Self-extinguishing polymeric compositions and production process

Abstract

The present patent of invention relates to an innovative composition with excellent non-flammable and self-extinguishing properties for composite materials, from which many useful molded materials can be produced, and also to the provision of inorganic compounds coated with an inert material, defined as a material that does not exhibit reactivity with the inorganic compounds. The present invention provides organic materials and, more particularly, relates to highly polymeric materials having excellent fire-retardant properties, such as those employed in the manufacture of molding and extrusion compositions, film sheets, fibers, textiles, papers, surface or coating compositions, impregnating agents, solid forms, rubbers, and the like. The invention may also be applied especially to wet-spun and dry-spun fibers, such as acrylic fiber, polyvinyl alcohol fiber and viscose rayon, and melt-spun fibers, such as nylon, polyester fiber, and other fibers, such as di- or triacetate cellulose fibers. The invention is also applicable to plastics and films, by adding said inorganic compounds prior to molding. Another noteworthy feature of this invention is that when, for example, fibers produced by the process are ignited, no toxic gas is generated before the fire is extinguished.

Description

[0001] Self-extinguishing polymeric compositions and production process. Field of application 0 01 This descriptive report refers to a patent application for inventions concerning new non-flammable composite materials and a method for producing them. More particularly, the invention relates to non-flammable composite materials for application in fibers, plastics, films, and other molded products. It is extremely practical and efficient, and can be used preventively in the protection of forests, agricultural crops, wood, plywood, particleboard, paper, cotton fabrics, rubber, paints, and varnishes, thus meeting the conditions to merit the protection now sought. 02The self-extinguishing polymeric compositions and production process, through improvements and the technology employed, aim to provide an innovative composition with excellent non-flammable and self-extinguishing properties for composite materials, from which many useful molded materials can be produced, and also to provide inorganic compounds coated with inactive material, which is defined as material that does not exhibit reactivity with inorganic compounds. The present invention will provide organic materials and, more particularly, will deal with highly polymeric materials with excellent fire-retardant properties, such as those used in the manufacture of molding and extrusion compositions, film sheets, fibers, textiles, papers, surface or coating compositions, impregnating agents, solid forms, rubbers, etc.The invention can also be applied especially to wet and dry spinning fibers, such as acrylic fiber, polyvinyl alcohol fiber, viscose rayon, and melt-spun fibers, such as nylon, polyester fiber, and other fibers, such as cellulose di- or triacetate fibers. The invention is also capable of being applied to plastics and films by adding said inorganic compounds before molding. Another striking feature of this invention is that when, for example, fibers applied by the method are ignited, no toxic gas is developed before the fire ceases. STATE OF THE ART 0. 03With the sole and exclusive purpose of providing veracity to the preamble of this description, the applicant will now provide, in the following paragraphs, a brief but consistent explanation of the state of the art regarding the problems and drawbacks of adding non-flammable or self-extinguishing properties to petroleum-derived products. This will allow a person skilled in the art to recognize its shortcomings, and subsequently clearly identify in the invention now claimed the novelty requirement mandated by the Industrial Property Law. 04 Over the past two decades, many petroleum-derived products have developed remarkably, and numerous types of plastics, synthetic fibers, resins, and films have become very popular and, in fact, everyday necessities. 05Petroleum-based products possess many excellent characteristics that cannot be expected from natural products. The uses of petroleum-based products have developed rapidly, especially in recent years. However, petroleum-derived products have one major common drawback, namely, their high flammability. From the users' perspective, the appearance of non-flammable or self-extinguishing materials has been a major concern, especially for interior materials, fibers for industrial and clothing use, and the architectural sector, because high possibilities of major disasters caused by the presence of easily flammable materials have been identified. In fact, many such cases have already been reported.007 The addition of non-flammable or self-extinguishing properties to products is now one of the most urgent problems to be solved, and, for this purpose, research is being carried out intensively worldwide. However, due to the products originally being made from petroleum, which is flammable, there has been little success in giving the products a non-flammable or self-extinguishing property. 