CA2045629A1 - Fire retardants - Google Patents
Fire retardantsInfo
- Publication number
- CA2045629A1 CA2045629A1 CA002045629A CA2045629A CA2045629A1 CA 2045629 A1 CA2045629 A1 CA 2045629A1 CA 002045629 A CA002045629 A CA 002045629A CA 2045629 A CA2045629 A CA 2045629A CA 2045629 A1 CA2045629 A1 CA 2045629A1
- Authority
- CA
- Canada
- Prior art keywords
- fire retardant
- phosphate
- retardant composition
- composition according
- retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- 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
- C08K5/49—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
- 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
Abstract
ABSTRACT
A fire retardant composition comprising: (i) at least one halogenated phosphate; and (ii) at least one phenol substituted with one or more halogen atoms. The fire retardant composition may be used in the production of plastic materials, as a fire retardant coating, and as a surface treatment to improve the fire retardancy of textiles and other fibres.
A fire retardant composition comprising: (i) at least one halogenated phosphate; and (ii) at least one phenol substituted with one or more halogen atoms. The fire retardant composition may be used in the production of plastic materials, as a fire retardant coating, and as a surface treatment to improve the fire retardancy of textiles and other fibres.
Description
WO9l/~307 PCT/AU~/00275 '': "' ',, ', " "
' ' :. ;' FIRE RETARDANTS ~;
' '~' ' ~' Thl~ lnventlon relates to flre retardant compo~ltlons whlch have partlcular appllcatlon as 1re retard~nt agent~ ln:
~ 1) Plastlc materlals (such as polyurethanes, epoxy r-sln~, and other thermoset, thermoplastic materlals) and precursor thereof.
' ' :. ;' FIRE RETARDANTS ~;
' '~' ' ~' Thl~ lnventlon relates to flre retardant compo~ltlons whlch have partlcular appllcatlon as 1re retard~nt agent~ ln:
~ 1) Plastlc materlals (such as polyurethanes, epoxy r-sln~, and other thermoset, thermoplastic materlals) and precursor thereof.
(2) Flre retardant coatlngs (lncluding polymerlc ~;~
coatlngs) such as paints. ~;
t3) Surface treatments to improve the flre ;~
retardancy of textlle yarns and flbre~, ln both synthetlc and natural flbres and ln blends thereof.
Tho lnventlon 19 based on an unexpected synerglstic or potentlatlng lnteractlon between two hitherto known ~ -~
cla~se~ of flre retardant~, namely (1) halogenated ~,, phosphates; and (11) phenol substltuted wlth one or more 30 halogen atoms. In partlcular, the comblnatlon of ~;;;
components (1) and (li) produces a flre retardant having slgnlflcantly superlor fire retardant propertles than elther of the fire retardants alone, or basgd on a mere comblnatlon of thelr known propertles.
Accordlng to one aspect of ~he lnventlon, there ls provlded a flre retardant composltion whlch comprises:
(i) at least one halogenated phosphate; and ; ;
~ ,, ,',:
i .
.~,,,,~, . '~' W O 91/00307 PC~r/AU90/00275 (ii) at least one phenol substituted with one or more halogen atoms.
Component (i) may be any halogenated phosphate which exhlblts fire retardant properties. For example, component ~i) may be selected from 2-chloroethanol phosphate:
1-3-dlchloro-2-propanol phosphate;
l-chloro-2-propanol phosphate:
2-3-dl-bromo-1-propanol phosphate;
oligomerlc chloroalkyl phosphonates, bls(2-chloroethyl)2-chloroethyl phosphonate;
trlchloroethyl phosphate (~CEP) trlchloropropyl phosphate (TCPP) dlmethyl monophosphate (DMMP).
15 TCEP and TCPP are partlcularly preferred.
Component (il) may be selected from compounds containlng one or more phenol rlngs whlch are substltuted wlth one or more halogen groups, preferably bromlne atoms. Compounds having a slngle phenol ring are 20 pre~erred i~ 2,4,6 tribromo phenol (TBP) ls partlcularly preerred.
~n a partlcularly preferred aspect of the lnventlon there 15 provlded a composltlon whlch comprises a mlxture o~:
25 (a) TCEP and/or TCPP: and (b) TBP.
The preclse weight ratlo of component (i) to component (ii) ls generally unlmportant. For example, the ratlo of component (1) to component (il) may be from 1:0.45 to 1:1.25. Component (i) i9 generally a liquid, ; and component (li) a solid. In a preferred embodlment of thls lnventlon, component (11) ls added to component (1) to form 8 gaturated or substantlally saturated solutlon, where the ratlo of component (1) to component (11) ls 35 about 1:0.86. A dlluent may be added to the mixture to 3 allow component ratios greater than those that form a ~aturated solutlon.
