Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/136—Phenols containing halogens

Definitions

• This invention relates to fire retardant compositions which have particular application as fire retardant agents in;
• Plastic materials such as polyurethanes, epoxy resins, and other thermoset, thermoplastic materials
• precursors thereof are plastic materials (such as polyurethanes, epoxy resins, and other thermoset, thermoplastic materials) and precursors thereof.
• the invention is based on an unexpected synergistic or potentiating interaction between two hitherto known classes of fire retardants, namely (i) halogenated phosphates; and (ii) phenol substituted with one or more halogen atoms.
• the combination of components (i) and (ii) produces a fire retardant having significantly superior fire retardant properties than either of the fire retardants alone, or based on a mere combination of their known properties.
• a fire retardant composition which comprises: (i) at least one halogenated phosphate; and (ii) at least one phenol substituted with one or more halogen atoms.
• Component (i) may be any halogenated phosphate which exhibits fire retardant properties.
• component (i) may be selected from
• TCEP trichloroethyl phosphate
• TCPP trichloropropyl phosphate dimethyl monophosphate
• Component (ii) may be selected from compounds containing one or more phenol rings which are substituted with one or more halogen groups, preferably bromine atoms.
• Compounds having a single phenol ring are preferred is 2,4,6 tribromo phenol (TBP) is particularly preferred.
• composition which comprises a mixture of: (a) TCEP and/or TCPP: and (b) TBP.
• the precise weight ratio of component (i) to component (ii) is generally unimportant.
• the ratio of component (i) to component (ii) may be from 1:0.45 to 1:1.25.
• Component (i) is generally a liquid, and component (ii) a solid.
• component (ii) is added to component (i) to form a saturated or substantially saturated solution, where the ratio of component (i) to component (ii) is about 1:0.86.
• a diluent may be added to the mixture to allow component ratios greater than those that form a saturated solution.
• the fire retardant composition of the invention is a liquid and does not appear to undergo any reactions at temperatures at least up to 73°C. At about 73°C the composition may change colour from a clear liquid to a darker colour (possibly due to bromine release). There appears to be an endothermic reaction at about 110°C.
• T h e f ire retardant composition is soluble in organic solvents such as methanol, ethanol, propanol, butanol, etc.; and is generally insoluble in aqueous solutions.
• a queous solutions may be prepared using commercial emulsifiers such as Teric (a registered trademark of ICI A ustralia Pty. Ltd. ) and using techniques as described in the examples set out below.
• W h en used as a fire retardant in plastics or resins the fire retardant is blended with the components used to form the resin.
• the fire retardant may be mixed with a polyol component (i.e. a hydroxyl containing polymer, see Encyclopedia of Chemical Technology, 3rd
• the polyol blend may, for example, contain from 5 to 80% of the fire retardant composition as hereinbefore described.
• the components of the polyol b lend are suitable for storage for a considerable period of time, i.e., up to six months or more, even at elevated temperatures.
• the polyol blend may additionally contain one or more basic materials, (such as an inorganic or organic base, for example an amine, such as trimethyl amine). W h en present, the base generally comprises from 0.01% to 15% (wt/wt) of the polyol blend.
• the polyol blend may also contain glycerol, silicone, water, CFC, an amine catalyst and a tin catalyst.
• the fire retardant composition may be mixed with both the polyol and isocyanate at the same
• Th e amounts of reactants used in the preparation of urethane foams on a weight basis may vary considerably according to well known methods in the art.
• the proportions of polyol and isocyanate are selected to provide approximately equal amounts ( molar equivalents) of hydroxy and isocyanate f unctionalities, with isocyanate being in slight excess.
• the fire retardant of the invention may constitute from 1 to 50% (wt/wt) of the reaction mixture.
• fire retardant enables high levels of fire retar d ancy to be achieved by the addition of the fire retar d ant into the precursors of polyurethane foam polymers.
• T h e fire retardant exhibits plasticising ef f ects w h ich in part enable cell structures in foams to be easily modified and controlled.
• the fire retardant is readily soluble in commercially available foam prepolymers and as such acts as a viscosity modifier. 4. Polyol blends containing the fire retardant of this invention are relatively stable.
