Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/40—Nitrogen atoms
  • C07D251/54—Three nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/06—Phosphorus compounds without P—C bonds
  • C07F9/08—Esters of oxyacids of phosphorus
  • C07F9/09—Esters of phosphoric acids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/06—Organic materials
  • C09K21/10—Organic materials containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/06—Organic materials
  • C09K21/12—Organic materials containing phosphorus

Definitions

• the present disclosure relates to the field of flame-retardant materials. More specifically, the disclosure relates to flame-retardant compounds, compositions, uses, and methods of producing thereof.
• Flame-retardant or fire-retardant (FR) compounds are substances added to manufactured products in order to reduce the risk of damage caused by fire. These compounds are applied to the products to minimize the probability of harm to humans, property, or the environment.
• the products can be made of polymer, wood, or textiles.
• the FR compound can be added as a raw material or as part of a composition that can be incorporated by impregnation, coating, or as a part of the product manufacturing process, such as in a master batch. By certain physical and chemical mechanisms, the added compound can prevent burning or slow the spread of a fire in the designated manufactured product.
• 'endothermic degradation' This refers to the energy required for compounds to break down when exposed to high temperatures, such as in a flame.
• 'thermal shielding' i.e., solid phase flame retardancy
• a third example is 'gas phase dilution', in which inert gases, such as carbon dioxide, ammonia, and water, are produced via thermal degradation. These gases act as diluents for the combustible gases, reducing the partial pressure of oxygen and slowing the reaction rate.
• inert gases such as carbon dioxide, ammonia, and water
• These gases act as diluents for the combustible gases, reducing the partial pressure of oxygen and slowing the reaction rate.
• Different flame retardant compounds have their own unique mechanisms of action, determined by their chemical structures. A compound's flame retardation effect can involve one or more mechanisms.
• Melamine is a type of FR that contains a high percentage of nitrogen and does not contain halogens. When melamine undergoes thermal decomposition, it produces inert gases such as NH3 and dilutes the combustible gases in the system to achieve the effect of flame retardation.
• a FR compound based on melamine has some issues such as low degradation temperature, sublimation, leeching, or bleeding during processing or out of the surface of the final product.
• the melamine moiety alone is not sufficient motif by itself to provide flame retardation through several dominant mechanisms of action.
• melamine is only slightly water soluble, which makes it challenging to include in water-based FR compositions. Hence, compositions that rely on melamine are not stable enough to remain homogeneously dispersed during the necessary processing time to implement the FR composition into a designated product.
• the disclosure is directed, in embodiments thereof, to a flame-retardant (FR) compound including a melamine-based positively charged polymer complexed with a phosphate- and/or borate-based negatively charged polymer(s).
• FR flame-retardant
• the advantageous FR compound may be utilized in products, such as plastic, wood, textiles, surface finishes, or coatings.
• a flame/fire can be suppressed, prevented, and/or delayed at the designated manufactured product upon an inclusion of the FR compound provided herein.
• the FR compound may inherently adapt multiple mechanisms of action to retard fire owing to its chemical structure. These may include, in accordance with some embodiments, but are not limited to, endothermic degradation, thermal shielding (via char formation towards solid phase flame retardancy), and gas phase dilution.
• the compound includes numerous melamine that potentially can undergo through a gas phase dilution mechanism of retardation.
• the compound includes numerous covalently bound monomeric units that potentially may act via a mechanism of endothermic degradation.
• the compound including a complex of electrostatically bound positively and negatively charged polymers may act via an additional endothermic degradation mechanism of retardation.
• the compound incorporates multiple units of phosphate which may act via thermal shielding retardation mechanism.
• the FR compound is advantageous as it incorporates well into FR compositions and/or manufactured products.
• a dispersion of FR composition typically based on water, remains stable upon the incorporation of the FR compound.
• the stability of the dispersion is demonstrated for the required duration of handling and/or manufacturing, in accordance with some embodiment, which makes the overall processing more efficient.
• this stable aqueous dispersion is attributed to the highly polar FR complex compound induced by the multiple charged moi eties.
• the complex structure including the electrostatically bound positively and negatively charged polymers, enables the incorporation of high molecular weight molecules, which are otherwise characterized as hydrophobic molecules by nature and may not be included in water compositions, according to some embodiments.
• the production method involves a chemical complexation that benefits from a solid-state chemical reaction.
• the production is facilitated by a by-production of ammonia gas.
• [A'] is represented by formula (CI-1): ination thereof.
• a compound represented by formula (I) is a neutral compound.
• a compound represented by formula (I) is capable of being homogeneously dispersed in a polar protic solvent.
• the solvent includes water.
• the dispersion in the polar protic solvent is stable for at least about 60 hours at room temperature.
• Z is and the compound is represented by the structure:
• the compound of formula (I) is for use as a fire retardant.
• the compound of formula (I) is characterized by a decomposition temperature of at least about 350°C at 25% (w/w) mass loss (Td2s), and of at least about 400°C at 50% (w/w) mass loss (Tdso) upon heating the compound at a heating rate of 20 °C/min under a nitrogen flow of 60 ml/min.
• Td2s mass loss
• Tdso mass loss
• the compound represented by formula (I) facilitates passing a standard flaming test.
• a compound represented by formula (I) facilitates passing a standard flaming test ASTM D6413/D6413M, when incorporated in a textile in an amount of between about 5% and about 50% (w/w).
• X is absent, or is selected from C1-C20 hydrocarbylene, wherein Y is a C1-C20 hydrocarbylene; e and n are integers from 1-1000; n 2 is an integer from 1-100; and
• [A'] is represented by formula (CI-1): ination thereof.
• the compound represented by formula (II) is a neutral compound.
• the compound of formula (II) is capable of being homogeneously dispersed in a polar protic solvent.
• the solvent includes water.
• the dispersion in the polar protic solvent is stable for at least about 60 hours at room temperature.
• X is absent, and the compound is represented by the structure:
• the compound of formula (II) is for use as a fire retardant.
• the compound is being characterized by a decomposition temperature of at least about 350°C at 25% (w/w) mass loss (Td2s), and at least about 400°C at 50% (w/w) mass loss (Tcho) upon heating the compound at a heating rate of 20 °C/min under a nitrogen flow of 60 ml/min.
• the compound of formula (II) when incorporated in textile or plastic material in an amount of at least 5%, facilitates passing a standard flaming test (such as ASTM D6413/D6413M or UL-94).
• a method of producing a compound of formula (I) or (II) includes: providing a first component, wherein the first component is represented by formula (I-N):
• Z is Ci-Cis alkylene, wherein W is Ci-Cis alkylene; and q is an integer from 1-1000; or wherein the first component is represented by formula (II-N):
• X is absent, or is selected from C1-C20 hydrocarbylene, O wherein Y is C1-C20 hydrocarbylene; n is an integer from 1-1000; and n 2 is an integer from 1-100; providing a second component of formula (CI-l-N): bination thereof;
• G + is a cationic counter ion
• G + is NH4 + and/or melaminium.
• the obtained mixture is a powder.
• the mixing is initiated in a solid phase.
• the mixing is performed by using a technique selected from: ball-milling, mortar and pestle, grinding, melting, pelleting, and any combination thereof.
• the mixture is supplemented with an acid.
• the heating is performed at a temperature of at least about 150 °C.