008 Non-flammable fibers are also urgently needed because fibers are now used everywhere and in homes, and most fire disasters have been due to the presence of easily flammable fibers. Unfortunately, despite many intensive studies, very little of use has been achieved in the way of adding non-flammability to fibers.009 Currently, for the preparation of an acrylic fiber, for example, polymers composed of acrylamide and halogen-containing monomers, such as vinyl bromide or vinyl chloride, have been used, but without satisfactory results. To provide sufficient flame retardant or self-extinguishing properties, more than 10% vinyl bromide must be incorporated; however, the effect is still very unsatisfactory. 010 In addition to the increased cost due to the use of large quantities of this expensive monomer, the physical and tensile properties of the fiber have been considerably reduced as the amounts of incorporated vinyl bromide have increased. Furthermore, these copolymers have resulted in poor processability in molding processes and also cause discoloration. 011 These factors have reduced the quality of the fiber and, consequently, reduced the commercial value of the fiber.Furthermore, even if the polymer could provide flame-retardant properties, appreciable to a certain extent, the result is still unsatisfactory, and moreover, when the fiber is ignited, toxic gases such as bromine gas or hydrogen bromide gas are generally released, significantly increasing the disaster. 12The state of the art reveals Brazilian patent BR 11 2018 003003-1, published on 09 / 18 / 2018, entitled COMPOSITION AND USE OF A COMPOSITION, which describes compositions comprising at least one thermoplastic polyurethane, at least melamine cyanurate, at least one first flame retardant containing phosphorus (F1) selected from the group consisting of alkyl esters of phosphoric acid and alkyl esters of phosphonic acid, wherein the alkyl radicals are selected from C1 to C12-alkyl radicals, and at least one flame retardant that continues to contain phosphorus (F2) selected from the group consisting of phosphinic acid derivatives, and for the use of such composition for the production of cable sheaths. The object presented in this patent is completely different from that proposed in this application. 013The state of the art also reveals Brazilian patent BR 11 2024003713-4, published on 05 / 28 / 2024, entitled METHOD FOR FORMING A POLYMERIC COMPOSITION, which describes a method for forming a polymeric composition that includes the steps of mixing in a molten state an ethylene-silane copolymer and a master batch of halogen-free flame retardant comprising a halogen-free flame retardant dispersed in an ethylene-vinyl acetate copolymer to form the polymeric composition, wherein the ethylene-silane copolymer is a random copolymer of ethylene and vinyltrimethoxysilane derived units and wherein the copolymer has a vinyltrimethoxysilane content of 0.5% by weight to less than 2% by weight based on the total weight of the ethylene-silane copolymer; and processing the polymeric composition into a plurality of particles. The object presented in this patent is completely different from what is proposed in this application.014 In view of the foregoing technical fundamentals, with the passage of time and the accumulation of experience, facts have pointed towards the development of new compositions with excellent non-flammable and self-extinguishing properties for composite materials, presenting several advantages, being quite practical and efficient, where its unique constructiveness eliminates the negative aspects known in the State of the Art, which is presented in this patent. OBJECTIVE OF THE PATENT 0. 15In order to overcome the problems presented, the inventor hereby applies for a Patent of Invention, entitled SELF-EXTINGUISHING POLYMERIC COMPOSITIONS AND PRODUCTION PROCESS, which fundamentally aims at the development of an innovative composition with excellent non-flammable and self-extinguishing properties for composite materials, from which many useful molded materials can be produced, and also to provide inorganic compounds coated with inactive material, which is defined as material that does not exhibit reactivity with inorganic compounds. Through research and studies, and always seeking innovations and practical solutions to differentiate their products from competitors, the inventors have developed this simple and efficient composition, capable of overcoming all the limitations and inconveniences reported in the State of the Art in an extremely effective way. 17The invention is basically comprised of an innovative idea that the non-flammability or self-extinguishing of materials is only effectively achieved when the following important factors described below are satisfactorily met: • Delaying the supply of oxygen; • Decreasing the temperature; • Formation of an extinguishing liquid capable of covering the ignition points. 