WO1986002114A1 - New fire-proofing chemical product and method for the production thereof as well as application of the product to a cellulosic material - Google Patents

New fire-proofing chemical product and method for the production thereof as well as application of the product to a cellulosic material Download PDF

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Publication number
WO1986002114A1
WO1986002114A1 PCT/FR1985/000263 FR8500263W WO8602114A1 WO 1986002114 A1 WO1986002114 A1 WO 1986002114A1 FR 8500263 W FR8500263 W FR 8500263W WO 8602114 A1 WO8602114 A1 WO 8602114A1
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product
solution
chemical formula
chemical
iii
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PCT/FR1985/000263
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French (fr)
Inventor
Jean-Marie Leroy
René Delobel
Michel Le Bras
Didier Le Maguer
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Ecole Nationale Superieure De Chimie De Lille
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Publication of WO1986002114A1 publication Critical patent/WO1986002114A1/en

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
    • 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
    • C07F9/90—Antimony compounds
    • C07F9/902—Compounds without antimony-carbon linkages

Definitions

  • the invention relates to new chemicals, in particular usable in flame retardant processes, to a process for manufacturing flame retardants, as well as to an application of the flame retardant to a cellulose-based material.
  • the invention will particularly find its application in the industries exploiting the textile, the paper, the wood, any other cellulosic product, as well as the polymers and plastics.
  • the fireproofing is a known treatment which consists in making little inflammable or hardly inflammable a traditionally flammable material.
  • flame retardant techniques are known in which flame retardants are used which are in the form of soluble flame retardants such as borax or boric acid, but unfortunately such flame retardants have solubility properties which make them unsustainable.
  • a flame retardant must be mainly insoluble in water and must not modify the physical properties of the base material.
  • the main purpose of the present invention is to provide a flame retardant product, in particular intended for a cellulose-based material so that the application of this flame retardant product to the base material makes it possible to obtain a resulting product benefiting from the following advantages:
  • the flame retardant does not modify the physical properties of the base material and does not impose any constraints on its use.
  • the product in particular intended for a cellulose-based material such as a textile material, enabling said base material to have non-flammability properties resistant to washing while leaving it its mechanical characteristics, is characterized in that it has the following chemical formula:
  • the process for manufacturing said product produced according to the present invention is characterized in that it consists:
  • the application of the product produced according to the present invention, on a cellulose-based material such as a textile material, allowing said base material to have non-flammable properties resistant to washing while leaving it its mechanical characteristics, is characterized by the fact that said product of the formula is grafted onto a cellulose ester
  • a flame retardant product grafted onto the cellulose of the base material, such as a textile material, is formed of an ester of cellulose produced by the action of ammonium pyrophosphate on a free radical in cellulose.
  • This cellulose ester has the following chemical formula:
  • a product comprising P & is used as a flame retardant.
  • N The binding of the flame retardant to the basic cellulosic material is chemical in nature and has a great cohesive force in order to resist washing.
  • the material will be impregnated during the fireproofing process with the product produced according to the present invention.
  • the resulting product will have better performance due to an increase in its non-flammability provided by the addition of antimony, nitrogen and phosphorus.
  • the product has the following chemical formula:
  • the process for manufacturing the product of chemical formula (l) comprises the following stages:
  • the first preparation (Sb 2 O 3 , HCl) is added to the second (triethanolamine, Na 2 CO 3 ) at a temperature of at least 80 ° C to obtain the reaction,
  • the temperature is maintained between 80 and 90 ° C, the speed of addition of the first preparation (Sb 2 O 3 , HCl) being limited by the temperature range and the formation of foams, - at the end of the addition, heat the solution to 100 ° C, so as to completely eliminate the foams,
  • a solution comprising between 18 and 19% by weight of antimony is recovered.
  • the solution obtained is enriched by repeating the various steps described above but by replacing the triethanolamine with the solution obtained.
  • This enrichment includes the following stages:
  • a solution of antimony oxide Sb 2 O 3 and concentrated hydrochloric acid is prepared which is gradually heated to a temperature of at least 90 ° C. and which is maintained at this temperature,
  • a second solution is prepared with the unenriched product and sodium carbonate Na 2 CO 3 , the first solution is reacted on the second at a temperature above 80 ° C. until a thick paste is obtained,
  • N-Sb-P synthesis product which has a chemical formula (ll)
  • a solution is prepared with the enriched product of chemical formula (i) in the presence of a solution of phosphoric acid H 3 PO 4 .
  • the precipitates obtained are assayed by filtration at different pH without washing with water.
  • the table below gives, as a function of pH, the N / Sb, P / Sb ratios, and the weight dosage in% of Sb.
  • an N-Sb-P synthetic product can be obtained which has the chemical formula (III) in a manner similar to the process which has just been described, by replacing the phosphoric acid H 3 PO 4 by pyrophosphoric acid H 4 P 2 O 7 .
  • a precipitate is obtained which is assayed at different pH. For a pH of
  • these products have the advantage of being soluble, which facilitates their application to the materials to be treated.
  • these products produced according to the present invention are capable of being grafted onto the material to be flame retarded.
  • N-Sb-P synthesis products which have chemical formulas analogous to (II) and (III) in a manner similar to the methods which have just been described, by replacing the acid.
  • phosphoric H 3 PO 4 by its salts or pyrophosphoric acid H 4 P 2 O 7 by its salts.
  • the N-Sb-P synthetic products of formula (II) or formula (III) can also be obtained from pyrophosphorous acid, its salts or also polyphosphates by means of processes similar to those which have just been described.
  • the products having the chemical formulas (I) or (II) or (III) or similar formulas to a cellulose-based material, in particular a textile material, or any other cellulosic or polymer or plastic material.