• chlorofluorocarbons may be reduced or omitted from the reaction mixture.
• CFCs chlorofluorocarbons
• the fire retardant in accordance with this invention enables polyurethane foams to be controlled during their blowing phase utilising carbon dioxide gas, f ormed as a reaction between water and isocyanate, as a blowing agent, enabling the elimination or reduction of C FCs and other volatile agents.
• the fire retardant of this invention also reacts as a
• a polyol blend which comprises a polyol and a fire retardant composition as h ereinbefore described, which is free of CFCs.
• Such polyol blends are generally used in the production of polyurethane foams where the blends are reacted with an isocyanate to form the polymer, with carbon dioxide production in the reaction being the expanding gas.
• a polyol blend which comprises a polyol, a fire retardant as hereinbefore described, and low levels of CFCs.
• low levels refers to 0.1% to 17% (wt/wt) of CFC in the polyol mix.
• Conventional polyol formulations generally contain 25% (wt/wt) CFCs or more. CFCs have been implicated in the depletion of the ozone layer, and hence the use of low levels is advantageous.
• Polyol blends containing low levels of CFCs may also contain glycerol, silicone, water, an amine, and a tin catalyst.
• the polyol blend may contain from 5 to 80% of the fire retardant composition as hereinbefore described.
• This invention also relates to polyurethane foams which incorporate fire retardants as described herein; and further relates to polyurethane foams when produced by the reaction of a polyol blend containing a fire retardant, with an isocyanate containing compound.
• the fire retardant compositions described herein may be incorporated into polymeric materials such as polyvinyl chloride (PVC), polyester, polyamide, polyimide, polypropylene, polyethylene, nylon, phenolic resin and acetal resin.
• polymeric materials such as polyvinyl chloride (PVC), polyester, polyamide, polyimide, polypropylene, polyethylene, nylon, phenolic resin and acetal resin.
• PVC polyvinyl chloride
• polyester polyamide
• polyimide polypropylene
• polyethylene polyethylene
• nylon nylon
• phenolic resin and acetal resin acetal resin
• the fire retardant of this invention is simply added to the various reaction mixtures which give rise to above polymeric material.
• the fire retardant is thus incorporated into the polymeric matrix.
• the fire retardant may react to some extent with the components of the reaction mixtures, as long as polymerization or conventional properties of the polymers are not a d versely effected.
• the fire retardant of this invention may also be incorporated into a pulp of cellulose or like fibres for the production of paper, cardboards, etc. Such material exhibits fire retardant properties.
• the fire retardant composition When used as a fire retardant coating or sur f ace treatment, the fire retardant composition may be d iluted with an organic solvent to form, for example, a mixture contains 1% to 90% (wt/wt) fire retardant, an d then sprayed onto a surface which is desired to be coated. On evaporation of the organic solvent, a stable surface coating remains.
• the fire retardant may be incorporated into conventional wood stains to yield a decorative surface.
• compositions of this invention may be applied to furnishings, drapes, carpets, tents, screen cloths, etc to impart fire retardancy. In such cases a stain release, deodorant and the like may be added to the mixture.
• deodorants refers to any compound or number of compounds which have an odour reducing effect, or which impart a pleasant smell to the human and/or animal nose. Deodorants or odour mo d ifiers are described, for example, in the Encyclopedia of Chemical Technology, 3rd Edition, Vol. 16, pp. 297-305, John Wiley & Sons, 1981.
• an aqueous fire retardant In t h e case of surface treatments of textiles, yarns and fabrics it is generally preferred to use an aqueous fire retardant. This is formed by the combination of the compound with a commercial emulsifying agent (such as ICI),
• SUBSTITUTE SHEET Teric 200 which is then diluted with water and applied to the fabric or textiles.
• Application may be by immersion and nip roller to achieve pick up weights of between 20 -90%.
• a high temperature treatment such as about 100°C-250°C
• the resultant cloth exhibits a high degree of fire retardancy. (See Example ).