18 According to the present invention, the first feature of the invention relates to compositions containing at least one of the inorganic compounds with phosphorus (P) and nitrogen (N), or either of them, and methods for producing the same and molded products from them. 019The invention relates to additives with certain characteristics. When the additives are heated by fire, non-flammable heavy gases are developed, which will cover the ignition sites and retard the oxygen supply. The thermal decomposition reaction must be an endothermic reaction that effects a reduction in temperature, and the byproducts released by the thermal decomposition must be extinguishable liquids. Based on the above idea, the invention finally discovered that some inorganic compounds containing at least one phosphorus (P) or nitrogen (N), or both, satisfy the three factors above. Among these compounds, especially inorganic compounds with phosphorus and nitrogen are the most effective.Examples of these compounds are ammonium phosphates, such as primary ammonium orthophosphate (NH4)H2PO4, secondary ammonium orthophosphate (NH4)2HPO4, tertiary ammonium orthophosphate (NH4)3PO4, ammonium pyrophosphates, such as primary ammonium pyrophosphate (NH4)H3P2O7, secondary ammonium pyrophosphate (NH4)2H2P2O7, and others such as (NH4)3HP2O7, (NH4)4P2O7, ammonium phosphites, such as (NH4)H2PO3, (NH4)2HPO3, ammonium hypophosphates, such as (NH4)2H2P2O6, (NH4)3HP2O6, ammonium hypophosphites such as (NH4)H2PO2, (NH4)2HPO2, ammonium metaphosphate such as (NH4)PO3 and ammonium dihydrogen phosphite. (NH4)H2PO3 and so on. 021 In addition to these examples, compounds with other metallic elements are also involved, for example, sodium ammonium phosphate NaNH4 HPO4, magnesium ammonium phosphate (NH4)MgPO4, ammonium phosphomolybdate (NH4)3PO412Mo3, ammonium phosphotungstate (NH4)3 PO412Wo3, ammonium cobalt phosphate (NH4) CoPO4, ammonium manganese phosphate (NH4) MnPO4.Furthermore, halogen-containing compounds such as difluoroammonium phosphate (NH4)PO2 F2, hexafluoroammonium phosphate (NH4)PF6, diaminophosphoric chloride Cl3P(NH2)2, nitrile triphosphoric chloride (PNCl2)3 and other compounds such as phosphoamide OP(NH2)2, metaphosphemic acid P3N3(OH)6 and its ammonium salt P3N3O6H3(NH4)3, ammonium trithiophosphate (NH4)3PO3. The hydrates of the above compounds are also included. 022 The compounds mentioned above satisfy all three factors. Especially, the release of inorganic liquid by thermal decomposition is most important. 0. 23The most effective inorganic liquids are phosphoric acid, phosphorous acid, hypophosphoric acid, and metaphosphoric acid. These inorganic acids have excellent extinguishing properties, covering and forming a nearly ideal monomolecular film over ignition sites, which has a strong effect on extinguishing fires. The objective of the present invention can also be achieved by using inorganic compounds containing phosphorus (P) in combination, with or without other inorganic compounds containing nitrogen (N). 25 Examples of these compounds are selected salts of phosphoric acid, phosphorous acid, metaphosphoric acid, metaphosphorous acid, hypophosphorous acid, pyrophosphorous acid, hypophosphoric acid, pyrophosphoric acid, and so on. Types of salts are, for example, sodium salt, potassium salt, lithium salt, beryllium salt, magnesium salt, calcium salt, zinc salt, cadmium salt, ammonium salt, and so on. 26Concrete examples are potassium dihydrogen phosphate KH2PO4, dipotassium hydrogen phosphate K2HPO3, potassium pyrophosphate K4P2O7, magnesium pyrophosphate Mg2P2O7, potassium metaphosphate (KPO3)n, potassium and sodium hydrogen phosphate NaKHPO4.7H2O, disodium dihydrogen pyrophosphate Na2H2P2O7, sodium metaphosphate (NaPO3)6, disodium dihydrogen hypophosphate Na2H2P2O6, trisodium phosphate Na3PO4.12H2O, disodium hydrogen phosphite Na2HPO3.5H2O, disodium phosphomolybdate Na2PO4.12MoO3, trilithium phosphate Li3PO4.1 / 2H2O, magnesium hydrogen phosphate MgHPO4.3H2O, disodium hydrogen phosphate Na2HPO4 and its hydrates. Na2HPO4.2H2O, Na2HPO4.7H2O, Na2HPO4.12H2O, sodium dihydrogen phosphate NaH2PO4.H2O, primary monomagnesium hydrogen phosphate MgH4(PO4)2.3H2O, trimagnesium phosphate Mg3(PO4)2.5H2O, secondary calcium phosphate CaHPO4.2H2O, primary calcium hydrogen phosphate CaH4(PO4)2, calcium phosphite CaHPO3, tertiary zinc phosphate Zn3(PO4)2.4H2O, secondary zinc phosphite ZnHPO3, zinc pyrophosphate Zn2P2O7, aluminum phosphate AlPO4, and so on. 0. 