  • This application allows the said basic materials to have non-flammability properties resistant to washing while leaving it its mechanical characteristics.
  • the fireproofing of a cellulosic material is carried out by first impregnating this basic material with a solution comprising ammonium pyrophosphate, urea, and one of the products produced according to the present invention. Next, the impregnated cellulosic material is heated to allow the chemical reaction and bridging to take place.
  • the impregnation is carried out at a temperature between 20 and 100 ° C., in one or more stages, and the chemical reaction and the bridging are carried out in one or more stages at a temperature between 100 and 200 ° C.
  • the overall duration of the treatment is variable according to the temperature but it will preferably always be less than two hours.
  • Ventilation is advantageously carried out during the chemical reaction in order to allow the reaction to continue and to avoid side reactions resulting in degradation of the cellulosic material. This ventilation makes it possible to eliminate the water and the products of the reaction.
  • a first solution is prepared with 480 grams of Sb 2 O 3 and 1,400 cm3 of 25% hydrochloric acid solution. This cold dissolution is first started then it is gradually heated to 95 ° C and the mixture is maintained between 90 and 95 ° C.
  • a second solution of 1,530 grams of triethanolamine is prepared, which is fluidized at 40 ° C. and 600 grams of Na 2 CO 3 . Then, the two solutions thus prepared are added at a temperature of at least 80o C.
  • the first solution (HCl, Sb 2 O 3 ) is continued to be added while maintaining the temperature of the mixture between 80 and 90 ° C.
  • the speed of addition being imposed on the one hand by the temperature and on the other hand by the formation of foams.
  • the temperature of the mixture is brought to 100 ° C. until total elimination of the foams. Then, let the flame retardant solution ripen and filter it.
  • the flame retardant solution comprises between 120 and 180 grams per liter of Sb.
  • a first solution of 100 grams of Sb 2 O 3 and 270 cm3 of HCl at 25% and a second solution containing the unenriched solution obtained previously with 200 grams of Na 2 CO is prepared. 3 , These two solutions are mixed while respecting the same parameters, which have been described above for the first mixture, until a thick paste is obtained to which the alcohol is added to make it more fluid.
  • the alcoholic solution is filtered and redistilled under a reduced pressure of 25 mm of mercury and at a temperature up to 110 ° C.
  • the solution enriched with 20% by weight of antimony can then be collected.
  • the flame retardant of the invention is also applicable inside Materials such as polymers or plastics in general, the flame retardant then being a filler included in the finished product.
  • Example 1 A cotton canvas with a density of 250 grams per m2 was treated with a solution of pyrophosphate-urea 210-380 grams per liter. One passage in an aqueous solution containing the product of formula (l) at a rate of 120 grams per liter of Sb Have been realised.
  • the quantity of phosphorus fixed is 2.2% by mass
  • the quantity of antimony fixed is 3.2% by mass.
  • the resistance loss is 21% in warp and 5% in weft.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Fireproofing Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

New chemical products, particularly usable in fire-proofing processes, method for producing fire-proofing products, as well as application of the fire-proofing product to a cellulosic material. The invention finds particularly its application in industries using textile products, paper, wood, and any other cellulosic product as well as polymers and plastic materials. The new chemical product is characterized in that it has the following chemical formula (I): Sb ADN(CH2-CH2-O)3 BD ADN(CH2-CH2-OH)3 BD2. The method for producing said product is characterized in that it comprises the reaction of antimony trioxide Sb2O3 with hydrochloric acid HCl, the preparation of a fluidified triethanolamine solution in presence of sodium carbonate Na2CO3, the reaction of the first preparation with the second preparation at a temperature higher than 80oC. The application of said product to a cellulosic material such as textile material, enabling said base material to present fire-proof properties, resisting to washings while retaining its mechanical characteristics, is characterized in that said fire-proofing product having the chemical formula (I) or (II) or (III) or formulas similar to formulas (II) or (III) is grafted to the cellulose.

Description

Titre : Produit chimique nouveau ignifugeant et procédé de fabrication d produit ainsi qu'application du produit sur un matériau à base de cellulo Title: New flame retardant chemical and process for manufacturing the product as well as application of the product to a cellulo-based material
L' invention est relative à des produits chimiques nouveaux, notamment utilisables dans des processus d'ignifugation, à un procédé de fabrication de produits ignifugeants, ainsi qu'à une application du produit ignifugeant sur un matériau à base de cellulose.The invention relates to new chemicals, in particular usable in flame retardant processes, to a process for manufacturing flame retardants, as well as to an application of the flame retardant to a cellulose-based material.
L' invention trouvera tout particulièrement son application dans les industries exploitant le textile, le papier, le bois, tout autre produit cellulosique, ainsi que les polymères et matières plastiques, L' ignifugation est un traitement connu qui consiste à rendre peu inflammable ou difficilement inflammable un matériau traditionnellement inflammable.The invention will particularly find its application in the industries exploiting the textile, the paper, the wood, any other cellulosic product, as well as the polymers and plastics. The fireproofing is a known treatment which consists in making little inflammable or hardly inflammable a traditionally flammable material.
On connait plusieurs techniques d' ignifugation dans lesquelles on utilise des produits ignifugeants qui se présentent sous la forme d' ignifuge soluble tel que le borax ou l'acide borique mais malheureusement de tels ignifuges présentent des propriétés de solubilité qui les rendent non durables.Several flame retardant techniques are known in which flame retardants are used which are in the form of soluble flame retardants such as borax or boric acid, but unfortunately such flame retardants have solubility properties which make them unsustainable.
