus been found that in general at least one milliequivalent, and preferably two milliequivalents of acid on one gram of basic resin will provide a product.

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 Consequently, despite the fact that the reaction products of basic resins with strong non-oxidizing inorganic acids.

   generally have reduced flammability and are effective flame retardants for certain purposes, I prefer, according to the invention, those
 EMI3.1
 reaction products of basic nitrogen-containing resins "with phosphoric acids, which contain at least two millieqpilralents phosphoric acid per gram of basic resin. In most cases, the resins
 EMI3.2
 Basics do not combine with more than 15 milliequivalents of phosphoric acid on one gram of basic resin.



   It has been found that combustible materials, * such as propellants
 EMI3.3
 products known as "wall b08l" dll and "fiber board" and cardboard, wood, including triplex, fabrics, paper etc. can be made less flammable, or completely flame retardant by coating them and / or impregnating them with the resin salt. The treatment can be carried out, for example, by first dispersing the insoluble, heat-cured and finely divided resin salt in a liquid carrier containing a film-forming binder .,
 EMI3.4
 po-eo a drying oil, an a2kyd'e resin. or another resin forming a film., a cellulose derivative, such as for example ce.3.ase-ethyl, celklox 3'r glgétai - .. de:

  -z, cescpPa pfis.tlar combustible by means of a brush, by atomization, or by other means suitable for the purpose, and drying the material treated so until it is * to- ± 6rmé a solid flame retardant film. The combustible material can be treated temporarily by applying the resin salts in an earlier period of condensation. One can e.g.

   cause the resin components to react in water in the presence of the strong non-oxidizing inorganic acid and treat the combustible material with the aqueous solution or the dispersion of the resin salt to such a degree of polymerization as the resin salt is still capable of forming a colloidal solution or dispersion and having excellent bonding and film-forming properties, and then heat-hardening the material treated thereby. By this treatment a protective film is generally formed on combustible materials. strong and flame retardant.

   In the case of fabrics, paper, wood or other porous combustible materials, the aqueous solution or the dispersion of the resin salt can also be employed as a
 EMI3.5
 impregnating liquid When used in this way, the fire retardant resin salt is deposited in and on the porous combustible material, which is impregnated therewith.



   The resin salt in a weak polymerization state can also be employed as a flame retardant adhesive for bonding to a surface of paper, foil sheets, or other laminate materials. In this case the paper, or the like, and, if desired, also the surface to which the materials are to be glued, are treated with the aqueous dispersion of the resin salt, as described above. : the two surfaces are pressed against each other and the film between the surfaces. is hardened, e.g. by heating. If the aqueous resin salt dispersion is so employed, its binding properties can be further improved by adding to the dispersion a known binder, eg wheat starch paste.

   It has also been found that incombustible materials, particularly metals, can be advantageously coated with resin salts by the same application methods.



  In this case, the potentially insulating properties of the coating are used to protect the metal against damage caused by: heat or to reduce the transmission of heat through said metal, when the latter is exposed to temperatures of flame.



   It should be further noted that the term "acid adsorbent" is pins. or less disappointing, because basic resins not only adsorb acids but apparently react chemically with said acids. In fact, the mechanism of acid adsorption is probably mainly that of a chemical reaction with some characteristics of adsorption. Therefore, when the term "acid adsorbent" is used in the present description, it is understood that said term also includes a chemical reaction. Further, in the description and in the claims
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 the terms "acid adsorbent resin" and anion exchange resin are both used.

   It is therefore understood that the class of resins thus designated comprises basic resins capable of forming resin salts of which

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 the acid can no longer be completely removed by treatment with an alkaline substance or other acid.



   It is known that recently a large number of resinous synthetic anion exchange substances which are mainly used have been manufactured.
 EMI4.1
 ment for water purification. The preparation and use of di-iss resins in the field of water purification and in fields of a similar nature have been described in detail in the US patents:

   
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 n 2.I5I.883e n 2.198.874 n bzz n 2.251.234 n 20259ai69, 'n 2.290.345 n .34I9a n 2.354.671 n 23560151 and n 2.362.086
Acid adsorbent resins are obtained, generally by condensing basic organic nitrogen-containing compounds, such as amino acids.
 EMI4.3
 nes9 or gamiain and other similar substances with aldehydes, hydroxylated aldehydes (s = res., starch etc.) or alternatively with mixtures of aldehydes and ketones, under conditions such as in the formation of the resinous structure not all basic groups combine with aldehyde groups ie od. that only resins containing free basic groups show anion exchange properties.