• a compound produced according to the herein disclosed method is provided, in accordance with some embodiments, a compound produced according to the herein disclosed method.
• the compound produced by the herein disclosed method is represented by formula (I):
• Z is Ci-Cis alkylene, wherein W is Ci-Cis alkylene; e and q are integers from 1-1000;
• [A'] is represented by formula (CI-1): mbination thereof.
• the compound produced by the herein disclosed method is represented by formula (II):
• [A'] is represented by the formula (CI-1): ination thereof.
• the compound produced by the herein disclosed method is capable of being homogeneously dispersed in a polar protic solvent.
• the compound produced by the herein disclosed method is characterized by a decomposition temperature of at least about 350°C at 25% (w/w) mass loss (Td2s), and at least about 400°C at 50% (w/w) mass loss (Tdso) upon heating the compound at a heating rate of 20 °C/min under a nitrogen flow of 60 ml/min.
• Td2s mass loss
• Tdso mass loss
• the compound produced by the herein disclosed method when incorporated in a textile or plastic material in an amount of at least about 5% (w/w), facilitates passing a standard flaming test.
• the impregnation is in wood, concrete, and/or textile.
• a flame-retardant composition including the herein disclosed compound, and an acceptable fire-retardant carrier, in a suitable amount, the composition being formulated for incorporation in textiles.
• the composition disclosed herein includes a polar solvent.
• the polar solvent is or includes water.
• a flame-retardant composition including the herein disclosed compound, and an acceptable fire-retardant carrier, in a suitable amount, the composition being formulated for incorporation in plastic material.
• the herein disclosed composition is stable for at least about 60 hours at room temperature.
• the herein disclosed composition further includes another fire retardant.
• a flame retarded plastic material including the compound disclosed herein, optionally in combination with other flame retardants.
• a textile article of manufacture made of or coated with the compound disclosed herein, optionally in combination with other flame retardants.
• Certain embodiments of the present disclosure may include some, all, or none of the above advantages.
• One or more technical advantages may be readily apparent to those skilled in the art from the figures, descriptions and claims included herein.
• specific advantages have been enumerated above, various embodiments may include all, some or none of the enumerated advantages.
• FIGURE 1 - shows a flowchart of steps of a method for producing a fire-retardant compound, according to some embodiments
• FIGURE 2 - shows a thermal gravimetric analysis (TGA) plot for poly(melamine-co-oxalyl) (starting material II-N-IV), acquired while heating the sample from 30 °C - 400 °C at a heating rate of 20 °C/min, under a nitrogen flow of 60 ml/min, according to some embodiments;
• TGA thermal gravimetric analysis
• FIGURE 3 - shows a thermal gravimetric analysis (TGA) plot for poly(melamine-co-oxalyl) tetraborate complex (compound IV-CI-1), acquired while heating the sample from 30 °C - 600 °C at a heating rate of 20 °C/min, under a nitrogen flow of 60 ml/min, according to some embodiments;
• TGA thermal gravimetric analysis
• FIGURE 4 - shows a thermal gravimetric analysis (TGA) plot for poly(melamine-co-oxalyl) polyphosphate complex (compound IV-CI-2), acquired while heating the sample from 30 °C - 600 °C at a heating rate of 20 °C/min, under a nitrogen flow of 60 ml/min, according to some embodiments;
• FIGURE 5 - shows a thermal gravimetric analysis (TGA) plot for poly(melamine-co-oxalyl) tetraborate polyphosphate complex (compound IV-CI-1-2), acquired while heating the sample from 30 °C - 600 °C at a heating rate of 20 °C/min of 60 ml/min, under a nitrogen flow, according to some embodiments;
• FIGURE 6 - shows an ASTM D6413/D6413M analysis report for the flammability resistance of a fabric of polyester/cotton (1 : 1) incorporating poly(melamine-co-oxalyl) polyphosphate complex (compound IV-CI-2), according to some embodiments;
• FIGURE 7 - shows an ASTM D6413/D6413M analysis report for the flammability resistance of a fabric of cotton incorporating poly(melamine-co-oxalyl) polyphosphate complex (compound IV-CI-2), according to some embodiments;
• FIGURE 8 - shows an ASTM D6413/D6413M analysis report for the flammability resistance of a fabric of polyester/cotton (1 : 1) incorporating melamine-functionalized polysiloxane polyphosphate complex (compound I-CI-2), according to some embodiments;
• FIGURE 9 - shows an ASTM D6413/D6413M analysis report for the flammability resistance of a fabric of cotton incorporating melamine-functionalized polysiloxane polyphosphate complex (compound I-CI-2), according to some embodiments;
• FIGURE 10- shows an ASTMD6413/D6413M analysis report for the flammability resistance of a fabric of polyester incorporating poly(melamine-co-urea) polyphosphate complex (compound VII-CI-2), according to some embodiments;
• FIGURE 11 - shows an ASTMD6413/D6413M analysis report for the flammability resistance of a fabric of cotton incorporating poly(melamine-co-urea) polyphosphate complex (compound VII-CI-2), according to some embodiments;
• FIGURE 12- shows an ASTMD6413/D6413M analysis report for the flammability resistance of a fabric of cotton incorporating poly(melamine-co-oxalyl) (starting material II-N-IV), according to some embodiments;
• FIGURE 13- shows an ASTMD6413/D6413M analysis report for the flammability resistance of a fabric of polyester incorporating poly(melamine-co-oxalyl) (starting material II-N-IV), according to some embodiments
• FIGURE 14 - shows a photograph of ABS polymer extrudate incorporating poly(melamine- co-oxalyl) (starting material II-N-IV) upon extrusion, according to some embodiments;
• FIGURE 15 - shows a photograph of ABS polymer extrudate incorporating poly(melamine- co-oxalyl) polyphosphate complex (compound IV-CI-2) upon extrusion, according to some embodiments;
• FIGURE 16 - shows a photograph of ABS polymer grains incorporating poly(melamine-co- oxalyl) (starting material II-N-IV), according to some embodiments;
• FIGURE 17 - shows a photograph of ABS polymer grains incorporating poly(melamine-co- oxalyl) polyphosphate complex (compound IV-CI-2), according to some embodiments;
• FIGURES 18A-B - show UL-94 vertical burning test analysis report for 3.2 mm ABS plastic sticks, which incorporated poly(melamine-co-oxalyl) polyphosphate complex compound (compound IV-CI-2), according to some embodiments;
• FIGURE 18A shows the performance specification, and
• FIGURE 18B shows the requirements for each criterion condition;
• FIGURE 19 - shows UL-94 horizontal burning test analysis report for 1.6 mm ABS plastic sticks, which incorporated poly(melamine-co-oxalyl) polyphosphate complex compound (compound IV-CI-2), according to some embodiments;
• FIGURE 20 - shows UL-94 horizontal burning test analysis report for 1.6 mm ABS plastic sticks, which incorporated melamine-functionalized polysiloxane polyphosphate complex compound (compound I-CI-2), according to some embodiments;
• FIGURE 21 - shows UL-94 horizontal burning test analysis report for 3.2 mm ABS plastic sticks, which incorporated poly(melamine-co-oxalyl) tetraborate complex compound (compound IV-CL1), according to some embodiments.