SU~STITUTE Sl-IEET j ,.. , . .. ,... . . ......... , , , ,: ...................... ., ;. .
,.. ,.. ~ . .... , - : ,., ~ . . : :- , - , . :
The fire retardant compos~tion of the invention is a liquid and does not appear to undergo any reactions at ;
temperatures at least up to 73C. At about 73C the composltlon 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 110C.
The flre retardant composltion i9 soluble in organ~c ~olvents such as methanol, ethanol, propanol, butanol, ~tc.; and ls generally lnsoluble ln agueou~ solutlons.
Aqueous solutlons may be prepared using commercial emul~lfiers such as Teric (a reg~stered trademark of ICl Australia Pty. Ltd.) and uslng technlques as descrlbed ln the examples set out below.
When used as a flre retardant in plastics or resins~
the 1re retardant is blended wlth the components used to form the re~in. For example, in the production of urethane resln~ or foams, the flre retardant may be mixed with a polyol component (i.e. a hydroxyl containing polymer, see Encyclopedia of Chemlcal Technology, 3rd Editlon, Vol. 11, p. 88, John Wlley and Sons, 1981) prlor to mlxlng of the polyol wlth an lsocyanate to glve a polyol blend. The polyol blend may, for example, contaln from 5 to 80% of the flre retardant composition as herelnbefore descrlbed. Ths components of the polyol blQnd are sultable for storage for a considerable period of tlme, i.e., up to six months or more, even at elevated ¦ temperatures.
The polyol blend may additionally contaln one or ~ 30 more basic materials, (such as an lnorganlc or organlc j base, for example an amlne, such as trimethyl amine).
When present, the base generally comprises from 0.01% to 15% (wt/wt) of the polyol blend. The polyol blend may also contaln glycerol, silicone, water, CFC, an amine ;~
catalyst and a tin catalyst.
Alternatively, the fire retardant composition may be mixed wlth both the polyol and isocyanate at the same '~
' UL.STITUTE S~EET
,: ""',:
WO 91/00307 PCr/AU90/00275 , time, to form a polyurethane polymer such as a polyurethane foam.
The amounts of reactants used in the preparation of ursthane oams on a weight basis may vary considerably according to well known methods in the art.
Conventlonslly, the proportlons of polyol and isocyanate are selected to provide approxlmately equal amounts (molar equivalents) of hydroxy and lsocyanate functlonalities, with isocyanate being in slight excess.
The flre retardant of the lnventlon may constltute from 1 to 50% (wt/wt) of the reaction mixture.
Particular advantages associated with the use of flre retardant composltions of the lnventlon ln the productlon of polyurethanes are as follows:
1. The flre retardant enables high levels of flre, retardancy to be achleved by the addltlon of the flre retardant lnto the precursors of polyurethane foam polymers.
2. The flre retardant exhlblts plastlclslng effects whlch ln part enable cell structures in foams to be ea~lly modlfled and controlled.
3. The flre retardant ls readily soluble ln commerclally available foam prepolymer~ and as such acts as a vlsco~lty modlfler.
coatlngs) such as paints. ~;
t3) Surface treatments to improve the flre ;~
retardancy of textlle yarns and flbre~, ln both synthetlc and natural flbres and ln blends thereof.
Tho lnventlon 19 based on an unexpected synerglstic or potentlatlng lnteractlon between two hitherto known ~ -~
cla~se~ of flre retardant~, namely (1) halogenated ~,, phosphates; and (11) phenol substltuted wlth one or more 30 halogen atoms. In partlcular, the comblnatlon of ~;;;
components (1) and (li) produces a flre retardant having slgnlflcantly superlor fire retardant propertles than elther of the fire retardants alone, or basgd on a mere comblnatlon of thelr known propertles.
Accordlng to one aspect of ~he lnventlon, there ls provlded a flre retardant composltion whlch comprises:
(i) at least one halogenated phosphate; and ; ;
~ ,, ,',:
i .
.~,,,,~, . '~' W O 91/00307 PC~r/AU90/00275 (ii) at least one phenol substituted with one or more halogen atoms.
Component (i) may be any halogenated phosphate which exhlblts fire retardant properties. For example, component ~i) may be selected from 2-chloroethanol phosphate:
1-3-dlchloro-2-propanol phosphate;
l-chloro-2-propanol phosphate:
2-3-dl-bromo-1-propanol phosphate;
oligomerlc chloroalkyl phosphonates, bls(2-chloroethyl)2-chloroethyl phosphonate;
trlchloroethyl phosphate (~CEP) trlchloropropyl phosphate (TCPP) dlmethyl monophosphate (DMMP).