27 Examples of inorganic compounds containing nitrogen are ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium nitrate, ammonium sulfate, ammonium bisulfate, and ammonium phosphates. In the application of this invention, two or more of the above compounds may also be used, for example, a combination of (NH4)H2PO4 and (NH4)NaHPO4, or a combination of KH2PO4, K2HPO4, and (NH4)2CO3 may be used. 29Another important feature of the present invention is that, in the application, the entire surface of the inorganic compounds is coated, if necessary, with inactive materials, which are defined as material that does not exhibit reactivity with the inorganic compounds. This is a very important point of this invention because without it, the present invention cannot be used in some cases. For example, when ammonium phosphate (NH4)H2PO4 is attempted to be used as an additive to a dope in the production of a self-extinguishing acrylic fiber, a serious problem arises. Because the compound is soluble in dimethylformamide, which is used as a solvent for a dope, and also because the compound is readily soluble in water, which is used in spinning and stretching baths, the compound added to the dope is easily washed away during the spinning, washing, and stretching processes. As a result, only small amounts of the compound can be retained in the filaments.Furthermore, the compound causes the fiber to turn yellow or brown. This discoloration greatly reduces the commercial value of the fiber. In addition, the inorganic compounds derived from dope result in problems in solvent recovery. To solve these problems, the inorganic compounds must be changed to physically and chemically inactive materials. The present invention has finally managed to remove this unavoidable defect by coating the compounds with physically and chemically inactive materials. The inactive materials used in this invention are, for example, polysiloxane, silicone oil, silicone grease, superior paraffin, saturated or unsaturated compounds of aliphatic or aromatic hydrocarbons with more than 10 carbon atoms, the so-called petrolatum, paraffin gel, petrolatum, liquid paraffin, mineral oil, and vegetable oil. 033A proposed coating method for said inorganic compounds is as follows. First, an inactive material such as solid paraffin is first dissolved in a solvent that can dissolve the inactive material, but not said inorganic compounds. The said inorganic compound is then suspended in this solution, and after all surfaces of the said powdered inorganic compound are contacted with the solution, the said inorganic compound is filtered or the solvent is evaporated without filtration. Thus, the surface of the inorganic compound is uniformly coated with fine inactive material. 34When powdered ammonium phosphate is coated with a solid paraffin, the compound is no longer soluble in dimethylformamide and water. Therefore, when ammonium phosphate is used as a flame retardant additive in the production of acrylic fiber, the coated ammonium phosphate added to a spinning solution does not flow during the spinning, stretching, and washing processes. Furthermore, the ammonium phosphate is no longer chemically active, so no fiber discoloration occurs. 35This coating is not always necessary, for example, in the case of melt-spun fibers, processes which do not involve the use of solvent and water. However, the coating is often useful to prevent staining. Another feature of the invention is that said inorganic compound is added in one of the processes in the production of molded materials. The compounds are desirably finely pulverized so that, for example, the compounds can pass through the holes of spinnerets without problems, such as titanium oxide for an opaque fiber. 037When said inorganic compound is added to a dope such as titanium oxide, it is quite advantageous and useful for large-scale production with high productivity, and for quality control. On the other hand, in the case of acrylic fiber production, said compound can also be effectively added by immersing gel fibers in an aqueous solution containing an inorganic compound immediately after stretching, thus the said inorganic compound can be incorporated into the fiber. The quantities of said inorganic compounds are generally less than 10% based on the molded materials. They can be increased or decreased depending on the non-flammability requirement. The method presented in this invention is surprisingly effective in adding non-flammability and self-extinguishing properties to the products; in fact, only a few percent of said compound is often sufficient to pass the most severe vertical non-flammability test. 39Another striking feature of this invention is that when, for example, fibers applied using this method are ignited, no toxic gas is developed before the fire ceases. 40 For example, the phosphoric acid released from ammonium phosphate by thermal decomposition, which covers the ignition sites as a nearly ideal monomolecular layer, transforms into pyrophosphoric acid or metaphosphoric acid, which is a polymeric material with excellent quenching properties; therefore, no toxic gas is developed. 41 In conclusion, the present invention will provide organic materials and, more particularly, will deal with highly polymeric materials with excellent fire-retardant properties, such as those employed in the manufacture of molding and extrusion compositions, film sheets, fibers, textiles, papers, surface or coating compositions, impregnating agents, solid forms, rubbers, etc. 42The invention can also be applied especially to wet and dry spinning fibers, such as acrylic fiber, polyvinyl alcohol fiber, viscose rayon, and melt-spun fibers, such as nylon, polyester fiber, and other fibers, such as cellulose di- or triacetate fibers. The invention is also applicable to plastics and films by adding said inorganic compounds before molding. 