Pour être exploité industriellement un ignifuge doit être principalement insoluble dans l' eau et ne doit pas non plus modifier les propriétés physiques du matériau de base.To be exploited industrially, a flame retardant must be mainly insoluble in water and must not modify the physical properties of the base material.
En effet, dans de nombreuses applications en particulier, lorsque le matériau est appelé à être utilisé en plein air ou lorsque le matériau est amené à être lavé, il est indispensable que des produits d' ignifugation utilisés soient non solubles dans l' eau pour conserver aux matériaux traités leurs propriétés ignifuges, On connait des techniques qui utilisent des produits insolubles tels que le WO3 et le SnO2, qui sont accrochés mécaniquement sur le matériau de base. Toutefois, ces produits présentent une faible résistance d' accrochage sur ledit matériau.In fact, in many applications in particular, when the material is to be used in the open air or when the material is to be washed, it is essential that the flame retardants used are insoluble in water in order to preserve to the materials treated their flame retardant properties, techniques are known which use insoluble products such as WO 3 and SnO 2 , which are mechanically attached to the base material. However, these products have a low bonding resistance on said material.
Il est connu par la demande de brevet française N° 84/13.395 un procédé d' ignifugation d'un matériau à base de cellulose et un produit ignifuge et fongicide greffé sur le matériau de base. Le but de cette invention est de présenter un produit ignifugeant greffé sur la cellulose du matériau de base ainsi que son procédé de réalisation en vue d' obtenir un produit résultant ui est insoluble dans l ' eau afin de su orter des lava es et Le produit ignifugeant et fongicide selon la demande N° 84/13.395 est remarquable par le fait qu'il forme un ester de cellulose réalisé par action du pyrophosphate diammonique sur le groupe hydroxyle de la cellulose, Les différentes études sur les techniques d'ignifugation tendent à prouver que les systèmes comportant de l'antimoine, un halogène, du phosphore et de l'azote constituent actuellement les meilleurs ignifuges pour les matériaux à base de cellulose.It is known from French patent application No. 84 / 13.395 a method of flame retardancy of a cellulose-based material and a flame retardant and fungicide product grafted onto the base material. The aim of this invention is to present a flame retardant product grafted onto the cellulose of the base material as well as its production method with a view to obtaining a resulting product which is insoluble in water in order to remove washes and The flame retardant and fungicide product according to application No. 84 / 13.395 is remarkable by the fact that it forms a cellulose ester produced by the action of ammonium pyrophosphate on the hydroxyl group of the cellulose. The various studies on the techniques of flame retardancy to prove that systems containing antimony, halogen, phosphorus and nitrogen are currently the best flame retardants for cellulose-based materials.
Le but principal de la présente invention est de proposer un produit ignifugeant, notamment destiné à un matériau à base de cellulose afin que l'application de ce produit ignifugeant sur le matériau de base permette d'obtenir un produit résultant bénéficiant des avantages suivants :The main purpose of the present invention is to provide a flame retardant product, in particular intended for a cellulose-based material so that the application of this flame retardant product to the base material makes it possible to obtain a resulting product benefiting from the following advantages:
- application sur des matériaux cellulosiques de différentes natures en particulier sur tous les types de tissus cellulosiques,- application on cellulosic materials of different natures, in particular on all types of cellulosic fabrics,
- insolubilité de l'ignifuge dans l'eau afin de supporter les lavages et être utilisable en extérieur,- insolubility of the flame retardant in water in order to withstand washing and to be used outdoors,
- ininflammabilité renforcée par la présence d'antimoine, de phosphore et d'azote. De plus, l'ignifuge ne modifie pas les propriétés physiques du matériau de base et n'apporte aucune contrainte à son utilisation.- non-flammability reinforced by the presence of antimony, phosphorus and nitrogen. In addition, the flame retardant does not modify the physical properties of the base material and does not impose any constraints on its use.
D'autres buts et avantages de la présente invention apparaîtront au cours de la description qui va suivre qui n'est cependant donnée qu'à titre indicatif et qui n'a pas pour but de la limiter.Other objects and advantages of the present invention will appear during the description which follows which is however given only for information and which is not intended to limit it.
Le produit notamment destiné à un matériau à base de cellulose tel qu'une matière textile, permettant audit matériau de base de présenter des propriétés d' ininflammabilité résistant au lavage tout en lui laissant ses caractéristiques mécaniques, est caractérisé par le fait qu'il présente la formule chimique suivante :The product, in particular intended for a cellulose-based material such as a textile material, enabling said base material to have non-flammability properties resistant to washing while leaving it its mechanical characteristics, is characterized in that it has the following chemical formula:
(l) : sb
Figure imgf000004_0001
(l): sb
Figure imgf000004_0001
Le procédé de fabrication dudit produit réalisé selon la présente invention, est caractérisé par le fait qu'il consiste :The process for manufacturing said product produced according to the present invention, is characterized in that it consists:
- à faire agir le trioxyde d'antimoine sur de l'acide chlorhydrique- to act antimony trioxide on hydrochloric acid
- à préparer une solution de triethanolamine fluidifiée en présence de carbonate de sodium, - à faire réagir la première préparation sur la seconde à une température supérieure à 80º C.to prepare a fluidized triethanolamine solution in the presence of sodium carbonate, - reacting the first preparation on the second at a temperature above 80º C.
L'application du produit réalisée selon la présente invention, sur un matériau à base de cellulose tel qu'une matière textile, permettant audit matériau de base de présenter des propriétés d'ininflammabilité résistant au lavage tout en lui laissant ses caractéristiques mécaniques, est caractérisée par le fait que l'on greffe sur un ester de cellulose ledit produit de la formuleThe application of the product produced according to the present invention, on a cellulose-based material such as a textile material, allowing said base material to have non-flammable properties resistant to washing while leaving it its mechanical characteristics, is characterized by the fact that said product of the formula is grafted onto a cellulose ester
(I). L'invention sera mieux comprise à la lecture de la description suivante.(I). The invention will be better understood on reading the following description.