• fire retardant or “flame retardant” refers to a substance, material or composition designed to reduce the flammability of other associated materials, inhibit the ignition and spread of fire, and enhance fire safety by slowing down the combustion process.
• thermogravimetric analysis refers to a method of thermal analysis in which the mass of a sample is measured over time as the temperature is elevated. TGA can be used to evaluate the thermal stability of a material.
• the term “decomposition temperature (Tdx)” refers to the temperature at which a material chemically decomposes and loses X % (w/w) of its mass, for example, a value of Td25 indicates the temperature at which the material loses 25% of its initial mass weight, at a defined TGA experimental conditions. Td is expressed in units of degrees Celsius (°C). This parameter determines the thermal survivability of the material, according to some embodiments.
• ASTM analysis/method/test refers to a standardized test by the American Society for Testing and Materials.
• a suitable ASTM to determine a fire retardant activity may be ASTM D6413/D6413M, UL-94, or others.
• the terms “wettability” and “water-compatibility” refers to the ability of water to maintain contact with a solid surface of the herein-detailed compound.
• the (direct or indirect) water compatibility characteristic of a compound induces stability of a polar medium, which includes water and/or other polar media, in which the compound is dispersed.
• the term “complex” refers to the association compound formed between oppositely charged oligomer and/or polymer entities. According to some embodiments, the complex is formed by an electrostatic interaction between oppositely charged polyionic oligomer and/or polymer, as well as other optional polar interactions. According to some embodiments, the oligomer and/or polymer can be organic, inorganic, or a combination thereof.
• polysiloxane refers to a polymer consisting of a silicon-oxygen repeating unit backbone.
• an organic group e.g. melamine-containing substituent, is intermittently or periodically bound to the silicone element.
• the term “counter ion” refers to a small molecule ion or a metal ion that accompanies an ionic species in order to maintain electric neutrality of the whole compound.
• the counter ion may be referred to as an anion or a cation, depending on whether it is negatively or positively charged.
• the counterion to an anion will be a cation, and vice versa.
• the terms “solid-state synthesis”, “solid-state reaction”, “solid-phase synthesis”, or “solid-phase reaction” refer to a chemical reaction from solid starting materials to form a new powder/ solid compound.
• C1-C20 hydrocarbylene refers to a hydrocarbon diradical of from 1 to 20 carbon atoms, in which each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched chain, cyclic (having three carbons or more, and including mono- and poly-cyclic, fused and non-fused polycyclic, and bicyclic) or acyclic., and substituted by one or more substituents or unsubstituted.
• alkyl group refers to any saturated aliphatic hydrocarbon, including straight-chain and branched-chain alkyl groups.
• alkyl groups include straight, branched, and cyclic alkyl groups.
• An alkyl group can be, for example, a Ci, C2, C3, C4, C5, Ce, C7, Cs, C9, C10, Cu, C12, C13, C14, C15, Ci6, C17, Cis, C19, or C20, group that is substituted or unsubstituted.
• Non-limiting examples of straight alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, docosyl, and the like.
• Branched alkyl groups include any straight alkyl group substituted with any number of alkyl groups.
• alkylene or "alkylene chain” refers to a straight or branched divalent hydrocarbon chain linking the rest of the molecule through a radical group, for example, methylene, ethylene, propylene, n-butylene, and the like.
• the alkylene chain is attached to the rest of the molecule through a single bond and to the radical group through a single bond.
• the points of attachment of the alkylene chain to the rest of the molecule and to the radical group is through one carbon in the alkylene chain or through any two carbons within the chain.
• alkenyl group refers to any unsaturated aliphatic hydrocarbon, including at least one carbon-carbon double bond.
• An alkenyl group can be, for example, a C2, C3, C4, C5, Ce, C7, Cs, C9, C10, Cu, C12, C13, C14, C15, Cie, C17, Cis, C19, or C20, group that is substituted or unsubstituted.
• alkenylene or “alkenylene chain” refers to a straight or branched divalent hydrocarbon chain linking the rest of the molecule to a radical group, containing at least one carbon-carbon double bond.
• the alkenylene chain is attached to the rest of the molecule through a single bond and to the radical group through a single bond.
• the alkenylene group can be substituted or unsubstituted.
• alkyne refers to a straight or branched hydrocarbon chain, containing at least one carbon-carbon double bond, and having from two to twenty carbon atoms.
• the alkyne chain is attached to the rest of the molecule through a single bond and to the radical group through a single bond.
• the alkyne group can be substituted or unsubstituted.
• alkynylene or “alkynylene chain” refers to a straight or branched divalent hydrocarbon chain linking the rest of the molecule to a radical group, containing at least one carbon-carbon triple bond, and having from two to twenty carbon atoms.
• the alkynylene chain is attached to the rest of the molecule through a single bond and to the radical group through a single bond.
• the alkynylene group can be substituted or unsubstituted.
• cycloalkyl group refers to a saturated or unsaturated cyclic hydrocarbon, including monocyclic or polycyclic groups.
• Non-limiting examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
• Cyclic alkyl groups also include fused-, bridged-, and spiro-bicycles and higher fused-, bridged-, and spiro-systems.
• cycloalkylene refers to a divalent saturated or unsaturated cyclic hydrocarbon, linked to the rest of the molecule through a radical group.
• the cycloalkylene is attached to the rest of the molecule through a single bond and to the radical group through a single bond.
• the cycloalkylene group can be substituted or unsubstituted.
• aryl group refers to an aromatic carbocyclic group.
• An aryl group can be monocyclic or polycyclic.
• Non-limiting examples of aryl groups include phenyl, toluyl, naphthyl, pyrrolyl, pyridyl, imidazolyl, thiophenyl, and furyl.
• Non-limiting examples of substituted aryl groups include phenyl, phenyl, naphthyl including 1 -naphthyl and 2-naphthyl.
• arylene refers to a divalent aromatic carbocyclic group, linked to the rest of the molecule through a radical group.
• the arylene is attached to the rest of the molecule through a single bond and to the radical group through a single bond.
• the arylene group can be substituted or unsubstituted.
• one or more moieties described herein can contain heteroatoms.
• the heteroatoms may include at least one element of nitrogen, oxygen, sulfur, or any combination thereof.
• one or more moieties described herein can be substituted or unsubstituted.
• optional substituents include hydroxyl groups, sulfhydryl groups, halogens, amino groups, nitro groups, nitroso groups, cyano groups, azido groups, sulfoxide groups, sulfone groups, sulfonamide groups, carboxyl groups, carboxaldehyde groups, imine groups, alkyl groups, halo-alkyl groups, alkenyl groups, halo-alkenyl groups, alkynyl groups, halo-alkynyl groups, alkoxy groups, aryl groups, aryloxy groups, aralkyl groups, arylalkoxy groups, heterocyclyl groups, acyl groups, acyloxy groups, carbamate groups, amide groups, ureido groups, epoxy groups, and ester groups.
• optional substituents include halogen, haloalkyl, hydroxy, alkoxy, haloalkoxy, cycloalkyl, aryl, heterocyclyl, heteroaryl, amido, alkylamido, dialkylamido, nitro, amino, cyano, azido, oxo, alkylamino, dialkylamino, carboxyl, thio, thioalkyl and thioaryl.