15 TCEP and TCPP are partlcularly preferred.
Component (il) may be selected from compounds containlng one or more phenol rlngs whlch are substltuted wlth one or more halogen groups, preferably bromlne atoms. Compounds having a slngle phenol ring are 20 pre~erred i~ 2,4,6 tribromo phenol (TBP) ls partlcularly preerred.
~n a partlcularly preferred aspect of the lnventlon there 15 provlded a composltlon whlch comprises a mlxture o~:
25 (a) TCEP and/or TCPP: and (b) TBP.
The preclse weight ratlo of component (i) to component (ii) ls generally unlmportant. For example, the ratlo of component (1) to component (il) may be from 1:0.45 to 1:1.25. Component (i) i9 generally a liquid, ; and component (li) a solid. In a preferred embodlment of thls lnventlon, component (11) ls added to component (1) to form 8 gaturated or substantlally saturated solutlon, where the ratlo of component (1) to component (11) ls 35 about 1:0.86. A dlluent may be added to the mixture to 3 allow component ratios greater than those that form a ~aturated solutlon.
SU~STITUTE Sl-IEET j ,.. , . .. ,... . . ......... , , , ,: ...................... ., ;. .
,.. ,.. ~ . .... , - : ,., ~ . . : :- , - , . :
The fire retardant compos~tion of the invention is a liquid and does not appear to undergo any reactions at ;
temperatures at least up to 73C. At about 73C the composltlon 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 110C.
The flre retardant composltion i9 soluble in organ~c ~olvents such as methanol, ethanol, propanol, butanol, ~tc.; and ls generally lnsoluble ln agueou~ solutlons.
Aqueous solutlons may be prepared using commercial emul~lfiers such as Teric (a reg~stered trademark of ICl Australia Pty. Ltd.) and uslng technlques as descrlbed ln the examples set out below.
When used as a flre retardant in plastics or resins~
the 1re retardant is blended wlth the components used to form the re~in. For example, in the production of urethane resln~ or foams, the flre retardant may be mixed with a polyol component (i.e. a hydroxyl containing polymer, see Encyclopedia of Chemlcal Technology, 3rd Editlon, Vol. 11, p. 88, John Wlley and Sons, 1981) prlor to mlxlng of the polyol wlth an lsocyanate to glve a polyol blend. The polyol blend may, for example, contaln from 5 to 80% of the flre retardant composition as herelnbefore descrlbed. Ths components of the polyol blQnd are sultable for storage for a considerable period of tlme, i.e., up to six months or more, even at elevated ¦ temperatures.
The polyol blend may additionally contaln one or ~ 30 more basic materials, (such as an lnorganlc or organlc j base, for example an amlne, such as trimethyl amine).
When present, the base generally comprises from 0.01% to 15% (wt/wt) of the polyol blend. The polyol blend may also contaln glycerol, silicone, water, CFC, an amine ;~
catalyst and a tin catalyst.
Alternatively, the fire retardant composition may be mixed wlth both the polyol and isocyanate at the same '~
' UL.STITUTE S~EET
,: ""',:
WO 91/00307 PCr/AU90/00275 , time, to form a polyurethane polymer such as a polyurethane foam.
The amounts of reactants used in the preparation of ursthane oams on a weight basis may vary considerably according to well known methods in the art.
Conventlonslly, the proportlons of polyol and isocyanate are selected to provide approxlmately equal amounts (molar equivalents) of hydroxy and lsocyanate functlonalities, with isocyanate being in slight excess.
The flre retardant of the lnventlon may constltute from 1 to 50% (wt/wt) of the reaction mixture.
Particular advantages associated with the use of flre retardant composltions of the lnventlon ln the productlon of polyurethanes are as follows:
1. The flre retardant enables high levels of flre, retardancy to be achleved by the addltlon of the flre retardant lnto the precursors of polyurethane foam polymers.
2. The flre retardant exhlblts plastlclslng effects whlch ln part enable cell structures in foams to be ea~lly modlfled and controlled.
3. The flre retardant ls readily soluble ln commerclally available foam prepolymer~ and as such acts as a vlsco~lty modlfler.