Dans la demande de brevet française N° 84/13.395 dont le texte fait partie intégrante de la présente description, on décrit un produit ignifugeant, greffé sur la cellulose du matériau de base, tel qu'une matière textile, formé d'un ester de cellulose réalisé par action du pyrophosphate diammonique sur un radical libre de la cellulose. Cet ester de cellulose présente la formule chimique suivante :In French patent application No. 84 / 13,395, the text of which forms an integral part of this description, a flame retardant product, grafted onto the cellulose of the base material, such as a textile material, is formed of an ester of cellulose produced by the action of ammonium pyrophosphate on a free radical in cellulose. This cellulose ester has the following chemical formula:
(IV) : Cellulose - P2O7(NH4)1+x H2-x avec o ≤x ≤1(IV): Cellulose - P 2 O 7 (NH 4 ) 1 + x H 2-x with o ≤x ≤1
Selon cette invention, on utilise comme agent ignifugeant un produit comprenant P &. N. La liaison de l'agent ignifugeant sur le matériau cellulosique de base est de nature chimique et présente une grande force de cohésion afin de résister au lavage.According to this invention, a product comprising P & is used as a flame retardant. N. The binding of the flame retardant to the basic cellulosic material is chemical in nature and has a great cohesive force in order to resist washing.
Dans cette invention, on utilise une solution de pyrophosphate diammonique et d'urée et on chauffe le matériau à base de cellulose, imprégné pour permettre à la réaction chimique d'estérification de se réaliser, de ce fait on obtient le pontage sur le radical libre de la cellulose du pyrophosphate diammonique.In this invention, a solution of ammonium pyrophosphate and urea is used and the cellulose-based material, impregnated, is heated to allow the chemical esterification reaction to take place, thus bridging is obtained on the free radical. of ammonium pyrophosphate cellulose.
Pour éviter la fragilité, au lavage de cet ester de cellulose, notamment par échange d'ions, par exemple des ions métalliques ou des cations, le matériau sera imprégné durant le procédé d'ignifugation avec le produit réalisé selon la présente invention.To avoid brittleness, on washing this cellulose ester, in particular by ion exchange, for example metal ions or cations, the material will be impregnated during the fireproofing process with the product produced according to the present invention.
De ce fait, le produit résultant aura de meilleures performances dues à un accroissement de son ininflammabilité procuré par l'apport d'antimoine, d'azote et de phosphore. Selon la présente invention, le produit présente la formule chimique suivante :Therefore, the resulting product will have better performance due to an increase in its non-flammability provided by the addition of antimony, nitrogen and phosphorus. According to the present invention, the product has the following chemical formula:
(I) : Sb p
Figure imgf000006_0001
(I): Sb p
Figure imgf000006_0001
Le procédé de fabrication du produit de la formule chimique (l) comporte les étapes suivantes :The process for manufacturing the product of chemical formula (l) comprises the following stages:
- on prépare une première solution d'oxyde d'antimoine Sb2O3 et d'acide chlorhydrique concentrée HCl que l'on chauffe progressivement jusqu'à une température d'au moins 90° C et que l'on maintient à cette température, - on prépare une deuxième solution de triethanolamine et de carbonate de sodium Na2CO3, en fluidifiant la triethanolamine à 40º C et en additionnant le carbonate de sodium Na2CO3 à ladite triethanolamine fluidifiée.- Preparing a first solution of antimony oxide Sb 2 O 3 and concentrated hydrochloric acid HCl which is gradually heated to a temperature of at least 90 ° C and which is maintained at this temperature , - preparing a second solution of triethanolamine and sodium carbonate Na 2 CO 3 , by fluidizing the triethanolamine at 40 ° C and adding the sodium carbonate Na 2 CO 3 to said fluidized triethanolamine.
- on additionne la première préparation (Sb2O3, HCl) sur la seconde (triethanolamine, Na2CO3) à une température d'au moins 80° C pour obtenir la réaction,the first preparation (Sb 2 O 3 , HCl) is added to the second (triethanolamine, Na 2 CO 3 ) at a temperature of at least 80 ° C to obtain the reaction,
- on maintient la température entre 80 et 90° C, la vitesse d'addition de la première préparation (Sb2O3, HCl) étant limitée par la fourchette de température et la formation de mousses, - en fin d'addition, on fait chauffer la solution jusque 100° C, ce de manière à éliminer totalement les mousses,- the temperature is maintained between 80 and 90 ° C, the speed of addition of the first preparation (Sb 2 O 3 , HCl) being limited by the temperature range and the formation of foams, - at the end of the addition, heat the solution to 100 ° C, so as to completely eliminate the foams,
- on laisse mûrir la solution résultante et on la filtre,- the resulting solution is left to mature and filtered,
- on élimine l'eau par distillation sous pression réduite et les sels résultants de la distillation par filtration du mélange résultant à chaud.- The water is removed by distillation under reduced pressure and the salts resulting from the distillation by filtration of the resulting mixture while hot.
Selon ce procédé, on récupère une solution comprenant entre 18 et 19 % pondéral en antimoine. Selon la présente invention, on enrichit la solution obtenue en recommençant les différentes étapes décrites ci-dessus mais en remplaçant la triethanolamine par la solution obtenue.According to this process, a solution comprising between 18 and 19% by weight of antimony is recovered. According to the present invention, the solution obtained is enriched by repeating the various steps described above but by replacing the triethanolamine with the solution obtained.