• a fire retardant composition as defined herein which additionally comprises one or more of the following:
• SUBSTITUTE SHEET application by spraying, dipping, painting and other methods well known in the art for the application of fire retardants.
• Trichloropropyl phosphate (TCPP) and trichloroethyl phosphate (TCEP) were obtained commercially from Akzo Chemicals under the trade names FYROL Pcf and FYROL Cef respectively. Both TCPP and TCEP are liquids at ambient temperatures.
• TCPP and TCEP are liquids at ambient temperatures.
• Tris 2,4,6 tribromophenol and Bis 2,4,6 Tribromophenol (TBP) were obtained from either Great Lakes Chemical Company, West Lafyette, Indiana, U.S.A. or from Bromine Compounds Limited, Beersheva, Israel. These compounds are flaky solids at ambient temperatures.
• Fire retardant compositions were prepared by mixing the brominated phenol with one or both of chlorinated phosphates, until all the brominated phenol is dissolved therein. Warming the chlorinated phosphate, for example to 70°C, promotes solubility of the brominated compound. Where TCPP and TCEP are used in combination, the weight ratio is usually 1:1 however this may vary.
• a range of fire retardant composition were prepared wherein the weight ratio of chlorinated phosphates (TCPP and TCEP) to brominated phenols was from 1:0.45 to 1:1.25.
• TCPP and TCEP chlorinated phosphates
• brominated phenols were from 1:0.45 to 1:1.25.
• a near saturated solution of fire retardant was prepared by dissolving 80g of TBP in lOOg of TCPP.
• Polyol blends containing no CFCs were prepared by deleting the CFC component in the above mix, and raising the amount of water to 2.44 g.
• the above formulations contain 50.5% (wt/wt) fire retardant.
• Formulations the same as above (in the presence and absence of CFC) were prepared which contain from 5 to 63% (wt/wt) fire retardant.
• the above polyol formulations were stable, and could be stored for at least 60 days at elevated temperatures of 60°C without any noticeable deleterious effects.
• Parameters checked include changes in both the viscosity and the colour of the blend and, when reacted with an isocyanate, changes in the reaction time profiles of, Cream, Rise & Gel times (as described in the Polyurethane
• Polyurethane foams are prepared by reacting a hydroxyl-containing polymer (polyol) with a polyfunctional isocyanate as shown in Scheme A, where (1) is polyfunctional isocyanate, (2) a polyol, and (3) a polyurethane
• Polyurethane foams were produced by mixing the polyol formulations with a polyisocyanate, SUPRASEC 5005 (a diisocyanato-diphenylmethane), obtained from ICI Australia Operations Limited.
• SUPRASEC 5005 a diisocyanato-diphenylmethane
• the amount of isocyanate used to react with the polyol was calculated by determining the total equivalents of hydroxyl groups in the polyol formulation, according to methods well known in the art, and described for example in Polyurethane Elastomers by C. Hepburn, Supra. Conventionally, the isocyanate is used in very slight excess. An index of x 1.05 is commonly used.
• the polyol blend of Example 2 would be mixed in a commercial mixer with 56 g of isocyanate. (Suprasec 5005)
• the following formulations were produced: 3a 3b 3c 3d
• Formulation 3a contains no fire retardant.
• Formulations 3c, 3e, 3g and 3h contain increasing amounts of the fire retardant composition of this invention.
• Formulations 3b, 3d and 3f contain increasing amounts of the commercially available fire retardant Fyrol Pcf
• test measures the % of oxygen that will support candlelight combustion. The lower the % oxygen index the more flammable is a material.
• Blend 3b (5.6g)(Conventional formulation) 22.5 Blend 3 ⁇ (5.6g) 23.0 Blend 3d (21g)(unstable foam) 23.5
• Blend 3h (53g) 28.5 These results show that foams produced using conventional fire retardants have a lower percentage oxygen index, and thus are more flammable than those foams produced utilising the fire retardant composition of this invention. It is to be noted that small increases in the percentage in oxygen index correspond to significant increases in fire retardancy. For example, a difference of 0.5 in the percentage oxygen index between formulation 3b (containing a conventional fire retardant) and formulation 3c (containing the fire retardant composition of this invention) is indicative of a significant decrease in lammability of the foam produced by composition 3c.