4. Polyol blends contalnlng the flre retardant of thl~ lnventlon are relatlvely stable.
The applicant has addltlonally found that where the flre retardant composltlon of thls lnventlon is used ln the productlon of polyurethane foams, chlorofluorocarbons (CFCs) may be reduced or omltted from the reactlon mlxture. The flre retardant in accordance with thls lnventlon enables polyurethane foams to be controlled durlng thelr blowlng phase utlllslng carbon dloxlde gas, formed as a reactlon between water and lsocyanate, as a blowlng agent, enabllng the ellmlnatlon or reductlon of CFCs and other volatlle agents. In thls lnstance, the flre retardant of this invention also reacts as a I Sl.IBSTITUTE S~EET_, - ,, ~........ . . . . . : . .. ~
` .` . . , ~ - ~ . -,, , . :. : - ~
.. , ,:. ~: . - - . -W09l/~307 PCT/AU90/0027~
The applicant has addltlonally found that where the flre retardant composltlon of thls lnventlon is used ln the productlon of polyurethane foams, chlorofluorocarbons (CFCs) may be reduced or omltted from the reactlon mlxture. The flre retardant in accordance with thls lnventlon enables polyurethane foams to be controlled durlng thelr blowlng phase utlllslng carbon dloxlde gas, formed as a reactlon between water and lsocyanate, as a blowlng agent, enabllng the ellmlnatlon or reductlon of CFCs and other volatlle agents. In thls lnstance, the flre retardant of this invention also reacts as a I Sl.IBSTITUTE S~EET_, - ,, ~........ . . . . . : . .. ~
` .` . . , ~ - ~ . -,, , . :. : - ~
.. , ,:. ~: . - - . -W09l/~307 PCT/AU90/0027~
reaction temperature modifier to o~ercome the excessive rapid exotherm generated in polyurethane foams when the isocyanate components in the foam are reacted wlth water to form carbon dioxlde.
In accordance wlth another aspect of the present lnventlon, there is provided a polyol blend whlch comprlses a polyol and a fire retardant composltion as hereinbefore described, which i8 free of CFCs. Such polyol blends are generally used in the productlon of polyurethane foams where the blends are reacted with an lsocyanate to form the polymer, wlth carbon dioxlde productlon ln the reactlon belng the expandlng gas.
In yet another aspect of the inventlon, there is provided a polyol blend which comprlses a polyol, a flre retardant as herelnbefore descrlbed, and low levels of CFCs. As used hereln, the term "low levels" refer~ to 0.1% to 17% (wt/wt) of CFC ln the polyol mlx.
Conventional polyol formulation~ 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 ls advantageous. Polyol blends contalnlng low levels of CFCs may also contaln glycerol, slllcone, water, an amlne, and a tin catalyst. The polyol blend may contaln from 5 to 80% of the fire retardant 25 composltlon as hereinbefore described. ~';
Thls lnvention also relates to polyurethane foams whlch lncorporate flre retardants as descrlbed herein;
and further relates to polyurethane foams when produced by the reactlon of a polyol blend contalning a flre retardant, wlth an isocyanate containlng compound.
In accordance wlth another aspect of this lnventlon, the flre retardant compositlons described hereln may ~e ;
incorporated lnto polymeric materials such as polyvinyl , chloride (PVC), polyester, polyamide, polyimide, polypropylene, polyethylene, nylon, phenolic resin and acetal resin. Such polymeric materlals may contain from 0.1 to 50% (wt/wt) of the fire retardant compositlon of , j SUBSTITUTE SHEET j , , thls invention. The fire retardant of this invention is simply addsd 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 adversely effected.
The fire retardant of this lnvention may also be lncorporated into a pulp of cellulose or llke flbres for the productlon of paper, cardboards, etc. Such material exhlblts flre retardant propertles.
When used as a flre retardant coatlng or surface treatment, the flre retardant composition may be dlluted wlth an organlc solvent to form, for example, a mlxture contalns 1~ to 90% (wt/wt) flre retardant, and then ~prayed onto a surface whlch 19 deslred to be coated. On evaporatlon of the organlc solvent, a stable surface coatlng remalns. In the treatment of exposed tlmber products, for example, the flre retardant may be lncorporAted lnto conventlonal wood stalns to yleld a decoratlve surface. In another lnstance, for example, composltlon~ of thls lnventlon may be applled to furnishlng~, drapes, carpets, tents, screen cloths, etc to lmp~rt flre retardancy. In such cases a staln release, deodorant and the llke may be added to the mlxture. The term "deodorants" used hereln refers to any compound or number of compounds whlch have an odour reduclng effect, or whlch lmpart a pleasant smell to the human and/or anlmal nose. Deodorants or odour modlflers are descrlbed, for example, ln the Encyclopedla of Chemlcal Technology, 3rd Edltlon, Vol. 16, pp. 297-305, John Wlley & Sons, 1981.