Cet enrichissement comporte les étapes suivantes :This enrichment includes the following stages:
- on prépare une solution d'oxyde d'antimoine Sb2O3 et d'acide chlorhydrique concentrée que l'on chauffe progressivement jusqu'à une température d'au moins 90° C et que l'on maintient à cette température,a solution of antimony oxide Sb 2 O 3 and concentrated hydrochloric acid is prepared which is gradually heated to a temperature of at least 90 ° C. and which is maintained at this temperature,
- on prépare une deuxième solution avec le produit non enrichi et du carbonate de sodium Na2CO3, on fait réagir la première solution sur la seconde à une température supérieure à 80° C jusqu'à l'obtention d'une pâte épaisse,- a second solution is prepared with the unenriched product and sodium carbonate Na 2 CO 3 , the first solution is reacted on the second at a temperature above 80 ° C. until a thick paste is obtained,
- on fluidifie ladite pâte résultante au moyen d'alcool,- said resulting paste is fluidized with alcohol,
- on filtre et on redistille le mélange alcoolique sous pression réduite pour le purifier. Grâce à ce procédé d'enrichissement, on obtient alors une solution de l ' ordre de 20 % pondéral en antimoine . De plus, l'intérêt de cet enrichissement est complété par une purification de la solution ignifuge résultante par élimination de triethanolamine. Selon la présente invention, afin d'obtenir des produits présentant des propriétés d' ininflammabilité encore plus importantes notamment par la présence de phosphore, on élabore des produits chimiques nouveaux qui présentent les formules chimiques suivantes :- The alcoholic mixture is filtered and redistilled under reduced pressure to purify it. Thanks to this enrichment process, a solution of the order of 20% by weight of antimony is then obtained. In addition, the advantage of this enrichment is supplemented by a purification of the resulting flame retardant solution by elimination of triethanolamine. According to the present invention, in order to obtain products having even greater non-flammability properties, in particular by the presence of phosphorus, new chemicals are produced which have the following chemical formulas:
Figure imgf000007_0001
Figure imgf000007_0001
Pour obtenir un produit de synthèse N-Sb-P, qui présente une formule chimique (ll), on prépare une solution avec le produit enrichi de formule chimique (i) en présence d'une solution d'acide phosphorique H3PO4.To obtain an N-Sb-P synthesis product, which has a chemical formula (ll), a solution is prepared with the enriched product of chemical formula (i) in the presence of a solution of phosphoric acid H 3 PO 4 .
On dose les précipités obtenus par filtration à différents pH sans lavage à l'eau. Le tableau ci-dessous donne en fonction des pH les rapports N/Sb , P/Sb , et le dosage pondéral en % de Sb.The precipitates obtained are assayed by filtration at different pH without washing with water. The table below gives, as a function of pH, the N / Sb, P / Sb ratios, and the weight dosage in% of Sb.
Solution ignifuge £Flame retardant solution £
Figure imgf000007_0002
Figure imgf000007_0002
On obtient donc un produit présentant la formule chimique (ll).We therefore obtain a product having the chemical formula (II).
Après lavage à l'eau et filtration, y = 0 et le produit est insoluble. Par contre, si y≥ 1,75 le produit est totalement soluble en solution aqueuse. Selon la présente invention, on peut obtenir un produit de synthèse N-Sb-P qui présente la formule chimique (lll) d'une manière voisine au procédé qui vient d'être décrit, en remplaçant l'acide phosphorique H3PO4 par de l'acide pyrophosphorique H4P2O7. En mélangeant la solution enrichie présentant la formule chimique (l) avec de l'acide pyrophosphorique H4P2O7 on obtient un précipité que l'on dose a différents pH. Pour un pH deAfter washing with water and filtration, y = 0 and the product is insoluble. On the other hand, if y ≥ 1.75 the product is completely soluble in aqueous solution. According to the present invention, an N-Sb-P synthetic product can be obtained which has the chemical formula (III) in a manner similar to the process which has just been described, by replacing the phosphoric acid H 3 PO 4 by pyrophosphoric acid H 4 P 2 O 7 . By mixing the enriched solution having the chemical formula (l) with pyrophosphoric acid H 4 P 2 O 7, a precipitate is obtained which is assayed at different pH. For a pH of
4, on obtient un rapport P/Sb de 0,68, un rapport N/Sb de 0,80, et un pourcentage pondéral en Sb de 17,65. Le produit proposé ainsi obtenu se présente sous la forme chimique (lll). Ce produit est soluble si y≥1,25 et est insoluble si y<1,25.4, a P / Sb ratio of 0.68 is obtained, an N / Sb ratio of 0.80, and a weight percentage of Sb of 17.65. The proposed product thus obtained is in the chemical form (III). This product is soluble if y≥1.25 and is insoluble if y <1.25.
Les deux derniers produits obtenus, c'est à dire celui de la formule chimique (ll) ou celui de la formule chimique (lll) présentent l'avantage de comporter du phosphore qui a un effet de synergie avec l'antimoine et l'azote et, de ce fait, les produits sont des meilleurs ignifuges que ceux contenant de l'antimoine seulement.The last two products obtained, that is to say that of the chemical formula (II) or that of the chemical formula (III) have the advantage of comprising phosphorus which has a synergistic effect with antimony and nitrogen and, therefore, the products are better flame retardants than those containing antimony only.
Par ailleurs, ces produits présentent l'avantage d'être solubles ce qui facilite leur application sur les matériaux à traiter. De plus, ces produits réalisés selon la présente invention, sont aptes à être greffés sur le matériau à ignifuger.Furthermore, these products have the advantage of being soluble, which facilitates their application to the materials to be treated. In addition, these products produced according to the present invention are capable of being grafted onto the material to be flame retarded.