43The invention is illustrated by the following examples, which should not be taken as limiting in any respect. All parts and percentages are by weight unless expressly stated otherwise. It is important to understand that the present Invention Patent presented here is illustrated in a demonstrative manner and is not limiting as to the application of the details, dimensions, capacities, and steps described. It is capable of other embodiments and of being practiced or executed in a variety of ways, without, logically, departing from the main inventive scope of the object whose protection is claimed. 45 To complement the present description in order to obtain a better understanding of the characteristics of the present Invention Patent and in accordance with a preferred practical embodiment thereof, a set of drawings is attached to the description, where, in an exemplary manner, the following is represented: Figure 1 – View of the structural formula. PREFERRED DESCRIPTION 0 46In accordance with the attached drawings, the SELF-EXTINGUISHING POLYMERIC COMPOSITIONS AND PRODUCTION PROCESS, the subject of this present Patent Application, refers to self-extinguishing polymeric compositions comprising a poly(ethylene oxide), preferably, and a flame retardant additive consisting of: (1) 10-25% by weight, in the total composition, of an ammonium or amine phosphate; and (2) 10-25% by weight, in the total composition, of a product obtained by bulk reaction, at a temperature between 80ºC and 230ºC, (a) at least one organic compound selected from the group consisting of (i) linear or cyclic compounds containing nitrogen having at least one >CnO or >CnS group and at least one –NH group—being part of the linear chain or ring, and (ii) amine compounds; with (b) an epoxyalkyl acid ester of formula: n STR1 n where n is an integer from 1 to 3;the reaction being carried out according to a molar ratio (a):(b) between 3:1 and 0.1:1, in w / w mol 0; 47 The invention also includes paints and coatings containing the aforementioned self-extinguishing polymeric compositions. 48 The invention also includes articles with self-extinguishing properties through the application of the aforementioned polymeric compositions. Example 1 0 49 A polymer comprising 93% acrylamide and 7% vinyl acetate was dissolved in dimethylacetamide to give a spinning solution. A diammonium hydrogen phosphate (NH4)2 HPO4 (3% based on the copolymer) that had been finely pulverized enough to pass through the holes of a spinneret and coated with paraffin (mf 68°C) was added to the dope. The solution was centrifuged by a usual process, then stretched 5 times its original length, washed and dried. Then the resulting filaments were subjected to annealing for relaxation. 51The fibers obtained exhibited excellent physical and textile properties similar to those of a conventional acrylic fiber and good whiteness. The analysis results showed that all the ammonium phosphate used was retained in each filament. A cloth made from the filaments was dried at 105°C for 3 hours and then subjected to a vertical ignition test. The flame ceased immediately after the removal of an igniter. On the other hand, the filaments were prepared similarly, except for the use of ammonium phosphate that was not coated with paraffin. The filaments obtained turned yellowish to brown during the drying and annealing processes. At the same time, the analysis showed that almost all the ammonium phosphate used was lost during the spinning and washing processes; therefore, only a small amount of ammonium phosphate was retained in the filaments.Example 2 054 A polymer comprising 94% acrylamide and 6% methyl acrylate was dissolved in a nitric acid solvent with a concentration of 69% at -5°C to give a 14% spinning solution. The polymer had a strong acid group of 10-. 5 equivalents per gram. 055 To this spinning solution, ammonium dihydrogen phosphate (NH4H2PO4) (3.2% polymer basis) was added, which had been finely pulverized enough to pass through the holes of a spinneret and coated with a solid paraffin. Then the solution was centrifuged in the usual wet manner in a coagulation bath containing 30% nitric acid at -3°C. 0 56 The filaments obtained were stretched, washed, and dried, then subjected to steaming for relaxation. The fibers obtained had good textile properties and whiteness. As a result of the analysis, it was found that all the ammonium phosphate used was retained within each filament. 57A flame-retardant property of a thick cloth made of fibers was tested by a vertical method (JIS, L1091-A-4), and it was demonstrated that the flame ceased immediately after the removal of the lighter. Example 3 058 A polymer was prepared containing 91% acrylamide, 3% vinyl bromide, and 6% acrylamide, and was dissolved in a dimethyl sulfoxide to give a dope. To this, ammonium dihydrogen phosphate (NH4)H2PO4 (1.5% based on the polymer) which had been finely pulverized and coated with a paraffin was added. Then, the wet solution was centrifuged in the usual manner. 059 The fibers obtained were essentially the same in textile property and whiteness as a conventional acrylic fiber. 