In the case of surface treatments of textiles, yarns and fabrlcs lt is generally preferred to use an aqueous fire retardant. Thls is formed by the combination of the compound with a commercial emulsifying agent (such as ICI
.', i SUeSTlTUTE SHEE~J
: ' ., ~
WO91/00307 PCT/AU90/0027~
~ 7 ~ 20A5629 Teric 200), which is then diluted with water and applied to the fabric or textiles. Application may be by immerslon and nip roller to achieve pick up weights of between 20 -90i~. Usually a high temperature treatment (CUch as about 100C-250C) of the fabric followY
application of the compound to stabilise both the compound and the fabric. The resultant cloth exhibits a high degree of flre retardancy. (See Example ).
Partlcular advantages associated wlth the use of the flre retardant compositlons in relation to fabrlc appllcatlons of the lnventlon are;
1. A good "hand" of feel of the fabrlc. Many flre retardants effect the feel of fabrlcs causlng them to eel stlff or "woody".
2. Good llght-fastness, the treated fabrlc exhlblts uv stablllty well in excess of requlred standards. ''~' 3. A hlgh level of wash retentlon, agaln well ln excess of standards.
4. Ease of applicatlon, that ls requlring a single treatment.
In accordance wlth another aspect of thls lnventlon, ;~, there 18 provlded a flre retard~nt composltlon as deflned heroln, whlch addltlonally comprlses one or mor~ of the "
~ollowlng:
(1) a deodorant:
~11) staln release compound; ;;
(ill) wood staln or palnt;
(lv) volatlle organlc solvent and/or lnorganlc solvent; and/or (v) emulslfylng agent.
In accordance wlth a further aspect of this lnventlon, there 19 provlded textiles; yarns; fabrlcs;
tlmber; wood-contalnlng products; or articles such as carpets, screen cloths, drapes or furnlshlngs; which have been treated wlth a flre retardant composltion as described hereln. By the term "treatment" is meant , "'", ; ~ ' ;'' ~ ' ;.~i! ., - .; ,' " ~ ; ' ' ' ~ ' ;
W O 91/00307 PC~r/AU90/0027~
appllcatlon by spraying, dipping, painting and other methods well known in the art for the application of fire retardants.
A number of embodiments of the present invention will now be further described, with reference to the followlng, non-llmlting example. It is to be understood that the followlng examples ln no way restrict the inventlon to those compounds, composltlons and methods speciflcally exempllfled, whlch are detalled ~y way of representative example only.
E~ 1 .
preDar~ on of Fire Retardant ComDositions:
Reagents:
(i) Trichloropropyl phosphate (TCPP) and trlchloroethyl phosphate (TCEP) were obtalned commerclally from Akzo Chemicals under the trade names FYROL Pcf and FYROL Cef respectively. Both TCPP and TCEP
are llqulds at amblent temperatures.
(il) Trls 2,4,6 tribromophenol and Bls 2,4,6 Tribromophenol (TBP) were obtalned from elther Great Lake~ Chemlcal Company, West Lafyette, Indlana, U.S.A. or from ~romlne Compounds Llmlted, Beersheva, Israel. These compounds are flaky sollds at amblent temperatures.
Flre retardant composltlons were prepared by mlxlng the bromlnated phenol wlth one or both of chlorlnated phosphates, untll all the bromlnated phenol 19 dlssolved thereln. Warmlng the chlorlnated phosphate, for example to 70-C, promotes solubllity of the brominated compound.
Where TCPP and TCEP are used ln combinatlon, the weight ratlo ls usually 1:1 however thls may vary.
A range of flre retardant composition were prepared wherein the welght ratlo of chlorlnated phosphates (TCPP
and TCEP) to bromlnated phenols was from 1:0.45 to 1 35 1:1.25. For Examples 2 to 6 listed below a near saturated solutlon of fire retardant was prepared by dlssolvlng 80g of TBP in lOOg o~ TCPP.
.;
j SU6STITUTE SHE~T I ~ :
., E$AMPLE 2 Polyol Blends ( stability of blends containing fire retardant):
The followlng components were mixed together in a standard commerclal mixer, or beaker, to give a common polyol blend:
- 31.5g Polyol - Daltolac 140 (trademark of ICI
Chemlcal Industrles Llmited) '~
- 2.29g Glycerol - 0.67g Slllcon - Dow Cornlng DC 193 - 0.44g Amlne - Dabco 33LV (33~ trlmethyl amlne) - 0.4g Water - 0.04g Tln - Dabco T12 catalyst (Dibutyl tin -dllaurate) - 14.57g CFC - Dupont Freon 11 ;
- 53.00g Flre retardant composltlon of Example 1.