• compounds described herein can contain an asymmetric atom (also referred as a chiral center), and some of the compounds can contain one or more asymmetric atoms or centers, which can thus give rise to optical isomers (enantiomers) and diastereomers.
• asymmetric atom also referred as a chiral center
• the present teachings and compounds disclosed herein include such enantiomers and diastereomers, as well as the racemic and resolved, enantiomerically pure R and S stereoisomers, as well as other mixtures of the R and S stereoisomers and pharmaceutically acceptable salts thereof.
• Optical isomers can be obtained in pure form by standard procedures known to those skilled in the art, which include, but are not limited to, diastereomeric salt formation, kinetic resolution, chiral separation by HPLC, simulated moving bed chromatography (SMB), and asymmetric synthesis.
• the present teachings also encompass cis and trans isomers (Z and E) of compounds containing alkenyl moieties (e.g., alkenes and imines). It is also understood that the present teachings encompass all possible regioisomers, and mixtures thereof, which can be obtained in pure form by standard separation procedures known to those skilled in the art, and include, but are not limited to, column chromatography, thin-layer chromatography, and high-performance liquid chromatography.
• Z is Ci-Cis alkylene, wherein W is Ci-Cis alkylene; e and q are integers from 1-1000;
• [A'] is represented by formula (CI-1): ination thereof.
• the compound is neutral.
• the charge is single or double, delocalized at the melamine moiety, and the formula may be further represented by formula (I’), (1(2+)), (I’(2+)), or any tautomer thereof.
• n and q are each independently integers from: 5-200, 100-200, 100-500, 200-300, 300-400, 400-500, 100-700, 500-600, 600-700, 700-800, 800-900, and 900-1000. Each possibility is a separate embodiment.
• formula (I) represents a compound of a complex.
• the complex includes a polysiloxane functionalized with a positively charged melamine moiety complexed together with a negatively charged inorganic polymer (CI-1), (CI-2), or a combination thereof.
• the complex includes cross-linked polymers.
• the complex includes partially cross-linked polymers.
• the cross-linking of the polymers is induced by polar and/or electrostatic interactions between the oppositely charged polymers and/or oligomers.
• the cross-linking of the polymers is induced by the structure of the polymer and/or oligomer neutral starting materials.
• the polysiloxane includes repeating units of SiCh array.
• the polysiloxane is a three- dimensional network of -O-Si-O- repeating moieties further bound to positively charged melamine moieties through the Si.
• the polysiloxane is a bulk silica.
• the polysiloxane may be an amorphous silica.
• the polysiloxane may be partially amorphous silica and partially crystalline.
• a symbol “ ”, as detailed in formula (I), denotes the point(s) of attachment of a radical to a defined portion(s) of the compound.
• the symbol denotes the point(s) of attachment of Si or O atoms of one monomer to consecutive Si or O atoms of another monomer.
• the symbol “ ”, as detailed in formula (I), denotes the point(s) of attachment of an organic substituent radical to a defined organic portion(s) radical of the compound.
• the organic portion(s) radical refers to any Ci-Cis alkylene, for example, , i.e. C 3 H 6 .
• Z is Ci-Cis alkylene
• W is Ci-Cis alkylene, according to formula (I).
• Ci-Cis alkylene is selected from the group consisting of CH2, C2H4, C3H6, C4H8, C5H10, CeHu, C7H14, CsHie, C9H18, C10H20, C11H22, C12H24, C13H26, C14H28, C15H30, C16H32, C17H34, and C18H36.
• the Ci-Cis alkylene is straight, branched, further substituted, unsubstituted, or containing heteroatom.
• Ci-Cis alkylene is CsEfc.
• Z is , i.e. C3H6, and the compound is represented by the structure of compound (I):
• the [A]' e of compound (I) is (CI-1), and the compound is represented by the structure of compound (I-CI-1):
• the [A]' e of compound (II) is (CI-2), and the compound is represented by the structure of compound (II-CI-2):
• X is absent, or is selected from substituted or unsubstituted C1-C20 hydrocarbylene, substituted or unsubstituted C1-C20 hydrocarbylene; e and n are integers from 1-1000; n 2 is an integer from 1-100; and
• [A'] is represented by formula (CI-1): ination thereof.
• n and e are each independently integers from: 5-200, 100-200, 100-500, 200-300, 300-400, 400-500, 500-600, 100-700, 600-700, 700-800, 800-900, and 900-1000.
• the compound of formula (II) is a complex consisting of oppositely charged polymers and/or oligomers.
• the first polymer is an organic polymer consisting of positively charged melamine-based monomers
• the second polymer and/or oligomer includes negatively charged monomers of borate or phosphate.
• the polymers are interacting via electrostatic interactions and/or via other polar interactions.
• the polymers are at least partially cross-linked.
• the (substituted or unsubstituted) Ci- C20 hydrocarbylene of X may include alkyl, alkylene, alkenyl, alkenylene, alkynyl, alkynylene, cycloalkyl, cycloalkylene, aryl, arylene, or any combination thereof.
• the symbol “ ”, as detailed in formula (II), denotes the point(s) of attachment of an organic substituent radical to a defined organic portion(s) radical of the compound.
• the organic portion(s) radical may refer to , i.e. C5H10.
• X is absent, and the compound is represented by the structure:
• the [A]' e of compound (III) is (CI-2), and the compound is represented by the structure of compound (III-CI-2):
• X is O
• the compound is represented by the structure:
• the [A]' e of compound (IV) is (CI-1), and the compound is represented by the structure of compound (IV-CI-1):
• the [A]' e of compound (IV) is (CI-2), and the compound is represented by the structure of compound (IV-CI-2):
• the [A]' e of compound (IV) includes (CI-1) and (CI-2), and the compound is represented by the structure of compound (IV-CI-1-2):
• X is wherein Y is a (substituted or unsubstituted) C1-C20 hydrocarbylene.
• the substituted or unsubstituted C1-C20 hydrocarbylene may include alkyl, alkylene, alkenyl, alkenylene, alkynyl, alkynylene, cycloalkyl, cycloalkylene, aryl, arylene, or any combination thereof.
• the [A]' e of compound (V) includes (CI-1), and the compoundsented by the structure of compound (V-CI-1):
• the [A]' e of compound (V) includes (CI-2), and the compoundsented by the structure of compound (V-CI-2):
• the [A]' e of compound (VI) includes (CI-1), and the compound is represented by the structure of compound (VI-CI-1):
• the [A]' e of compound (VI) includes (CI-2), and the compoundsented by the structure of compound (VI-CI-2):
• the [A]' e of compound (VII) is (CI-2), and the compound is represented by the structure of compound (VII-CI-2):
• the [A]' e of compound (VII) is (CI-1), and the compound is represented by the structure of compound (VII-CI-1):
• the [A]' e of compound (VIII) is (CI-1), and the compound is represented by the structure of compound (VIII-CI-1):
• the [A]' e of compound (VIII) is (CI-2), and the compound is represented by the structure of compound (VIII-CI-2):
• the [A]' e of compound (IX) is (CI-1), and the compound is represented by the structure of compound (IX-CI-1):
• the [A]' e of compound (IX) is (CI-2), and the compound is represented by the structure of compound (IX-CI-2): Compound (IX-CI-2)
• the compound is characterized by a watercompatibility that is higher by at least about 1.5-3-fold compared to its corresponding uncharged starting material, for example, about 3-5-fold, about 5-6-fold, about 6-8-fold, about 8-10-fold, or about 10-13-fold. Each possibility is a separate embodiment. According to some embodiments, the compound is more hydrophilic compared to its corresponding uncharged starting material.