0 60The analysis showed that all the ammonium phosphate used was retained within each filament without flowing out during the production processes. A fabric made from the fiber was dried at 105°C for 4 hours, and a fire protection test was performed using vertical and 45°C methods. The fabric showed perfect self-extinguishing properties. Conversely, a plush carpet was made from the fiber, and a fire protection test was conducted by lighting a urotropin tablet placed on the carpet. The flame self-extinguished immediately after the urotropin tablet burned. Example 4 0 62 A polymer was prepared containing 60% acrylamide and 40% vinyl chloride, and the polymer was dissolved in dimethyl acetamide to give a spinning solution. To this solution, diammonium hydrogen phosphite hydrate (NH4)2 HPO3.H2O (2% based on the polymer) that had been finely pulverized and coated with a paraffin was added.63 Next, the wet solution was centrifuged in the usual way. 64A shaggy carpet made from the obtained fibers was tested by igniting a urotropin tablet placed on the carpet. The flame was extinguished immediately after the urotropin burned. Example 5 065 A polymer comprising 94% acrylamide and 6% methyl acrylate was dissolved in dimethylformamide to give a spinning solution. Conversely, a finely powdered ammonium dihydrogen phosphate was suspended in an alkaline solution containing isotactic polypropylene, then filtered and washed with petroleum ether. By this procedure, all surfaces of the powdered ammonium phosphate were uniformly coated with the thin film of polypropylene. This (3% polymer basis) was added to the spinning solution from which the fibers were prepared by dry spinning. A cloth made from the obtained fibers was dried at 105°C for about 3 hours, then subjected to a non-flammability test using a vertical method.It was demonstrated that the cloth had an excellent self-extinguishing property. Example 6 0. 66 This example is essentially the same as example 5, except for the use of paraffin (mp 70°C) instead of polypropylene. The coating method is that a finely powdered ammonium dihydrogen phosphate was suspended in a solution of benzene or petroleum ether containing about 5% solid paraffin (mp 78°C), then filtered and dried. Thus, the entire surface of the powdered ammonium phosphate was uniformly coated with very fine paraffin. The ammonium phosphate was no longer soluble in dimethylformamide and water. The fibers obtained in this example showed excellent self-extinguishing properties in a vertical flame retardant test. Example 7 067 This example is the same as example 1, except that ammonium metaphosphite (NH4)PO2 was used instead of diammonium hydrogen phosphate. 0 68The fibers obtained in this example exhibited good self-extinguishing properties. Example 8 069 To an acetone dope of cellulose acetate (acetate value per glucose unit: 1.8), a finely pulverized diammonium hydrogen phosphate (NH4)2HPO4 (3.5% based on cellulose acetate) coated with a solid paraffin at 65°C was added, then the dope was centrifuged dry by a usual method. The centrifugation capability was excellent and made no difference compared to a conventional case. 070 Using a cloth made from the fibers thus obtained, a vertical flammability test was performed. The flame was extinguished immediately after a gas burner was removed. The same test was performed for conventional cellulose acetate fibers. In this case, a cloth of the conventional fiber caught fire easily and burned in one second.Example 9 071 In the case of spinning polyvinyl alcohol fiber, ammonium dihydrogen phosphate (2.5% based on polyvinyl alcohol) that had been coated with a paraffin at 78°C was added to a polyvinyl alcohol dope, then the dope was spun in a saturated aqueous solution of sodium sulfate in the usual manner. The fibers thus obtained were dried at 100°C for 4 hours. The non-flammability of the fiber was tested by a vertical method. The flame was extinguished immediately after the removal of an igniter. Example 10 0. 72 In a viscose rayon fiber production process, a finely powdered triammonium phosphate hydrate (NH4)3PO4.3H2O (2.5% cellulose basis) that had been coated with paraffin (m.p. 69°C) was added to a spinning solution. This solution was spun wet in the usual manner. The spinning capacity showed no difference compared to usual cases. The fibers obtained exhibited satisfactory self-extinguishing properties. Example 11 073 Polyethylene terephthalate containing sodium ammonium hydrogen phosphate NaNH4HPO4 (3.5% polymer basis) was melt-extruded to make chips. Using the chips, melt spinning was performed. The spinning capacity and elasticity were good and did not differ from conventional cases. The fibers obtained had good whiteness and good textile properties. 