Selon la présente invention, on peut obtenir des produits de synthèse N-Sb-P qui présentent des formules chimiques analogues à (ll) et (lll) d'une manière voisine aux procédés qui viennent d'être décrits, en remplaçant l'acide phosphorique H3PO4 par ses sels ou l'acide pyrophosphorique H4P2O7 par ses sels. Les produits de synthèse N-Sb-P de formule (ll) ou formule (lll) peuvent également être obtenus à partir de l'acide pyrophosphoreux, de ses sels ou encore des polyphosphates au moyen de procédés voisins à ceux qui viennent d'être décrits.According to the present invention, it is possible to obtain N-Sb-P synthesis products which have chemical formulas analogous to (II) and (III) in a manner similar to the methods which have just been described, by replacing the acid. phosphoric H 3 PO 4 by its salts or pyrophosphoric acid H 4 P 2 O 7 by its salts. The N-Sb-P synthetic products of formula (II) or formula (III) can also be obtained from pyrophosphorous acid, its salts or also polyphosphates by means of processes similar to those which have just been described.
On peut donc appliquer les produits présentant les formules chimiques (l) ou (il) ou (lll) ou des formules analogues sur un matériau à base de cellulose notamment une matière textile, ou tout autre produit cellulosique ou polymère ou matières plastiques. Cette application permet aux dits matériaux de base de présenter des propriétés d' ininflammabilité résistant au lavage tout en lui laissant ses caractéristiques mécaniques. En particulier, on réalise l'ignifugation d'un matériau cellulosique en imprégnant tout d'abord ce matériau de base avec une solution comprenant du pyrophosphate diammonique, de l'urée, et un des produits réalisés selon la présente invention. Ensuite, on chauffe le matériau cellulosique imprégné pour permettre à la réaction chimique et au pontage de se réaliser.It is therefore possible to apply the products having the chemical formulas (I) or (II) or (III) or similar formulas to a cellulose-based material, in particular a textile material, or any other cellulosic or polymer or plastic material. This application allows the said basic materials to have non-flammability properties resistant to washing while leaving it its mechanical characteristics. In particular, the fireproofing of a cellulosic material is carried out by first impregnating this basic material with a solution comprising ammonium pyrophosphate, urea, and one of the products produced according to the present invention. Next, the impregnated cellulosic material is heated to allow the chemical reaction and bridging to take place.
Selon un mode particulier de l'application, l'imprégnation est réalisée à une température comprise entre 20 et 100° C, en une ou plusieurs étapes, et la réaction chimique et le pontage se réalisent en une ou plusieurs étapes à une température comprise entre 100 et 200° C. La durée globale du traitement est variable selon la température mais elle sera de préférence toujours inférieure à deux heures.According to a particular mode of application, the impregnation is carried out at a temperature between 20 and 100 ° C., in one or more stages, and the chemical reaction and the bridging are carried out in one or more stages at a temperature between 100 and 200 ° C. The overall duration of the treatment is variable according to the temperature but it will preferably always be less than two hours.
On réalise avantageusement pendant la réaction chimique une ventilation afin de permettre la poursuite de la réaction et d'éviter les réactions secondaires ayant pour conséquence une dégradation du matériau cellulosique. Cette ventilation permet d'éliminer l'eau et les produits de la réaction.Ventilation is advantageously carried out during the chemical reaction in order to allow the reaction to continue and to avoid side reactions resulting in degradation of the cellulosic material. This ventilation makes it possible to eliminate the water and the products of the reaction.
L'exemple suivant permet de réaliser un produit de synthèse N-Sb selon la présente invention et présentant une formule chimique (l).The following example makes it possible to produce an N-Sb synthesis product according to the present invention and having a chemical formula (1).
Pour préparer ce produit, on prépare une première solution avec 480 grammes de Sb2O3 et 1.400 cm3 de solution d'acide chlorhydrique à 25 %. On commence d'abord cette dissolution à froid puis on chauffe progressivement jusqu'à 95° C et on maintient le mélange entre 90 et 95° C.To prepare this product, a first solution is prepared with 480 grams of Sb 2 O 3 and 1,400 cm3 of 25% hydrochloric acid solution. This cold dissolution is first started then it is gradually heated to 95 ° C and the mixture is maintained between 90 and 95 ° C.
Par ailleurs, on prépare une deuxième solution de 1.530 grammes de triethanolamine que l'on fluidifie à 40° C et de 600 grammes de Na2CO3. Ensuite, on additionne les deux solutions ainsi préparées et ce à une température d'au moins 80º C.Furthermore, a second solution of 1,530 grams of triethanolamine is prepared, which is fluidized at 40 ° C. and 600 grams of Na 2 CO 3 . Then, the two solutions thus prepared are added at a temperature of at least 80º C.
Lorsque le mélange des deux solutions arrive à une température de 80° C, on continue d'ajouter la première solution (HCl, Sb2O3) en maintenant la température du mélange entre 80 et 90° C. La vitesse d'addition étant imposée d'une part par la température et d'autre part par la formation de mousses. En fin d'addition, on est amené à chauffer un peu le mélange pour maintenir la température à 85° C. En fin d'addition de la solution (HCl, Sb2O3) on porte la température du mélange à 100° C jusqu'à élimination totale des mousses. Fuis, on laisse mûrir la solution ignifuge et on la filtre. A ce stade du procédé, la solution ignifuge comprend entre 120 et 180 grammes par litre de Sb.When the mixture of the two solutions reaches a temperature of 80 ° C., the first solution (HCl, Sb 2 O 3 ) is continued to be added while maintaining the temperature of the mixture between 80 and 90 ° C. The speed of addition being imposed on the one hand by the temperature and on the other hand by the formation of foams. At the end of the addition, it is necessary to heat the mixture a little to maintain the temperature at 85 ° C. At the end of the addition of the solution (HCl, Sb 2 O 3 ) the temperature of the mixture is brought to 100 ° C. until total elimination of the foams. Then, let the flame retardant solution ripen and filter it. At this stage of the process, the flame retardant solution comprises between 120 and 180 grams per liter of Sb.