Polyol blends contalning no CFCs were prepared by deletlng the CFC component ln the above mlx, and ralsing the amount of water to 2.44 g.
The above formulations contain 50.5% (wt/wt) fire r-tardant. Formulations the same as above (in the pre~ence and absence of CFC) were prepared which contain from 5 to 63~ (wt/wt) fire retardant.
The above polyol formulations were stable, and could bo stored for at leaQt 60 days at elevated temperatures of 60-C without any noticeable deleterious effects.
Parameters checked lnclude changes in both the vlscoslty and the colour of the blend and, when reacted wlth an lsocyanate, changes in the reaction time proflles of, Cream, Rlse & Gel times (as descrlbed in the Polyurethane Handbook, Hansen Publishers, New York, 1985, Ed. ~unter Oertel), when compared wlth fresh blends of the same formulatlon. No notlceable changes were observed.
. . ,, ;;
t 35 ,1 , ~ , ,,~ ' .
i ,~ ~ ' ;' . -- . .
W091/~307 PCT/AU90/00275 - lo - 2045629 E~AMPLE 3 A Standard Polyurethane Blend wlth Varying Levels of Fire Retnrdant (E~ample 1) Compared to a Commonly UsQd Fire Rstardant (FYrol Pcf):
Polyurethane foams are prepared by reacting a hydroxyl-containlng polymer (polyol) with a polyfunctional isocyanate as shown in Scheme A, where (1) 19 polyfunctlonal lsocyanate, ~2) a polyol, and (3) a polyurethane Scheme A:
O O
OCN - R - NCO ~ HO - R ' - OH C - NH - R - HNC - OR ' - O
(1) (2) (3) whsreln R and R' are alkyl, alkoxy or the llke optionally subqtltuted wlth one or more substltuents.
A detailed revlew of polyurethanes 18 to be found in Polyureth~ne Elastomers, by C. Hepburn, Applled Science Publlshers, 1982, whlch ls lncorporated herein by reference.
Polyurethane foams were produced by mixlng the polyol formulations with a polyisocyanate, SUPRASEC 5005 (a dilsocyanato-diphenylmethane), obtained from ICI
Australia Operations Llmlted. The amount of lsocyanate used to react wlth the polyol was calculat~d by determining the total equivalents of hydroxyl groups ln the polyol formulation, according to methods well known ln the ~rt, 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.
Thus, the polyol blend of Example 2 would be mixed in a commercial mixer with 56 g of lsocyanate. (Suprasec 5005) The following formulations were produced:
3a 3b 3c 3d Daltolc 140 31.5~ 31.50 31.50 31.50 Glycerol 2.29 2.29 2.29 2.29 Sllicone 0.67 0.67 0.67 0.67 ~, ; SU~STITUTE SHEET j . - , -WOgl/00307 PCTtAU90/0027i ~' ' - 11 - 2045629 . .
3a 3b 3c 3d (cont) (cont) (cont) (cont) Amlne 0.44 0.44 0.44 0-4 Tln 0.04 0.04 0.04 0.04 Water 0.44 0.44 0.44 0.44 CFC (Fll)14.57 14.57 14.57 14.57 Example 1 0 0 5.60 0 Fyrol Pcf 0 5.60 0 21.00 Isocyanate56.00 56.00 56.00 56.00 1 0 "' 3e 3f 3g 3h Daltolc 140 31.50 31.50 31.50 31.50 Glycerol 2.29 2.29 2.29 2.29 Slllcone 0.67 0.67 0.67 0.67 Amlne 0.44 0.44 0.44 0.44 Tln 0.04 0.04 0.04 0.04 Water 0.44 0.44 0.44 0.44 CFC (Rll)14.57 14.57 14.57 14.57 Example 121.00 0 31.00 53.00 Fyrol Pcf 0 31.00 0 0 Isocyanate56.00 56.00 56.00 56.00 * All quantlties are ln grams.
Formulatlon 3a contalns no flre retardant.
Formulatlon~ 3c, 3e, 3g and 3h contaln lncreaslng amounts of tho flre retardant composltlon of thls lnventlon.
Formulatlons 3b, 3d and 3f contaln lncreaslng amounts of tho commerclally avallable flre retardant Fyrol Pcf (trlchloropropyl phosph~te).
On reactlon the varlous formulatlons gave rlse to polyurethane foams.