74 A cloth made from the fibers was dried at 105°C for 3 hours, then subjected to a vertical flammability test. The cloth showed satisfactory self-extinguishing properties. Example 12 0 75This example is the same as example 11, except that ammonium phosphomolybdate (NH4)3PO4.12MoO3 (5% on a polymer basis) was used instead of sodium ammonium phosphate. A flammability test for a fabric made from the obtained fibers that were dried at 105°C for 4 hours showed a perfect self-extinguishing property. Ammonium phosphotungstate (NH4)3PO4.12WO3 was also found to have a similar effect to ammonium phosphomolybdate. Example 13 0 76A finely powdered ammonium dihydrogen phosphate was suspended in a petroleum ether containing 3% silicone grease and then filtered. When the petroleum evaporated, all surfaces of the powdered ammonium phosphate were uniformly coated with the thin film of silicone grease. A mixture of 97% nylon and 3% of the above-coated phosphate was melt-extruded to give nylon filaments. A cloth made from the filaments was dried at 105°C for 5 hours, then its non-flammability was tested by the vertical method. The flame ceased easily and the cloth was considered to have good self-extinguishing properties. Example 14 0 77A film was prepared by an inflation method using chips of polyethylene containing 4% ammonium dihydrogen phosphate. Because the film thus prepared contained powdered inorganic materials, its transparency was somewhat reduced; however, the film had good physical properties. A portion of the film (30 mm × 150 mm) was placed vertically and lit at the bottom; the flame ceased immediately after a lighter was removed. Example 15 0 78 To a spinning solution consisting of 85% dimethylformamide and 15% polyacrylamide, a powdered hypophosphate (NH4)2H2P2O6 (5.5% polyacryl-based) was added. Using this dope, a film was prepared by a wet process. The resulting film was stretched biaxially. A portion of the film (30 mm × 150 mm) was hung vertically and ignited at the bottom. The film did not burn and proved to be self-extinguishing. Example 16 0 79A 92.7% polymethyl methacrylate prepolymer was uniformly mixed with 8.3% ammonium sodium hydrogen phosphate (NH4NaHPO4.4H2O), which was then coated with paraffin. Polymerization was continued until completion between two glass plates at 100°C. 80 The resulting polymethyl methacrylate sheet exhibited good flame-retardant properties. Example 17 0 81 92.5% polystyrene was mixed with 7.5% ammonium dihydrogen phosphate (NH4H2PO2) to make chips. 82 From the chips, molded materials were made, all of them non-flammable. Example 18 0 83 98.8 parts of a copolymer comprising 94% acrylonitrile, 6% vinyl acetate, and 1.2 parts ammonium hypophosphite (NH4)2H2P2O6, which had been finely pulverized and coated with a polyethylene, was dissolved in dimethylformamide to make a spinning solution. The solution was centrifuged dry in the usual manner. 84Using the fibers thus obtained, a carpet was prepared. A flame-retardant property was tested using a urotropin method (Example 3). When the urotropin was burned, the flame was immediately extinguished. Example 19 0 85 This example is the same as example 1, except that 4% ammonium phosphohexafluoride NH4PF6 was used as a flame retardant additive. The fibers obtained in this example showed appreciable flame retardant properties. When NH4PO2F2 was used as an additive, a similar result was obtained. Example 20 0 86 99 parts of a copolymer comprising 91% acrylonitrile, 3% vinyl bromide, and 6% vinyl acetate, and 1 part ammonium metaphosphate NH4PO3 were dissolved in a dimethylacetamide to make a spinning solution. The spinning solution was spun wet in the usual manner. The fibers obtained had good self-extinguishing properties. Example 21 0 87This example was the same as example 11, except that 5% ammonium magnesium phosphate (NH4MgPO4) was used as a flame retardant additive. 88 The fibers obtained in the example showed excellent self-extinguishing properties and good whiteness. 089 Ammonium cobalt phosphate NH4CoPO4 and ammonium manganese phosphate NH4MnPO4 showed similar effects as flame retardant additives. Example 22 0 90 95 parts of a copolymer comprising 92.7% acrylonitrile, 7% vinyl acetate, and 0.3% sodium metall sulfonate, and 5 parts of diaminophospho trichloride Cl3P(NH2)2, which had been previously coated with a paraffin, were dissolved in dimethyl acetamide to give a spinning solution. The fibers obtained from this spinning solution showed good flame-retardant properties. Example 23 0 91A polymer comprising 94% acrylamide, 5.7% methyl acrylate, and 0.3% metall sulfonate was dissolved in dimethylformamide to give a spinning solution. The ammonium salt of metaphosphimic acid P3N3O6H3(NH4)3.H2O was pulverized and coated with a silicone grease using a method similar to that described in Example 13. 3.8% (based on the copolymer) of the above coated material was added to the dope from which an acrylic fiber was prepared by dry spinning. 92 The textile properties and whiteness of the fiber were similar to those of conventional acrylic fibers. A cloth made from the obtained fiber showed good self-extinguishing properties in a vertical test. Example 24 0 93A copolymer comprising 93% acrylonitrile and 7% vinyl chloride was dissolved in dimethylacetamide to give a spinning solution. Primary magnesium phosphate hydrate MgH4(PO4)2.3H2O (3% based on the copolymer) that had been previously coated with a 69°C melting paraffin was added to this solution, and the solution was wet centrifuged, followed by stretching 5 times its original length, then washed and dried. After drying, the fibers were steam-annealed. The fibers obtained had similar textile properties and good whiteness. Analytical data showed that all the magnesium phosphate was retained in the fiber. 