  Typical diacid adsorbent or anion exchange resins suitable to be employed for the formation with strong inorganic acids of flame retardant or potentially insulating compositions are the following classes: Resins formed by condensing: 1) aromatic amines or compounds. aromatic polyamines substituted in the meta position with aldehydes and / or carbohydrates with or without ketones;
 EMI4.4
 2) aliphatic polyalkylenic polyamines with aldehydes and ketones;

   3) aliphatic polyalkylenic polyamines with phenols and aldehydes; 4) A strongly basic derivative of cyanamide with a weakly basic derivative of cyanamide and with an aldehyde, as described in more detail below.



   You can also add a carbohydrate.



   According to the invention there are employed as aldehydes aliphatic aldehydes, especially formaldehyde or a formaldehyde-producing substance such as para-formaldehyde and trioxymethylene, acetaldehyde.
 EMI4.5
 or cyclic aldehydes, such as furfdrah. The term "aldehyde" as used in the present specification and in the claims does not include hydroxylated aldehydes. or their polymers? especially carbohydrates (sugar, starch etc.) which will be mentioned specifically where they can be used.

   This distinc- tion is made, because sugars which may or may not contain aldehyde groups., Are not necessarily equivalent to al- dehydes in the formation of fire-retardant resin saltso
Many effective ion exchange resin or resin mixtures can be obtained by varying the above-mentioned components, or by condensing them together with other forming ingredients.
 EMI4.6
 resin; by way of example, anion exchangers can be produced in which the strongly basic quaternary ammonium hydroxides are employed instead of, or added to, an organic amine, eg. e. at the .. gn ani rli 11th;

   or hydroxylated aldehydes and hydroxylated ketones, especially carbohydrates (sugar, starch etc.) may be used in combination with, or instead of, aldehydes in classes 2) and 3); or amines are reacted with a derivative of a polyvalent organic acid and with a
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 aldehyde (e.g. an amide of an aminoalkylmalonic acid.

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  ROOC- CH2- CONH (CH) n NH2, obtained by --reaction of an aliphatic polyamine with a malonic ester, can be condensed with formaldehyde. It is obvious to those skilled in the art that all of these variations and still other variations can be made while remaining within the scope of the invention.



   Preferably the resins are combined with as much acid as possible o In general resins of the types described above will combine with between one and about fifteen milliequivalents of acid on one gram of resin o In some cases it is possible to use a much larger amount of acid, eg 25 milliequivalents or more, on one gram of resin.



   Anion exchange resins and acid adsorbing resins are generally suitable for the preparation of flame retardant resin salts, but resins of Class 4) form more stable resin salts which are generally better flame retardants. In this preferred class of resins it is necessary to employ an aldehyde as one of the resin forming agents. While it is possible to employ a carbohydrate in combination with the aldehyde, it is not possible to employ a carbon hydrate in combination with the aldehyde. 'use in the process according to the invention a carbohydrate instead of the aldehydes because the mixture thus formed, since it does not contain aldehyde, will no longer constitute a resin salt. flame retardant as defined above;

   said mixture shows a tendency to crystallize, which causes it to largely lose its resinous properties, and its resistance to water is inferior.



   The above preferred class of resins comprises co-condensation products of a strongly basic cyanamide derivative and a weakly basic cyanamide derivative with an aldehyde. The formula of cyanamide is CN2H2 and its structure can be indicated as NC-NH2 or as HN = C. = NH.

   Some of the most important cyanamide derivatives, which can be employed according to the present invention are shown in the diagram.
 EMI5.1
 Sü1l'c.1'G: Cymamide Strongly basic derivatives Weakly basic guanidine derivatives) 3 9 ux êe 'A / ¯¯¯¯¯¯¯¯¯¯¯ ##. / Thi 1-carbemylguanidîne (also called: \) dicyandiaKtidej dicyandiamidine or guanylic urea) l.zine
The strongly basic character of guanidine is generally attributed to the fact that the guanidinium ion (C (NH2) 3 resonates between three equivalent structures:

      
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The resonance energy of these three structures makes the guanidinium ion more stable than the guanidine itself, thus promoting the right side of equilibrium:
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The guanidine derivatives for which two equivalent structures can be written for the corresponding ion, although a little less basic, generally still constitute strong bases, In order to form

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 the preferred ce-condensation products of class 4), according to the invention, a strongly basic derivative of cyan amide can be employed, ie.

   guanidine or one of its equivalents, as will be described below, which will produce "spots" 'basic areas in resinous structures' having two equivalent resonant groups o The weakly basic derivative of the oyanamide chosen to form the preferred co-condensation products should contain the group H2N-C = X, in which X can represent 0, S, NH or N-, said group being capable of reacting with aldehydes, to form resins.