• the compound is capable of being homogeneously dispersed in a polar protic solvent.
• the compound is capable of being homogeneously dispersed in a polar protic solvent that is water.
• the polarity of the complex compound which is induced by the charged moieties and represented in formulas (I) and/or (II), facilitates dispersion thereof within the polar protic solvent.
• the polarity induced by the (stabilized) charged moieties of the complex compound, as represented in formulas (I) and/or (II) facilitates its dispersion in water.
• the dispersion of the compound in the polar protic solvent is stable for at least about 60 hours at room temperature, for example, for at least about 80 hours, 100 hours, 120 hours, 140 hours, 160 hours, or 180 hours.
• the polar protic solvent may include methanol, ethanol, butanol, isopropanol, water, or a combination thereof.
• the polar protic solvent includes water.
• the polar protic solvent may be incorporated in a FR composition.
• the FR composition incorporates water as the polar protic solvent.
• the FR composition is used to facilitate the application of the FR compound to a designated manufactured product, such as textile.
• the FR compound is hydrophilic and is, therefore, dispersed in a polar protic solvent.
• the FR compound is hydrophilic and is, therefore, well dispersed in water.
• the FR compound is hydrophilic due to polarity induced by the stabilized charged moieties of the complex.
• the charged moieties may include borate, phosphate, and charged melamine, as detailed herein.
• the polarity induced by the (stabilized) charged moieties of the complex compound facilitates its homogenous incorporation in a master batch.
• a master batch is a mixture of additives dispersed in a carrier resin and it is used in plastics manufacturing to modify properties such as FR, color, mechanical properties, etc. The additives are blended and extruded together with the resin.
• the FR compound disclosed herein is homogenously dispersed in a master batch.
• the dispersion is facilitated by the polarity of the complex compound.
• the dispersion is facilitated by the charged moieties of the complex compound.
• the dispersion of the herein disclosed FR compound is maintained homogenous throughout the production process. In some embodiments, the dispersion of the herein disclosed FR compound is maintained homogenous throughout the extrusion process. In some embodiments, the herein disclosed FR compound facilitates the production of a homogeneous product. In some embodiments, the herein disclosed FR compound facilitates the production of a smooth product.
• the compound of formula (I) and/or (II) is characterized by a decomposition temperature of at least about 350 °C at 25% (w/w) mass loss (Td 25 ) upon heating the compound at a heating rate of 20 °C/min under a nitrogen flow of 60 ml/min, for example, at least about 400 °C, at least about 425 °C, at least about 450 °C, or at least about 500 °C.
• a decomposition temperature of at least about 350 °C at 25% (w/w) mass loss (Td 25 ) upon heating the compound at a heating rate of 20 °C/min under a nitrogen flow of 60 ml/min, for example, at least about 400 °C, at least about 425 °C, at least about 450 °C, or at least about 500 °C.
• Td 25 mass loss
• the compound of formula (I) is characterized by a decomposition temperature of at least about 400°C at 50% (w/w) mass loss (Tdso) upon heating the compound at a rate of 20 °C/min under a nitrogen flow of 60 ml/min, for example, at least about 450 °C, at least about 475 °C, at least about 500 °C, or at least about 600 °C.
• a decomposition temperature of at least about 400°C at 50% (w/w) mass loss (Tdso) upon heating the compound at a rate of 20 °C/min under a nitrogen flow of 60 ml/min, for example, at least about 450 °C, at least about 475 °C, at least about 500 °C, or at least about 600 °C.
• Tdso mass loss
• the compound of formula (I) and/or (II) exhibit high thermal stability which is reflected in its capability to effectively retard flame at high temperatures, as detailed.
• the compound of formula (I) and/or (II) is characterized by a heat stability region that spans up to at least about 550 °C, for example, at least about 600 °C, at least about 600 °C, or at least about 650 °C. Each possibility is a separate embodiment.
• the compound of formula (I) or (II) disclosed herein is capable to retard flame when incorporated into paint, textile, plastic, coating, and/or impregnation. According to some embodiments, the compound is capable to retard flame when impregnated in wood, concrete, and/or textile. Each possibility is a separate embodiment.
• the compound of formula (I) or (II) disclosed herein is characterized by flame retardation activity.
• the compound disclosed herein is capable to retard flame when incorporated into a plastic material.
• the compound disclosed herein is characterized by a flame retardation activity when incorporated into textiles. The compound disclosed herein prevents the burning of the textiles in which it is incorporated.
• the compound exhibits flame retardation activity according to ASTM D6413 / D6413M-15 vertical flammability test.
• the compound is capable of minimizing a char length by at least about 2-fold compared to a corresponding melamine-based neutral polymer.
• the compound of formula (I) or (II) disclosed herein when incorporated in a textile or plastic material in an amount of at least about 5% (w/w), facilitates passing a standard flaming test.
• the herein disclosed compound facilitates passing a standard when incorporated in a textile or plastic material in an amount of at least 2%, 5%, 7%, 10%, 15%, 20%, 25%, 30%, 35%, or 40% (w/w) .
• Each possibility is a separate embodiment.
• the compound of formula (I) or (II) disclosed herein enables passing a standard flaming test ASTM D6413/D6413M.
• the compound of formula (I) or (II) disclosed herein enables passing a standard flaming test ASTM D6413/D6413M, when incorporated in a textile in an amount of at least about 2%, 5%, 7%, 10%, 15%, 20%, 25%, 30%, 35%, or 40% (w/w).
• the incorporation of the herein disclosed FR compound in textiles or plastic material can be, in some embodiments, in an amount of between about 5% and about 50% (w/w).
• the incorporation of the herein disclosed FR compound can be, in some embodiments, in an amount of between about 10% and about 40%, between about 20% and about 40%, or between about 10% and about 30%.
• each possibility is a separate embodiment.
• the compound of formula (I) or (II) disclosed herein enables passing a standard flaming test (e.g., UL-94), when incorporated in a plastic material, such as ABS, in an amount of at least about 2%, 5%, 7%, 10%, 15%, 20%, 25%, 30%, 35%, or 40% (w/w).
• a standard flaming test e.g., UL-94
• the herein disclosed compound enables passing a standard flaming test (e.g., UL-94), when incorporated in a plastic material in an amount of between about 15% and about 50% (w/w), for example, 20-50%, 20-45%, 20-40%, 25-40%, or 30-40% (w/w) of the plastic material.
• a standard flaming test e.g., UL-94
• the FR compound may display several possible mechanisms of action towards fire retardation.
• the advantageous FR compound includes a plurality of melamine moieties that can form ammonia gas when exposed to a flame/fire.
• the inert gas dilutes the combustible gas, such as oxygen, thereby reducing the flame potential near the FR compound and the designated manufactured product in which it is implemented.
• the advantageous FR compound disclosed herein includes high molecular weight polymers.
• the high molecular weight polymers include numerous covalent bonds that can break during an exposure to a fire/flame while absorbing the evolved heat energy, through an endothermic degradation.
• the advantageous FR compound which includes polyphosphate units, can form a protective blocking char layer when exposed to a fire/flame.