Puis, on élimine l'eau par distillation sous une pression réduite de 25 mm de Hg à une température allant jusque 110º C. Après cristallisation et filtration à chaud on obtient 960g de solution présentant entre 18 et 19 % pondéral de Sb.Then, the water is removed by distillation under a reduced pressure of 25 mm Hg at a temperature up to 110 ° C. After crystallization and hot filtration, 960 g of solution are obtained having between 18 and 19% by weight of Sb.
Ensuite, pour l'enrichissement de la solution on prépare une première solution de 100 grammes de Sb2O3 et de 270 cm3 d'HCl à 25 % et une seconde solution contenant la solution non enrichie obtenue précédemment avec 200 grammes de Na2CO3, On mélange ces deux solutions en respectant les mêmes paramètres, qui ont été décrits ci-dessus pour le premier mélange, jusqu'à l'obtention d'une pâte épaisse à laquelle on ajoute l'alcool pour la fluidifier.Then, for the enrichment of the solution, a first solution of 100 grams of Sb 2 O 3 and 270 cm3 of HCl at 25% and a second solution containing the unenriched solution obtained previously with 200 grams of Na 2 CO is prepared. 3 , These two solutions are mixed while respecting the same parameters, which have been described above for the first mixture, until a thick paste is obtained to which the alcohol is added to make it more fluid.
On filtre et on redistille la solution alcoolique sous une pression réduite de 25 mm de mercure et à une température allant jusque 110° C.The alcoholic solution is filtered and redistilled under a reduced pressure of 25 mm of mercury and at a temperature up to 110 ° C.
On peut alors recueillir la solution enrichie à 20 % pondéral en antimoine.The solution enriched with 20% by weight of antimony can then be collected.
A la suite de cette préparation, on analyse le produit, ce produit présente alors un rapport N/Sb de 3 ce qui répond à la formule chimique (l).Following this preparation, the product is analyzed, this product then has an N / Sb ratio of 3, which corresponds to the chemical formula (1).
D'autres mises en oeuvre de la présente invention, à la portée de l'Homme de l'Art, aurient pu être envisagées sans pour autant sortir du cadre de celle-ci. Notamment le produit ignifugeant de l'invention est également applicable à l'intérieur de Matériaux tels que des polymères ou des matières plastiques en général, le produit ignifugeant étant alors une charge incluse dans le produit fini. Exemple 1. Une toile de coton de densité 250 grammes par m2 a été traitée par une solution de pyrophosphate-urée 210-380 grammes par litre. Un passage dans une solution aqueuse contenant le produit de formule (l) à raison de 120 grammes par litre de Sb a été réalisé.Other implementations of the present invention, within the reach of ordinary skill in the art, could have been envisaged without departing from the scope thereof. In particular, the flame retardant of the invention is also applicable inside Materials such as polymers or plastics in general, the flame retardant then being a filler included in the finished product. Example 1. A cotton canvas with a density of 250 grams per m2 was treated with a solution of pyrophosphate-urea 210-380 grams per liter. One passage in an aqueous solution containing the product of formula (l) at a rate of 120 grams per liter of Sb Have been realised.
Après chauffage du tissu imprégné, la quantité de phosphore fixée est de 2,2 % en masse, la quantité d'antimoine fixée est de 3,2 % ene masse. La perte de résistance est de 21 % en chaine et de 5 % en trame.After heating the impregnated fabric, the quantity of phosphorus fixed is 2.2% by mass, the quantity of antimony fixed is 3.2% by mass. The resistance loss is 21% in warp and 5% in weft.
Après 10 lavages en machine en présence d'un détergent, la quantité de phosphore fixée n'a pas diminué. Les surfaces brûlées lors des essais d'ignifugation sont de 30 cm2 dans le sens chaine et 34 cm2 dans le sens trame (Test exécuté suivant Norme française G 07 113). After 10 machine washes in the presence of a detergent, the quantity of phosphorus fixed did not decrease. The areas burned during fireproofing tests are 30 cm2 in the warp direction and 34 cm2 in the weft direction (Test performed according to French standard G 07 113).

Claims

REVENDICATIONS
1. Produit chimique nouveau, notamment utilisable dans des processus d'ignifugation, permettant au dit matériau de base de présenter des propriétés d' ininf lammabilité résistant aux lavages tout en lui laissant ses caractéristiques mécaniques, caractérisé par le fait qu'il présente la formule chimique suivante :1. New chemical product, in particular usable in fireproofing processes, allowing said basic material to have flame retardant properties resistant to washing while leaving it its mechanical characteristics, characterized in that it has the formula following chemical:
^ ^
Figure imgf000012_0001
^ ^
Figure imgf000012_0001
4. Produit selon la revendication 1, caractérisés par le fait qu'ils présentent des formules analogues aux formules chimiques (II) et (III), obtenus par réaction des sels des acides à base de phosphore, tels que notamment acide orthophosphorique, pyrophosphorique, pyrophosphoreux, ainsi que des polyphosphates avec le produit chimique présentant la formule (I).4. Product according to claim 1, characterized in that they have formulas analogous to the chemical formulas (II) and (III), obtained by reaction of the salts of acids based on phosphorus, such as in particular orthophosphoric acid, pyrophosphoric acid, pyrophosphorous, as well as polyphosphates with the chemical having the formula (I).