  It should be noted that the strongly basic derivative of cyanamide contains, in addition to the structures with basic resonance, this same group which is reactive with respect to the aldehyde. Although the present invention is not limited by any special theory, it is likely that typical co-condensation products of preferred class 4) can be represented by formula I in case of a product obtained from guanidien, urea and formaldehyde and by formula II in the case of a product obtained starting from guanidine, melamine and formaldehyde:
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It should be noted that in said structures, the guanidine segment can, by attracting a hydrogen ion, resonate between the two equivalent structures;

   
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In a similar co-condensing structure l-arbamyl guanidine (dicyandiaminie or guanylic urea) provides an acid adsorbing segment, which after reacting with H can be represented as follows:

   
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As a result, it is generally possible to employ as strongly basic derivatives of cyanamide compounds which, condensed with an aldehyde
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 and with a weakly basic derivative of cyanamide produce a resinous-adsorbent strudure of idea containing the group R13IIC '= NRs in which R may represent Es CH33 C 115 or another alkyl group This class of strongly basic compounds, designated in the description and in the claims as strongly basic derivatives of cyanamide "includes guanidin, gumidin 1-catbemy> that etao As weakly basic derivatives of cyanamide it is generally possible to use compounds containing the reactive group H2N ... c '= X5' in which X may represent an oxygen atom or a sulfur atom,

   an NH or N-group said class of weakly basic compounds, designated in the description and in the claims as weakly basic derivatives
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 of eyanamide includes urea, thioutine, disndiine9 melamine etc. in general, compounds containing said reactive group, which in combination with an aldehyde, 1) in the resinous structure will form the group
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The resins of the preferred class (4) generally cyana- have a higher nitrogen content than the resins of the other three classes;

   I believe that said high nitrogen content contributes to the reduction of the combustibility of the basic resin itself ,, and in conjunction with the inorganic acid-!)
 EMI7.4
 has a tendency to produce a resin salt forming a bulkier and less combustible carbonaceous mass when exposed to flames.



   Instead of reacting a strongly basic derivative of e.g. mide, such as e.g. guanidine (and a weakly basic derivative) with formaldehyde and 1-acid, it is also possible to convert, partially or
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 entirely, dicyandiamide which is weakly basic in guanidine (or guanylic urea) which is strongly basic by conventional methods, the acid.

   by heating with an acid - after that we can add an acid and formaldehyde and if necessary unconverted dicyandiamide from urea or another weakly basic derivative
The fire retardant and potentially heat insulating resin salt, when heat cured, is a solid product, substantially insoluble in water, the chemical character of which is very different from simple mixtures of an acid. or a salt with a resin.

   The essays
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 containing only simple mixtures of careable diacids or salts with or without resins or other organic materials are not resistant to leaching; in mixtures of this nature, the acid or the salt retains its characteristics.
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 physical and chemical characteristics such as the liquid or crystalline state, the melting point etc. In the resin salt, on the contrary, \)
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 the acid or acidic salt is chemically combined, thus losing its chemical and physical characteristics - d6 - ,, adventagous, but retaining the capacity to convert the resin into a carbonaceous mass, if this is exposed to the
 EMI7.9
 warmth
In order to prepare a fire retardant resin salt.,

   the resin can be condensed in the presence of 1-acid or the acid salt, or the resin can be prepared in advance and then contacted with an aqueous salt solution.
It is advantageous, in order to obtain a high degree of flame retardancy, to coat the combustible materials with the resin salt while said ep is still soluble in water and incompletely polymerized and to cure the resin on or in the resin. material processed.