• the char layer containing phosphorus may create a barrier between the burned and unbumed parts of the product, thereby preventing the fire from spreading. Therefore, in accordance with some embodiments, the FR compound provided herein may act as FR by multiple synergized mechanisms, and thus may serve as a highly performing FR compound.
• the compound of formula (I) and/or (II) disclosed herein is a fire retardant.
• the compound is physically mixed during and/or after a manufacturing process to obtain a product that is resistant to burning.
• the product may include but is not limited to thermoplastic polymer, thermosetting polymer, metal, paint, fabric, wood, liquid, gel, or a combination thereof. Each possibility is a separate embodiment.
• the compound is used to retard flame when incorporated into paint, coating, and/or in impregnation.
• the compound is used to retard flame when incorporated into paint, coating, and/or in impregnation.
• the compound is used to retard flame when impregnated in wood, concrete, and/or textile.
• the herein disclosed compound of formula (I) or (II) is for use as fire retardant.
• the wood product, into which the compound may be incorporated as FR may be selected from furniture, building, instrument, paper, decoration, art piece, or toy. Each possibility is a separate embodiment.
• the textile product in which the compound may be incorporated as FR, may include but is not limited to cloth, uniform, curtain, household-related product, lab coat, firefighter fire extinguishing uniform, or custom. Each possibility is a separate embodiment.
• the textile product may include but is not limited to fibers of cotton, silk, wool, viscose, polyester, nylon, polyaramid, Nomex, Kevlar, pyrovatex, linen, rayon, lyocell, cellulose, modacrylic, polybenzobisoxazole (PBO), polybenzimidazole (PBI), polysulfonamide (PSA), polyphenylene sulfide, polyacrylic, oxidized polyacrylic, partially oxidized polyacrylic (including partially oxidized polyacrylonitrile), polyether-ketone, or novoloid.
• PBO polybenzobisoxazole
• PBI polybenzimidazole
• PSA polysulfonamide
• polyphenylene sulfide polyacrylic, oxidized polyacrylic, partially oxidized polyacrylic (including partially oxidized polyacrylonitrile), polyether-ketone, or novoloid.
• the thermoplastic polymer or thermosetting polymer product in which the compound may be incorporated as FR includes but is not limited to rubber, polypropylene, polyethylene, polystyrene, polyamide, polyimide, polyester, polyurethane, polycarbonate, polyacrylate, urea formaldehyde, polysulfone, epoxy, neoprene polynitrile, polyphenol, polyolefin, polyvinyl, polyvinyl chloride (PVC), silicone, poly styrene-butadiene, fluorinated poly ethylene-propylene, acrylonitrile butadiene styrene (ABS), ethylene vinyl acetate, polyphenylene oxide, polyethylene terephthalate (PET), polyether, a block copolymer thereof, derivatives thereof, fluoropolymer and co-polymer thereof, further cross-linked form thereof, or a combination thereof.
• rubber polypropylene
• polyethylene polystyrene
• polyamide
• the plastic-containing product in which the FR compound may be incorporated may be selected from but is not limited to electronic device, textile, toy, instrument, furniture, and insulation material. Each possibility is a separate embodiment.
• the FR compound is physically mixed during and/or after a product manufacturing process to obtain a product that is resistant to burning.
• the compound may be incorporated into the product as part of a masterbatch, i.e. during the product’s manufacturing.
• the compound may be applied as part of a concentrated mixture of pigments and/or additives blended and extruded together in a carrier matrix, such as resin or wax.
• the compound-incorporated matrix is utilized to add the FR compound to a manufactured plastic-containing product.
• the matrix may be used for coloring or for imparting other properties.
• the imparted properties may include fire retardation.
• the FR compound may be incorporated into the manufactured product as a raw and/or undiluted compound to introduce fire retardation.
• the FR compound may be applied to a product material or composition upon product’s manufacturing.
• the application of the FR compound may be performed by using a method selected from but not limited to dip coating, spray coating, layer-by-layer deposition, spreading, or a combination thereof. Each possibility is a separate embodiment.
• the FR compound is homogeneously dispersed into the applied FR composition used to implement it in the product, before, and/or after product manufacturing.
• the FR compound is stably and homogeneously dispersed in a FR composition used for, but not limited to, coating, impregnation, textiles, master-batch, pigments, or additives.
• a FR composition used for, but not limited to, coating, impregnation, textiles, master-batch, pigments, or additives.
• the advantageous stable FR dispersion facilitates the processing of the FR compound.
• the advantageous stable FR dispersion facilitates the processing of the rest of the additives implemented in the designated product’s manufacturing.
• a method of fire retardation includes incorporating the herein disclosed compound(s) of formula (I) or (II) in or onto paint, coating an/or impregnation.
• a method of fire retardation the method including incorporating the herein disclosed compound of formula (I) or (II) in impregnation of wood, concrete, and/or textile. Each possibility is a separate embodiment.
• a method of fire retardation including incorporating the herein disclosed compound of formula (I) or (II) in a plastic material.
• a method of producing the compound disclosed herein the method includes: providing a first component, wherein the first component is represented by formula (I-
• - Z is Ci-Cis alkylene, wherein W is Ci-Cis alkylene; and q is an integer from 1-1000; or wherein the first component is represented by formula (II-N):
• G + is a cationic counter ion; mixing the first and the second components to obtain a mixture; and heating the mixture to produce the compound of formula (I) or (II).
• a general route of synthesis of formula (I) is set forth in Scheme 1
• a general route of synthesis of formula (II) is set forth in Scheme 2:
• [GA] e is represented by the structure of (CI-l-N) and/or (CI-2-N), wherein [GA] e comprising G + and [A'];
• G is a natural form of the G + cationic counter ion
• [A'] e is the negatively charged form of (CI-l-N) and/or the (CI-2-N), i.e. (CI-1) and/or (CI-2), and is represented by the structures:
• manufacturing method 100 includes, in accordance with some embodiments, step 110 providing a first component, such as formula (I-N) or formula (II-N).
• a second component such as (CI-l-N) and/or (CI-l-N) is provided, according to some embodiments.
• the first and the second components are mixed to obtain a reaction mixture. According to some embodiments, the two components are solids.
• the mixing may be done, according to some embodiments, via a solid-state synthetic technique, such as ball milling, to grind the two solids together, and later on to obtain a homogeneous product, in accordance with some embodiments.
• the reaction mixture is heated up (to a high temperature of above 150 °C) to provide the FR compound.
• ammonia gas is formed during the synthesis. The ammonia escapes from the reaction mixture and, thereby, facilitates the complexation of the FR product, in accordance with some embodiments.
• the molar ratio between the total e provided and the n or q provided is between 1 : 10 and 10: 1, for example, between 1 :7 and 7: 1, between 1 :3 and 3: 1, or 1 :5 and 5: 1.
• the molar ratio between e and n or q is about 2: 1-1 :2, for example, 2: 1, 1.5: 1, 1.2: 1, 1 : 1, or 1 :2.
• the molar ratio between e and n or q is 1.2: 1.
• the cationic counter ion G + of formula (CI-l-N) and/or (CI-2-N) is a metal cation or a positively charged small molecule.
• the metal can be an alkali metal, alkaline earth metal, transition metal, or main group metal. Each possibility is a separate embodiment.