96After a cloth made from the obtained fibers was dried at 105° for 3 hours, it was subjected to a flame retardancy test using a vertical method. The cloth showed excellent self-extinguishing properties. When the same inorganic compound was used without paraffin coating, the resulting fibers turned yellowish during the drying and annealing processes. Example 25 0 98A polymer comprising 91% acrylamide and 9% methyl acrylate was dissolved in a 46% aqueous solution of sodium thiocyanate to prepare a spinning solution having a copolymer concentration of 11%. To this solution, a paraffin-coated disodium phosphate powder Na2HPO4 (3% based on the copolymer) was added. The solution was spun in a spinning bath consisting of a 12% aqueous solution of sodium thiocyanate at -3°C. The textile properties and whiteness of the fiber obtained were similar to those of a conventional acrylic fiber. Analysis showed that all the sodium phosphate used was retained in the fiber. A thick cloth made from the fiber was subjected to a vertical flame retardant test (JIS L1091-A-4). The cloth was found to have excellent self-extinguishing properties. Example 26 0100A copolymer comprising 91% acrylonitrile, 3% vinyl bromide, and 6% acrylamide was dissolved in a dimethyl sulfoxide to prepare a spinning solution. To this, 1.5% (based on the copolymer) of an equimolar mixture consisting of a paraffin-coated disodium hydrogen phosphate hydrate Na2HPO4.12H2O and ammonium carbonate was added. From this spinning solution, an acrylic fiber was prepared in the usual manner. Analysis showed that all inorganic materials were retained in the fiber. A cloth made from the obtained fibers showed excellent self-extinguishing properties in both a vertical and a 45° test. A terrycloth made from the fiber showed perfect non-flammability by a urotropin test (Example 3). 102Although preferred embodiments of the invention have been described, modifications and variations are obviously possible in light of the above teachings. Therefore, it should be understood that within the scope of the appended claims, the invention may be practiced in a manner other than that specifically described.

Claims

1 / 2 CLAIMS 1) SELF-EXTINGUISHING POLYMERIC COMPOSITIONS AND PRODUCTION PROCESS, comprising a poly(ethylene oxide), preferably, and a flame retardant additive characterized by (1) 10-25% by weight, in the total composition, of an ammonium or amine phosphate; and (2) 10-25% by weight, of the total composition, of a product obtained by bulk reaction, at a temperature between 80ºC and 230ºC, (a) at least one organic compound selected from the group consisting of (i) linear or cyclic compounds containing nitrogen having at least one >CnO or >CnS group and at least one –NH group—being part of the linear chain or ring, and (ii) amine compounds; with (b) an epoxyalkyl acid ester of formula: n STR1 n where n is an integer from 1 to 3;the reaction being carried out according to a molar ratio (a):(b) between 3:1 and 0.1:1, w / w mol 2) SELF-EXTINGUISHING POLYMERIC COMPOSITIONS AND PRODUCTION PROCESS, according to claim 1, characterized by comprising applications in organic vegetable fiber, cotton fabric, rubber, paint and varnish, wood, plaster, cement, drywall, civil construction in general, containing in the form of finely pulverized crystals coated with an inactive material at least one inorganic compound in an amount of up to 10% based on the total weight of the active ingredient; 2 / 2 being selected and having more than 10 carbon atoms, and vegetable oil, said inorganic compound comprising an ammonium salt of an acid selected from the group consisting of phosphoric acid and metaphosphoric acid, said synthetic fiber being made of an acrylamide polymer; 3) SELF-EXTINGUISHING POLYMERIC COMPOSITIONS AND PRODUCTION PROCESS, according to claim 2, characterized by comprising a production process in which, during the production of the synthetic fiber, said inorganic material is added to a spinning solution and this spinning solution is extruded through holes in a row. 4) SELF-EXTINGUISHING POLYMERIC COMPOSITIONS AND PRODUCTION PROCESS, according to claim 2, characterized by the inorganic compounds being finely pulverized and then coated with an inactive material being selected from organic ions having more than 10 carbon atoms, and vegetable oil, and the coated inorganic compounds being added to the spinning solution.5) Self-extinguishing polymeric compositions and production process, according to claim 2, characterized in that the polymer comprises 91-94% acrylamide monomer. 6) Self-extinguishing polymeric compositions and production process, according to claim 2, characterized in that the synthetic fiber comprises ammonium dihydrogen phosphate, diammonium hydrogen phosphate or triammonium phosphate.

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