   Particularly the ex- materials
 EMI7.10
 highly combustible - such as triplex "fiber board" and uwall board ". Materials which require a high degree of flame retardancy are preferably coated with an aqueous solution of the resin salt and then exposed to conduits. '- Polymerization operations, thus, with heat, to effect the curing of the resin salt in situ. When the salts of the preferred resins of class 4) with phosphoric acids are treated pe

   they will form a skin

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 uninterrupted, extremely adherent layer with excellent flame retardant properties In this case the flame retardant action of the resinous coating on the combustible material will be particularly effective, because it is not hampered by the presence of other materials, such as film-forming binders or fillers which generally consist of organic combustible materials or inert inorganic diluents, which therefore have a tendency to more or less reduce the effectiveness of the coating.
The degree of fireproofing depends on the thickness of the film.



  The thicker the film, or the greater the weight of the coating per unit area, the more effective the protection will be.



   In the water-soluble state many resin salts have a tendency to polymerize slowly, so that it is generally necessary to use them rather soon after their preparation, which is very well possible in the case of 'industry. In the manufacture of "wall board". for example one can prepare in the morning resin salt solutions sufficient for a day's production. Said solutions can be applied to “wallboards” during the last phases of the manufacturing process.



   It will not always be practical, however, to make use of the above method of application. In many cases it is desirable to provide customers with a product which remains stable during use and which can be applied as desired. For this purpose, according to the invention, the resin salt is polymerized until it is solid, in which state it will be stable. The solid resin salt is then dispersed in a finely divided condition in a liquid carrier comprising a binder which forms a film, with or without a volatile diluent. The combustible materials may be coated with said compositions by means of atomization or dip painting or in other effective manner.

   When the diluted evaporates; a film forms which causes the solid resin salt dispersed therein to adhere to the surface. It has been found that among the dandruff-forming agents the drying oils, eg linseed oil, tung oil and dehydrated castor oil are suitable for the purpose, despite the fact that the film dries up. The dried oil containing the resin salt reduces the effectiveness of said salt, not only because the oil film itself is more or less flammable, but also because said film is hard enough to hamper the strength a little. The carbonaceous mass formed at the expense of the resin salt when exposed to flame temperatures. When using drying oils it will be advantageous to use customary paint thinners and desiccants to complete the composition.

   Film forming resins, especially alkyd resins, are more effective film forming resins than drying oils.



   Among the alkyd resins those modified with drying oil are preferred. Said resins are not very combustible, if they have been well dried, but they somewhat hinder the formation of carbonaceous mass, which more or less reduces the effectiveness of the resin salt. In this case also, the usual paint thinners can be used to complete the composition.



   Cellulose ethers and cell esters in general, and especially methyl cellulose, ethyl cellulose and cellulose acetate, are particularly effective film formers. Said cellulosic derivatives can be dissolved in a suitable solvent (water? Alcohol etc.) after which the fully polymerized and finely divided solid resin salt can be dispersed in the solution.

   Cellulose derivatives hamper the effectiveness of the resin salt less than do drying oils or alkyd resins. Although we have mentioned the above film-forming agents as typical examples, it goes without saying that other film-forming agents can be used, while still being within the scope of the invention.



   You can also add pigments and fillers. The following specific examples serve to indicate how the invention can be put into practice.

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 Example 1. a) 119 grams of guanidine carbonate and 126 grams of melanin were added to 322 grams of aqueous formaldehyde (37%). After 20 minutes
 EMI9.2
 42.â cc of concentrated phosphoric acid (85% H3PO4) were added in small portions until the evolution of carbonic acid stopped. The mixture was stirred continuously until an aqueous, low viscous dispersion formed.



   The dispersion suddenly solidified, after being heated on a steam bath for about 15 minutes. The gel was cut into small pieces and dried at a temperature of about 105 G The dry gel was then washed with water, to remove any excess unbound phosphoric acid, until that the wash water was free of phosphate. There is thus obtained a resin phosphate having excellent flame retardant and potentially insulating properties. The resin phosphate is remarkably insoluble in water, because the phosphoric acid is chemically bound to the resin.

   The solid product thus obtained differs, therefore greatly from a simple mixture of phosphoric acid, or of a salt thereof with a xesinem. It is practically
 EMI9.3
 insoluble in water o It is resistant to treatments with HC19 H2S04 'and EBr9 thus showing that the phosphate resin is more stable than the sulphate, the hydrobloride or the hydrobromide. It is irreversible in the sense that a considerable part of the phosphoric acid combined with the resin can no longer be removed by treatment with alkaline materials.