• the metal is lithium, sodium, potassium, cesium, cerium, magnesium, manganese, iron, calcium, strontium, cobalt, titanium, aluminum, copper, cadmium, or zinc.
• the cationic counter ion can be silver, barium, strontium, nickel, chromium, cobalt, manganese, lead, tin, or mercury. Each possibility is a separate embodiment.
• the second component formula (CI-l-N) and/or (CI-2-N) is a metal salt, for example, a lithium salt, a sodium salt, a potassium salt, a cesium salt, a cerium salt, a magnesium salt, a manganese salt, an iron salt, a calcium salt, a strontium salt, a cobalt salt, a titanium salt, an aluminum salt, a copper salt, a cadmium salt, or a zinc salt.
• a metal salt for example, a lithium salt, a sodium salt, a potassium salt, a cesium salt, a cerium salt, a magnesium salt, a manganese salt, an iron salt, a calcium salt, a strontium salt, a cobalt salt, a titanium salt, an aluminum salt, a copper salt, a cadmium salt, or a zinc salt.
• a metal salt for example, a lithium salt, a sodium salt, a potassium salt, a cesium salt, a cerium salt,
• the cationic counter ion is natural basic amino acids lysine, arginine or histidine, non-natural basic amino acid, EDTA, or a quaternary ammonium cation. Each possibility is a separate embodiment.
• quaternary ammonium salts corresponding to the quaternary ammonium cation can originate from an amine moiety.
• the second component formula (CI-l-N) and/or (CI-2-N) is an ammonium salt.
• (the second component) formula (CI-l-N) and/or (CI-2-N) is a melaminium salt.
• the corresponding amine is a moiety of ammonia, melamine, triethyl amine, diisopropyl amine, ethanol amine, diethanol amine, triethanol amine, morpholine, N- methylmorpholine, piperidine, N-methylpiperidine, N-ethylpipendine, dibenzylamine, piperazine, pyridine, pyrazole, imidazole, or pyrazine.
• ammonia melamine
• triethyl amine diisopropyl amine
• ethanol amine diethanol amine
• triethanol amine morpholine
• N-methylmorpholine piperidine
• N-methylpiperidine N-ethylpipendine
• dibenzylamine piperazine
• pyridine pyrazole
• imidazole imidazole
• pyrazine a moiety of ammonia, melamine, triethyl amine, diisopropyl amine
• an ammonium salt of formula (CI-l-N ) and/or (CI- 2-N) is an ammonia salt, a melamine salt, a triethyl amine salt, a trimethyl amine salt, a diisopropyl amine salt, an ethanol amine salt, a diethanol amine salt, a triethanol amine salt, a morpholine salt, an N-methylmorpholine salt, a piperidine salt, an N-methylpiperidine salt, an N-ethylpiperidine salt, a dibenzylamine salt, a piperazine salt, a pyridine salt, a pyrazole salt, a pyridazine salt, a pyrimidine salt, an imidazole salt, or a pyrazine salt.
• an ammonium salt of formula (CI-1- N) and/or (CI-2-N) is an ammonium salt.
• G + is NEU + , i.e. ammonium cation.
• G + is melaminium cation.
• the mixing of the first component and the second component is initiated in a solid phase.
• the reaction is a solid- state synthesis.
• the first and second components are in a solid state at the initial reaction conditions.
• the reaction is devoid of a solvent.
• the mixing further includes a solvent or a combination of solvents.
• the mixing is performed by using a technique selected from: ball-milling, mortar and pestle, grinding, melting, pelleting, and any combination thereof.
• a technique selected from: ball-milling, mortar and pestle, grinding, melting, pelleting, and any combination thereof.
• the obtained mixture is a powder. According to some embodiments, the obtained mixture is a solid.
• reaction mixture is supplemented with an acid.
• the supplemented acid is boric acid.
• the heating of the reaction mixture is performed at a temperature of at least about 100 °C. According to some embodiments, the heating of the reaction mixture is performed at a temperature of at least about 150 °C, for example, at least about 180 °C, at least about 210 °C, at least about 230 °C, at least about 260 °C, or at least about 290 °C. Each possibility is a separate embodiment.
• the reaction involves the production of a neutral gas.
• the reaction involves the production of an ammonia gas.
• the produced ammonia gas is released and evacuated from the reaction mixture during the production of the FR complex compound.
• the evacuation of ammonia by-product further induces complexation in the FR compound.
• the complex includes fewer or no counter ions compared to the first component starting material.
• the reduction of a counter ion, i.e., formerly an ammonium counter ion induces the charged/electrostatic interaction between the positive and negative polymer/oligomer.
• the release of the ammonia as a neutral species stabilizes the positive charges in the positive polymer to be further complexed with the negative polymer/oligomer, thereby employing the advantageous stability of the final FR complex compound.
• the entropically favored release of ammonia gas may thermodynamically favor the complexation process.
• the compound produced by the method disclosed herein is represented by the formula (I):
• Z is Ci-Cis alkylene, wherein W is Ci-Cis alkylene; e and q are integers from 1-1000;
• [A'] is represented by formula (CI-1): mbination thereof.
• the compound produced by the method disclosed herein is represented by the formula (II):
• X is absent, or is selected from C1-C20 hydrocarbylene, O wherein Y is a C1-C20 hydrocarbylene; e and n are integers from 1-1000; n 2 is an integer from 1-100; and
• the compound produced by the method disclosed herein is capable of being homogeneously dispersed in a polar protic solvent.
• the compound produced by the method disclosed herein is characterized by a decomposition temperature of at least about 350°C at 25% (w/w) mass loss (Td2s), and at least about 400°C at 50% (w/w) mass loss (Tdso) upon heating the compound at a heating rate of 20 °C/min under a nitrogen flow of 60 ml/min.
• the compound produced by the method disclosed herein enables passing a standard flaming test when incorporated in textile or plastic material in an amount of at least about 2% (w/w), between about 5% and about 50% (w/w), or in any other minimum amount or range amount disclosed herein.
• the compound produced by the method disclosed herein enables passing a standard flaming test ASTM D6413/D6413M, when incorporated in textile in an amount of at least about 2% (w/w), between about 5% and about 50% (w/w), or in any other minimum amount or range amount disclosed herein.
• the compound produced by the method disclosed herein enables passing a standard flaming test UL-94, when incorporated in plastic material in an amount of at least about 2% (w/w), between about 5% and about 50% (w/w), or in any other minimum amount or range amount disclosed herein.
• a flame-retardant composition including the herein disclosed compound and an acceptable fire-retardant carrier, in a suitable amount, the composition being formulated for incorporation in textiles.
• the composition includes a polar solvent.
• the polar solvent is or includes water
• the herein disclosed compound is homogenously dispersed in the herein disclosed composition, including the polar solvent, such as water.
• the composition is being stable for at least about 60 hours at room temperature.
• the herein disclosed composition further includes another fire retardant.
• a flame-retardant composition including the herein disclosed compound and an acceptable fire-retardant carrier, in a suitable amount, the composition being formulated for incorporation in plastic material.
• a flame retarded plastic material including the herein disclosed compound.
• a flame retarded plastic material including the herein disclosed compound, optionally in combination with other flame retardants.
• a textile article of manufacture made of or coated with the compound disclosed herein, optionally in combination with other flame retardants.