• the foam produced from blends 3b, 3d and 3f was inferior when compared to foams produced using the same level of the fire retardant of the invention, insofar as flammability and stability are concerned.
• Formulations according to blends 3b, 3d and 3f were also produced, where the fire retardant Fyrol Pcf was replaced with halogenated phosphates, trichloroethyl phosphate (TCEP), and dimethylmono phosphate (DMMP), and with tribromophenol (TBP).
• TCEP trichloroethyl phosphate
• DMMP dimethylmono phosphate
• TBP tribromophenol
• the percentage oxygen index of the foams produced using halogenated phosphates generally corresponded to those obtained using the fire retardant Fyrol Pcf (TCPP).
• the foams produced using TBP were of very poor quality and possessed a very low percentage oxygen index, below about 19.
• Example 1 The formulation of Example 1 was advantageous as stable foams could be produced in the presence of large quantities of fire retardant (see blends 3g and 3h). In contrast, formulations containing more than 21 g of Fyrol Pcf or other halogenated phosphates were physically inferior (poor dimensional stability and low closed cell count) and gave rise to unstable foams. Foams produced using the fire retardant TBP were of very poor quality and were generally unstable regardless of the amount of TBP used.
• Example 1 The fire retardant composition of Example 1 was diluted in methanol to give 20% (w/w) fire retardant composition. This material was sprayed onto needled polypropylene (a ribbed wall covering manufactured by Melded Fabrics Pty Ltd of Melbourne) and allowed to dry. Dry pick up weight was 15.7%
• the material was then washed 10 times with hot water containing a detergent.
• the treated material exhibits excellent fire retardancy as measured by ASTM method FMVSS 302, a horizontal burn test (see - International Plastics Flammability Handbook, Author Jurgen Troitzsch, published by Hanser Publishers ISBN 3-446-13571-5, Section
• samples of 6mm Plywood 200mm by 200mm were thoroughly dried by placing them in an oven at 60 Deg C for 24 hours prior to the test.
• One half of each sample is liberally coated on both sides with a mixture comprising 20 parts of Example 1 and 80 parts of 1,1,1,trichloroethane (solvent) and allowed to dry.
• Other samples were also made at the same time and in a similar manner using no fire retardant, and equivalent amounts of the fire retardants TCEP, TCPP, DMMP and TBP. After drying the samples were cut into 10mm wide strips so that the sample size is 6mm by 10mm by 200mm with approximately one half of the sample (10 by 100mm) having a coating of fire retardant.
• a mixture is formed with 85% of the fire retardant compound (Example 1) and 15% Teric 200 (ICI).
• the Teric 200 is heated to 50 Deg C to liquify it and the fire retardant is slowly added whilst the temperature is kept at 50 dec C. This is then allowed to cool.
• This mixture is further added to water at the rate of 200 grams per litre, with constant agitation.
• the fabric to be treated is immersed in the solution and run through nip rollers to give a pick up weight of between 40 to 100% (usually 70%). In some instances a stain release, deodorant, uv stabiliser or other treatment may be added to the mixture.
• the wet fabric is then stretched and exposed to hot air at between 120 and 160°C for several minutes.
• Sample Woven fabric comprising 65% polyester and 35% cotton having a nominal mass of 220 grams per square metre, colour navy.
• Sample Woven fabric comprising 100% wool having a nominal mass of 388 grams per square metre and a thickness of 1.3 mm.
• compositions and methods have been advanced merely by way of explanation and many modifications may be made thereto without departing from the spirit and scope of the invention which includes every novel feature and combination of novel features herein disclosed.

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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Fireproofing Substances (AREA)

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• 1990
  • 1990-06-28 KR KR1019910702004A patent/KR920702699A/ko not_active Application Discontinuation
  • 1990-06-28 EP EP90909570A patent/EP0479829A1/de not_active Withdrawn
  • 1990-06-28 CA CA002045629A patent/CA2045629A1/en not_active Abandoned
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