  The product exposed for two minutes at a temperature of 750 C in an electric oven formed a carbonaceous mass of a volume several times greater than that of the original product and this bulky mass remained substantially intact for the entire duration of the process. the ordeal. b) The low viscosity aqueous dispersion obtained according to a) was applied, before being hot gelatinized, to one side of a piece of
 EMI9.4
 Garlic "waliboard" means a brush. The wetted part was heated to a temperature of about 90'00 for three hours, whereby the eBI1- s-4- vaporora treated while a uniform coating of hot-cured resin salt formed. on the part.

   The coated part exhibited greatly reduced flammability on the coated side of the coating. c) 25 parts by weight of guanidine carbonate, 25 parts by weight of melamine and 62 parts by weight of aqueous formaldehyde (37%) were
 EMI9.5
 added to 60 parts of eara I. (The mixture was added very gradually and with vigorous stirring, 42.5 parts by weight of phosphoric acid (85%).
 EMI9.6
 In a practical test a piece of wood fiber board was covered with this resin salt solution by spraying.

   The treated part was then passed through a hot air furnace with a length of
 EMI9.7
 of about $ 1 meag heated to a temperature of about 0l C with a speed of 169 meters per minute o In another practical test a piece of untreated "fiber board" was subjected to preheating in the passing through a drying oven. The resin salt solution was applied by spraying and the part was immediately afterwards subjected to the action of a pressing cylinder with a metal surface, the temperature of said metal surface being about 260 G.



   In both cases we obtained a piece of "fiber board" coated with a film of salt of fire-retardant resin very adherent and of excellent appearance.



   Plastic agents can be added to the resin salt solution.
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 fiants (poeo la p = toJllene sulfonamide) and pigments. d) 200 kilograms of titanium dioxide (Rutile) 400 kg of salt
 EMI9.9
 of fire-retardant resin of 19Ex; Example 1 a) and 500 kg of alkyd resin (Falkyd n A: 3) were ground in an ordinary paint mill and then dispersed in a mixture containing 118 kga of Solvesso 1 3 thinner. kga of cobalt-based drying agent and 6 kg of lead-based drying agent.

   The com-

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 resulting position will remain stable and can be shipped and stored. e) 11.9 grams of guanidine carbonate and 12.6 grams of melamine were added to 32.4 cc of aqueous formaldehyde (37%). The solution was left alone for two hours. Then add about 1.5 cc of concentrated phosphoric acid (85% H3PO4) in droplets until the evolution of CO2 stopped and the mixture was stirred continuously and carefully until what it thickens. Then 8 cc of concentrated phosphoric acid (85% H3PO4) was added and heating was continued until the mixture gelatinized.

   The gel was cut into small pieces, dried at a temperature of about 100 ° C., washed with running water for about 24 hours (the pH of the washing water was then about 6). dried again and ground in a bead mill. 6.3 grams of the finely ground resin resulting from this treatment was then dispersed in a solution containing 50 cc of 95% ethyl alcohol and 1 gram of ethyl cellulose. The composition resulting from this treatment is stable. Said composition can be applied to paper, cardboard, fabrics and other combustible materials by immersion in the form of a coating applied by rollers, by means of a syringe spray brush. , and by other means appropriate to the purpose.



     After the water and alcohol have evaporated from the coating, a flame retardant material coated with the resin salt is obtained which is bound to said material by means of the ethyl cellulose film. When the coated side of the resin salt is exposed to flames, a flame retardant and insulating carbonaceous mass will form. f) 12.5 grams of melanin, 125 grams of guanidine carbonate and 35 grams of aqueous formaldehyde (37%) were added to 400 cc. of water.



  To this mixture was gradually added 12.5 grams of concentrated phosphoric acid (85% H3 PO4). Samples of a lightweight fabric were immersed in an impregnator bath containing the above liquid composition, to which small amounts (e.g. less than 5% by weight of the composition) of a plasticizer can be added. e.g. the. de- paratoluene- sulfonamide, or urea.



  The impregnated fabric is squeezed out and then placed in a furnace at a temperature of 95 ° C. to be dried and cured for about 90 minutes. The fabric treated in this way is flame resistant. g) the aqueous resin dispersion according to Example 7 (c) was employed as an adhesive agent to bond (l) paper to paper, - (2) paper to wood, and (3) wallpaper to a board. "insulator.