• the following examples are presented in order to more fully illustrate some embodiments of the invention. They should, in no way be construed, however, as limiting the broad scope of the invention.
• One skilled in the art can readily devise many variations and modifications of the principles disclosed herein without departing from the scope of the invention.
• starting material II-N- V for Compound V
• starting material II-N-VI for compound VI
• Starting material II-N-VIII (for compound VIII) utilizes the addition reaction of the amine moieties of melamine with isocyanate moieties of a 4,4 ‘ -methylenebi s(phenylisocyanate).
• Poly(melamine-co-oxalyl) (see Example 2) (173 gr) and ammonium polyphosphate were mixed (100 gr) and ball-milled together in a ball -milling machine. The mixture was then transferred into a glass beaker coated with aluminum foil with multiple ventilation holes to allow the escape of the evolved ammonia gas. The beaker was placed in an oven and heated for 2 h at 230 °C. The reaction mixture was then allowed to cool down to room temperature, followed by drying in the milling machine.
• the compound poly(melamine-co-oxalyl) polyphosphate complex (compound IV-CI- 2) is prepared by using melamine polyphosphate. Preparation of poly(melamine-co-oxalyl) tetraborate complex compound
• Poly(melamine-co-urea) (see Example 3) (294 gr) and ammonium polyphosphate (100 gr) were mixed and ball-milled together in a ball-milling machine. The mixture was then transferred into a glass beaker coated with aluminum foil with multiple ventilation holes to allow the escape of the evolved ammonia gas. The beaker was placed in an oven and heated for 2 h at 240 °C. The reaction mixture was then allowed to cool down to room temperature, followed by drying in the milling machine.
• a comparative experiment was conducted to evaluate an alternative synthetic pathway for preparing the poly(melamine-co-oxalyl) polyphosphate complex (compound IV-CI-2), utilizing phosphoric acid (instead of the abovementioned disclosed polyphosphate reagent).
• the starting material poly(melamine-co-oxalyl) (starting material II-N-IV) was combined with an aqueous solution of phosphoric acid (50% w/w) at ambient temperature. After an incubation period of 50 minutes, the reaction was terminated, and the resulting powder was washed. Analysis of the recovered powder indicated that the starting polymer (poly(melamine-co-oxalyl)) had undergone hydrolysis of at least approximately 60%. This result demonstrated that the use of phosphoric acid in aqueous solution significantly reduced the formation of the desired complex compound.
• the solid phase method (as in Examples 4-9 above), surprisingly, yielded the desired complex compounds, without detectable hydrolysis.
• the preparation method utilizing polyphosphate reagent preserved the high molecular weight of the melamine-based polymer, enabling the formation of the flame-retardant complex compounds while maintaining polymer integrity and high molecular weight.
• Thermogravimetric analysis TGA
• TGA Thermogravimetric analysis
• FIG. 2 shows a thermogram of a sample of poly(melamine-co-oxalyl) (starting material II-N-IV) demonstrating a non-significant thermal resistance.
• FIG. 3 shows a thermogram of a sample of poly(melamine-co-oxalyl) tetraborate complex (compound IV-CI-1) demonstrating a significant thermal resistance over a region of at least about 550 °C.
• FIG. 4 shows a thermogram of a sample of poly(melamine-co-oxalyl) polyphosphate complex (compound IV-CI-2) demonstrating a significant thermal resistance over a region of at least about 550 °C.
• thermogram 5 shows a thermogram of a sample of poly(melamine-co-oxalyl) tetraborate polyphosphate complex (compound IV-CI- 1-2) demonstrating a significant thermal resistance over a region of at least about 600 °C.
• Dispersion compositions containing the tested compounds were prepared; these contained a surfactant, a wetting agent, a thickener, and acrylic binder emulsion, all of which are standard components in the following flammability tests.
• the dispersion compositions appeared homogenous and remained stable for more than a week. No phase separation was observed.
• composition including the herein disclosed complex compound
• stability of the composition is advantageous since it facilitates the application of the composition to textiles via methods such as spraying, screen printing, or roll-to-roll processes.
• test fabrics were impregnated with the dispersions, and then squeezed to a controlled pick-up of dispersion, followed by drying and curing at 150-160 °C for 3 minutes.
• the tests were performed on fabrics made of cotton, polyester, or a combination thereof.
• the inclusion of the add-on compound in the tested specimen was 5-50% (w/w), or preferably 10- 40% (w/w).
• the objective of this test is to determine whether a fabric including a fire-retarding compound will continue to burn after the source of ignition is removed.
• a specimen of fabric in a size of 12 inches was suspended in an enclosed chamber, secured on three sides. The cut edge of the fabric on the bottom was exposed to a controlled methane flame for 12 seconds. After exposure to the flame, afterflame, afterglow, and char length were measured.
• test results demonstrate the fire-retardant activity of the advantageous complex compounds disclosed herein when incorporated into manufactured textile products.
• it shows the advantage of incorporating a complex consisting of oppositely charged polymer and/or oligomer, as opposed to incorporating a neutral melamine-polymer alone.
• incorporation of FR compounds in plastic materials shows the advantage of incorporating a complex consisting of oppositely charged polymer and/or oligomer, as opposed to incorporating a neutral melamine-polymer alone.
• the compounds disclosed herein were incorporated into plastic material, such as ABS to obtain FR retarded plastic material. Comparable incorporations were performed using corresponding neutral starting materials. The form/shape/texture and the homogeneity of the FR retarded plastic materials were visually examined and compared, after the extrusion.
• FR compound of poly(melamine-co-oxalyl) polyphosphate complex (compound IV-CI-2) in an amount of 30-40% (w/w) of the FR retarded plastic material was mixed with Xibond synergistic agent in an amount of 2-5% (w/w) of the FR retarded plastic material, and with ABS grains in an amount of 55-65% (w/w) of the FR retarded plastic material.
• the obtained mixture was introduced into an extruder and melted at a temperature of above about 220 °C.
• the same procedure was performed using poly(melamine-co-oxalyl) (starting material II-N-IV). As can be seen in FIG.
• FIG. 16 shows a corresponding photo of FR retarded plastic grains that were obtained from the inhomogeneous extrudate incorporating the poly(melamine-co-oxalyl) (starting material II-N-IV). The grains are rough and inhomogeneous.
• FIG. 17 shows a corresponding photo of FR retarded plastic grains that were obtained from the homogeneous extrudate incorporating the poly(melamine-co-oxalyl) polyphosphate complex (compound IV-CI-2). The grains in this case are smooth and homogeneous.
• V-0, V-l, and V-2 assessed how the material responded when positioned vertically and exposed to a 20 mm flame applied twice for 10 seconds each. During testing, the afterflame and afterglow times were recorded, along with observations of whether flaming drips ignited a cotton indicator placed below. Material was classified as V-0, V-l, or V-2 based on how quickly it extinguished and whether it produced flaming drips. V-0 material exhibited the fastest self-extingui shing and produced no flaming drips, while V-l material was allowed slightly longer afterflame times but still could not ignite the cotton. This test provided a rigorous measure of flame retardance for a vertically mounted component.
• HB Horizontal Burning
• test results demonstrate the fire-retardant activity of the advantageous complex compounds disclosed herein when incorporated in plastic products.

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