Limited O ygen Index ANSI/ASTM D 2863-77:
~hls test, ls an Australian and Internatlonal Standard of flammability (see Polvurethane Hand~ook, Ed.
Gunter Oertel, 11985, Carl Hanser Verlag, pp. 495-496).
'~
13~
~, ' .
~ ;t~83~7 P(~/A'~
, 3aslcally, the test measures the % of oxygen that will support candlelight combustion. The lower the ~ oxygen index the more flammable is a material.
R0sults:
~ Oxygen Index Blend 3a, (no fire retardant) 19.5 Blend 3b ~5.6g)(Conventlonal formulatlon) 22.5 Blend 3c (5.6g) 23.0 10 Blend 3d (21g)(unstable foam) 23.5 Blend 3e (21g) 24.6 Blend 3f (31g)(unusable foam) 25.0 Blend 3g (31g) 27.5 Blend 3h (53g) 28.5 These results show that foams produced uslng conventional flre retardants have a lower percentage oxygen lndex, and thus are more flammable than those foams produced utllislng the flre retardant compositlon of thl~ lnventlon. It ls to be noted that small lncreases in the percentage in oxygen lndex correspond to slgnlflcant increases ln flre retardancy. For example, a dlfference of 0.5 ~n the percentage oxygen lndex between formulatlon 3b (contalnlng a conventlonal flre retardant) and formulatlon 3c ~contalnlng the flre retardant compo~ltlon of this lnventlon) 18 lndlcative of a slgnl1cant decrease ln flammablllty of the foam produced by composltlon 3c.
The lncrease ln flre retardancy observed ln foams contalnlng the flre retardant composltlon of Example 1 ls belleved to result from a synerglstlc interactlon between the components of the flre retardant, namely TCPP and ;
TBP. ;~
~he foam produced from blends 3b, 3d and 3f, was ;
inferlor when compared to foams produced using the same level of the flre retardant of the lnventlon, insofar as flammablllty and stablllty are concerned.
Formulations according to blends 3b, 3d and 3f were ''' ' ''~:
:, , ! SUBSTITUTE SHEET ! : :~ ~
~ ,., .. ~
WO91/00307 PCT/AU~/00275 ~ -also produced, where the fire retardant Fyrol Pcf was replaced with halogenated phosphates, trichloroethyl phosphate (TCEP), and dimethylmono phosphate (DMMP), and wlth trlbromophenol (TBP). The percentage oxygen lndex of the foams produced uslng halogenated phosphates generally corresponded to those obtalned uslng the flre retardant Fyrol Pcf (TCPP). The 4Oams produced uslng T8P
were of very poor quallty and possessed a very low percentage oxygen index, below about 19.
These results show that the combination of a halogenated phosphate and a phenol substltuted with one or more halogen atoms interact synergistlcally to produce foams havlng decreased flammabillty, when compared to foams produced uslng elther of the components alone.
These results are surprlsing and unexpected.
The formulation of Example 1 was advantageous as ~table foams could be produced in the presence of large quantltles of 1re retardant (see blends 3g and 3h). In contra~t, formulatlons contalnlng more than 21 g of Fyrol Pcf or other halogenated phosphates were physlcally infsrlor ~poor dlmenslonal stabllity and low closed cell count) and gave rlse to unstable foams. Foams produced uslng the flre retardant TBP were of very poor quallty and were generally unstable regardless of the amount of T~P used.
The improved stabllity of foams produced uslng the flre retardant composition of Example 1 was unexpected, partlcul~rly as the independent components of the flre retardant of Example 1 dld not glve rlse to stable foams when large quantities were used (blends 3d and 3f).
Large quantities of the fire retardants of this invention may be incorporated into polyurethane foams without disturbing their structure. This is advantageous as foams which are highly flame resistant may be 35 produced. ;
, . ~ , .
SUe~TlTUTE SHEET i ., .
E~AMPLE 4 Soluble Fire Retardants:
The fire retardant composltlon of Example 1 was dlluted ln methanol to glve 20% (w/w) flre retardant composltlon. Thls material was sprayed onto needled polypropylene (a rlbbed wall coverlng manufactured by Melded Fabrlcs Pty Ltd of Melbourne) and allowed to dry.
Dry pick up welght was 15.7%
The materlal was then washed 10 times wlth hot water contalnlng a detergent.