   Said materials were bonded together by applying the aqueous dispersion of resin salt to both surfaces by means of a brush; the surfaces were pressed together - and then heated. h) In order to improve the binding properties, a mixture of dry wheat starch with water containing 5-10% by weight of starch, and having the consistency of a fluid paste (such as those of which generally used for decorating walls with wallpapers) was mixed in equal parts with the aqueous resin dispersion according to Example 7 (c) and used as described in Example 7 (g).

   Improved adhesion was thus obtained, especially in cases where the wallpaper was attached to the "fiber board".



   A comparison of the parts, treated according to Examples 7 (g) and 7 (h), with control parts, in which the adhesive agent was only constituted by the wheat starch paste used according to Example 7 (h) which did not contain a resin salt, showed a marked improvement in the flame retardant properties of the materials according to Examples 7 (g) and 7 (h) over those of the control materials.



    Example 2.



   60 grams of urea and 90 grams of guanidine carbonate were added to 300 cc of aqueous formaldehyde (37%). The solution was stirred without external heating for 35 minutes and there was an initial slight rise in temperature (up to 51 ° C). Then 22.7 cm3 of concentrated sulfuric acid (specific gravity 1.84) were added in small portions with stirring.

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 continuously, until the evolution of C02 stopped. This solution can be applied to combustible materials as described in Examples 1 (b) and 1 (c);

   or alternatively the solution can be heated for about 100 minutes on a steam bath, until it becomes viscous, and it can then be dried at a temperature of 120 ° C.
 EMI11.1
 until its weight remains constant. The white, powder-hardened and soiled material which results from this treatment can be softened to the desired degree washed until it is free of water-soluble matter; , and it can then be dispersed in a solvent containing a forming agent
 EMI11.2
 de-pcllieule, as described in Examples 1 (d) and lue) Example: 3 25: p2 g of melamine and 2308 of guanidine carbonate were added to 64.4 g of aqueous formaldehyde (37%).

   The mixture was stirred and
 EMI11.3
 add 9 cc of concentrated sulfuric acid (specific gravity 1.75) in small portions. When the addition was complete, there was no further evolution of CO2 and the pH had dropped to about 5 This composition can be applied to combustible materials as described in Examples 1 (b) and 1 (c), or the mixture can be heated on a steam bath and
 EMI11.4
 gelatinized in five minutes. The gel can be dried at a temperature of 110 ° C., until its weight remains constant. The product. described above has very marked flame retardant and potentially isolating properties.



    Example 4
24 g of dicyandiamide were mixed with 42.5 g of phospho-
 EMI11.5
 rique- (85%), 5 cc. 25 g of urea and 100 tbsp of aqueous formaldehyde (37%) were added and the mixture was allowed to boil under reflux for at least three hours; Considerable amounts of guanidine (and / or: guanyl urea) were formed before or during condensation with formaldehyde.



  There was a pronounced increase in pH and the phosphate of an anion exchange resin was formed. The mixture was cooled.



  It can be used as a plaster for combustible sutfaces.
 EMI11.6
 



  Exe !!!: Qle 3 .... ±, 18.IJ 1 g of dihydrochloride of m. phenylene diamine, 93 g of concentrated HCl (36%) and 50 cm3 of water were stirred at room temperature and 12 g of aqueous formaldehyde was added. The temperature of the mixture rose to 45 ° C and a dark-colored resin precipitated out almost immediately.



  Said solid hydrochloride was separated from the solution and dried at 105 ° C. for 18 hours.



  Example 6
18.1 g of hydrochloride of m. phenylene diamine, 8.4 g of dicyandiamide, 1.7 g of concentrated HCl and 70 g of water were heated on a bath of
 EMI11.7
 steam for 24 hours. The bigusnidylbenzene hydrochloride solution was cooled to 50 ° C. and a mixture of 36.2 g of m. Dichloride was added. phenylene diamine and 3.4 g of concentrated HCl. The mixture was allowed to cool to a temperature of 30 ° C., after which 52.7 g of aqueous formaldehyde (37%) were slowly added. Almost immediately. The mixture gelatinized and the temperature rose to about 80 C.

   The dark colored solid resin hydrochloride was dried at 103 ° C. for 18 hours.



  It had very pronounced flame retardant properties and resistance to combustion. Exposed in the furnace to a temperature of 750 C, a carbonaceous mass is produced, porous and insulating with respect to heat. The mass is sufficiently resistant to combustion.



   The products according to Examples 4 and 5 are suitable for use in combination with film-forming agents, as described in Examples 1 (d) and 1 (e).