5. Procédé de fabrication d'un produit selon la revendication 1, caractérisé par le fait qu'il consiste : - à faire agir du trioxyde d'antimoine Sb2O3 sur de l'acide chlorhydrique HCl,5. A method of manufacturing a product according to claim 1, characterized in that it consists: - in causing antimony trioxide Sb 2 O 3 to act on hydrochloric acid HCl,
- à préparer une solution de triethanolamine fluidifiée en présence de carbonate de sodium Na2CO3,to prepare a fluidized triethanolamine solution in the presence of sodium carbonate Na 2 CO 3 ,
- à faire réagir la première préparation sur la seconde à une température supérieure à 80°C.- reacting the first preparation on the second at a temperature above 80 ° C.
6. Procédé de fabrication d'un produit selon les revendications 1 et 5, caractérisé par le fait que Ton enrichit la solution obtenue, cet enrichissement consiste :6. A method of manufacturing a product according to claims 1 and 5, characterized in that Ton enriches the solution obtained, this enrichment consists:
- à faire agir du trioxyde d'antimoine Sb2O3 sur de l'acide chlorhydrique HCl,- to act antimony trioxide Sb 2 O 3 on hydrochloric acid HCl,
- à préparer une solution avec le produit de formule chimique (I), non enrichi, et du carbonate de sodium Na2CO3,- to prepare a solution with the product of chemical formula (I), not enriched, and sodium carbonate Na 2 CO 3 ,
- à faire réagir la première préparation sur la seconde à une tempéra ture supérieure à 80°C.- to react the first preparation to the second at a temperature ture above 80 ° C.
7. Procédé de fabrication d'un produit selon les revendications 2 et 5, caractérisé par le fait qu'il consiste à préparer une solution avec le produit de la formule chimique (I) en présence d'acide phosphorique H3PO4, le précipité permettant d'obtenir une synthèse du produit N-Sb-P de formule chimique (II).7. A method of manufacturing a product according to claims 2 and 5, characterized in that it consists in preparing a solution with the product of the chemical formula (I) in the presence of phosphoric acid H 3 PO 4 , the precipitate allowing a synthesis of the N-Sb-P product of chemical formula (II) to be obtained.
8. Procédé de fabrication d'un produit selon les revendications 3 et 5, caractérisé par le fait qu'il consiste à préparer une solution avec le produit de formule chimique (I) en présence d'acide pyrophosphorique H4P2O7, le précipité permettant d'obtenir une synthèse du produit N-Sb-P de formule chimique (III).8. A method of manufacturing a product according to claims 3 and 5, characterized in that it consists in preparing a solution with the product of chemical formula (I) in the presence of pyrophosphoric acid H 4 P 2 O 7 , the precipitate making it possible to obtain a synthesis of the N-Sb-P product of chemical formula (III).
9. Procédé de fabrication d'un produit selon les revendications 4 et 5, caractérisé par le fait qu'il consiste à préparer une solution avec le produit de formule chimique (I) en présence des sels des acides à base de phosphore, tels que notamment acide orthophosphorique, pyrophosphorique, pyrophosphoreux, ainsi que des polyphosphates, le précipité permettant d'obtenir une synthèse de produits N-Sb-P de formules chimiques analogues à (II) ou à (III).9. A method of manufacturing a product according to claims 4 and 5, characterized in that it consists in preparing a solution with the product of chemical formula (I) in the presence of salts of phosphorus-based acids, such as in particular orthophosphoric, pyrophosphoric, pyrophosphorous acid, as well as polyphosphates, the precipitate making it possible to obtain a synthesis of N-Sb-P products of chemical formulas analogous to (II) or to (III).
10. Application du produit selon les revendications 1 ou 2 ou 3 ou 4, sur un matériau à base de cellulose, tel qu'une matière textile, permettant au dit matériau de base de présenter des propriétés d'ininflammabilité résistant aux lavages tout en lui laissant ses caractéristiques mécaniques, caractérisée par le fait que l'on greffe sur la cellulose le dit produit ignifugeant de formule chimique (1) ou (II) ou (III) ou de formules analogues aux formules (II) ou (III). 10. Application of the product according to claims 1 or 2 or 3 or 4, on a cellulose-based material, such as a textile material, allowing said base material to have flammability properties resistant to washing while it leaving its mechanical characteristics, characterized by the fact that the fire-retardant product of chemical formula (1) or (II) or (III) or of formulas analogous to formulas (II) or (III) is grafted onto the cellulose.
PCT/FR1985/000263 1984-09-26 1985-09-25 New fire-proofing chemical product and method for the production thereof as well as application of the product to a cellulosic material WO1986002114A1 (en)

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US6066198A (en) * 1998-03-27 2000-05-23 Ricardo Cuevas B. Process and product for rendering a substance flame resistant

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US2520103A (en) * 1949-02-15 1950-08-22 American Cyanamid Co Method of treating fibrous cellulosic materials to impart flame resistance thereto, compositions therefor, and products thereof
FR2461739A1 (en) * 1979-07-18 1981-02-06 Dufour Deren Ets E Flameproofing of fibrous materials by antimony oxide pptn. - from soln. of antimony tri:chloride and tert. amine contg. added base

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US2519388A (en) * 1948-12-09 1950-08-22 American Cyanamid Co Treatment of fibrous cellulosic materials to impart flame resistance thereto, compositions therefor, and products thereof
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EP0437416A2 (en) * 1990-01-11 1991-07-17 Ciba-Geigy Ag Compositions containing a 2,2',2"-nitrilotriethanol-cyclometallate
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