  Example 7.



   9.4 g of phenol, 14.6 g of triethylenic tetramine and 24.3 g of aqueous formaldehyde (37%) were mixed thoroughly, with cooling.

 <Desc / Clms Page number 12>

 outside the water; 25 g of aqueous formaldehyde was then added and the mixture was heated on the steam bath, until gelatinized.



  The gel was dried at 125 Ce. This basic resin is flammable. If we
 EMI12.1
 reacted with about 3 milliequv'lents of phosphoric acid per gram of basic resin., a resin salt will be formed with very low resistance. This salt in combination with a film-forming agent and a solvent is valuable as flame retardant and insulator against potential heat.



    Example 80
 EMI12.2
 A mixture of 12 g of ethyl ethyl tetramine, 25 g of H3PO4 (5%), 35 g of aqueous formaldehyde (37%) and 125 g of acetone was heated under reflux for one hour. The light acetone layer was separated from the heavier viscous layer containing the resin. The viscous polymer can be applied to combustible materials, either before or after they had been heat cured Example 2.268 g of the so-called "Acidity resintl" resin (an ion exchange product manufactured by the Permutit Company) were contacted with 4244 g
 EMI12.3
 of an aqueous solution of phosphoric acid containing 9.2% Ho Po 3 and the mixture was stirred for one hour.

   The resin salt was washed for de-
 EMI12.4
 wash off some excess acid, until the wash water was acid free, after which the salt was dried for 24 hours at a temperature of approx.
 EMI12.5
 ron l00 C and ground. 100 parts of the phosphate- resin resulting from this. Very soon were mixed with 100 parts of a commercial varnish containing dehydrated castor oil and a resin (manufactured by Devoe and Raynolds Co. Inc.) The resulting composition was applied to cardboard panels which were then coated. were then dried. The cardboard panels coated in this way showed remarkable flame retardant properties.
 EMI12.6
 



  Instead of the "deAciditen" resin, other anion exchange products, such as "Amberlite IR-4 (manufactured by" Resinous Products and Chemical Compazy ") or Ionac A 203 M (manufactured by by the American Cyaiadde Company ") can be used to form resin salts with flame retardant and potentially heat insulating properties.



   It should be further noted that the solid resin salt according to the present invention can also be used to form molded or otherwise non-flammable articles or can be used in the form of a powder. to protect combustible materials against fire.


    

Claims (1)

CLAIMS AND SUMMARY. A flame retardant composition comprising a salt of a nitrogen-containing basic anion exchange resin and a non-oxidizing inorganic acid. 2. Flame retardant composition according to claim 1, characterized in that the salt of the anion exchange resin is derived from phosphoric acid. EMI12.7 3. A flame retardant composition according to claim 1-2. characterized in that the anion exchange resin is a condensation product of an aldehyde, a strongly basic derivative of cyanamide and. of a weakly basic derivative of cyanamide. 4. Flame retardant composition according to claim 3. characterized in EMI12.8 what the aldeliyde employed is formaldehyde. , 5 Flame retardant composition according to claims 3-4, characterized in that the strongly basic derivative of cyanamide is guanidine, 6. Flame retardant composition according to claims 3-5, characterized in that the weakly basic derivative of cyanamide is melamine. 7. Flame retardant composition according to claims 3-5, characterized in that the weakly basic derivative of cyanamide is urea. <Desc / Clms Page number 13> 8. Flame retardant composition according to claims 107. characterized in that the resin is an incomplete condensation product. 9. Flame retardant composition according to claims 108, characterized in that it also contains a film-forming material. 10. Flame retardant composition according to claim 9, characterized in that the film-forming material is a drying oil, an alkyd resin and / or a cellulose derivative. 11. Flame retardant composition according to claims 1-10, characterized in that it also contains starchy materials, gums and / or proteins. 12, Method for improving resistance to. fire using a flame retardant composition according to claims 1-11, characterized in that the surface of the object to be treated is coated with a- solution of a salt of a basic anion exchange resin- containing l nitrogen and a stiff non-oxidant. 13. The method of claim 12, characterized by that the resin is used in incompletely condensed condition. 14. A method for improving the fire resistance using a flame retardant composition according to claims 1-11, characterized in that the condensation is carried out on the surface of the object. 15. Articles whose fire resistance is improved by using the flame retardant compositions according to claims 1-11 or by using the process according to les- claims 12-14.