The treated materlal exhlblts excellent fire retardancy as measured by ASTM method FMVSS 302, a horlzontal burn test ~see - Internatlonal Plastlcs Flammabillty Handbook, Author Jurgen Troltzsch, publlshed by Hanser Publlshers ISBN 3-446-13571-5, Section 8.3.1.2). In thls test, a slab of materlal 8 lnchQs x 3 lnCheJ wa8 held horlzontally ln a flame ~nd the rate of burn back mea~ured. Results classlfy samples ln this test a~ "8elf Extlnguishlng". ~he treated materlal dld not burn.
In contrast, non-treated materlal was completely consumed by flame, which rapldly spread down the strlp of material.
Needled polypropylene treated ln the same manner 25 (includlng washlng) as above, wlth equlvalent amounts of ;~
TCPP, TCEP, DMMP or T3P shows slgnlflcant burn back ;~
(about 83 mm/mlnute) and consumptlon of material.
.;' ',,: ',',':
~AMPLe 5 Flre ~etard~nt Co~tina For Timber:
ln thls example samples of 6mm Plywood (200mm by 200mm) were thoroughly drled by placlng 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 wlth a mixture comprising 20 parts of Example 1 and 80 parts of l,l,l,trichloroethane (solvent) and allowed to dry.
Other samples were also made at the same tlme and in a . ,:'"'",;,'~
';~
_ , .
, SUBSTITUTE SH~ET ~
. .. . . .
- 15 - ~0456Z9 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 50 that the sample size is 6mm by 10mm by 200mm wlth approxlmately one half of the sample (10 by 100mm) having a coatlng of flre retardant. The samples were then held downwards at an angle of 45 Deg wlth the untreated end in the lower acpect. The untreated end of each sample was llt. ~urning i8 observed as the flame travels upward.
~n the case of those samples treated wlth the flre retardant of Example 1, burnlng ceased upon the flame reaching the treated area. In all the other samples tested, complete burnlng took place wlth the sample~
belng consumed.
E~AMPLE 6 As ~ Sur~ce Trentment for Te~tlles:
In one example a mlxture is formsd with 85% of the flre retardant compound (Example 1) and 15% Terlc 200 (IC~). The Terlc 200 is heated to 50 Deg C to llqulfy it and the flre retardant 15 910wly added whllst the temperature ls kept at 50 dec C. Thl~ ls then allowed to cool. Thls mlxture ls further added to water at the rate of 200 grams per lltre, wlth constant agltatlon.
The fabrlc to be treated 19 lmmersed ln the solutlon and run through nlp roller~ to glve a plck up welght of between 40 to 100% (usually 70%). In some lnstances a st~ln relea~e, deodorant, uv stablllser or other treatment m~y be added to the mlxture. The wet fabric ls i 30 then stretched and exposed to hot alr at between 120 and 160-C for several mlnutes.
TESTS
Austral~an Standard 1530 (parts 2 & 3) TESTS FOR
FLAMMABILITY OF MATERIALS AND SIMULTANEOUS DETERMINATION
OF IGNITION, FLAME PROPAGATION, HEAT RELEASED AND SMOKE
IND B
Thls is an Australlan standard test (for a detailed .. . .
'VBSTITUTE SHEE~r i ., ~i reference, see International Plastics Flammabillty Handbook, Author Jurgen Troitzsch, published by Hanser Publlshers ISBN 3-446-13571-5 Section 8.2.16 which is incorporated hereln by reference) and in the~e examples testlng was carried out at the Australlan Wool Testlng Authorlty Ltd. North Melbourne, Vlctoria, Australia.
In one sample tested agalnst the AS 1530 part 2 test (a vertlcal burn test, flame applied to the bottom of a strlp of materlal) ths followlng test results were obtalned:
Sample: Woven fabrlc comprlslng 65% polyester and 35%
cotton havlng a nomlnal mass of 220 grams per square metre, colour navy.
Dry plck up welght of flre retardant actlve ~;;
lngredlents as per Example 6 was 10.8%
Reeults: (AWTA test # 7-428445-fn) Treated Untreated Result ranae ;~
Speed Factor 0 44 0-60 20 Sproad Factor 0 23 0-40 ~;
Heat Index 1 12 0-Upwards Flammablllty Index 1 85 0-lOO
In these tests, hlgh values reflect undeslrable i~
r-sults. It ls cl~ar from the above data that treatment wlth the flre retardant ls most advantageous. ;
In another sample tested agalnst the AS 1530 part 3 tost (~ample moved towards a radiant heat source) the followlng test results were obtalned: ~' Sample: Woven fabric comprisiny 100% wool having a nominal mass of 388 grams per square metre and a thlckness of 1.3 mm.
Dry pick up weight of fire retardant active ingredients as per Example 6 was 11.3%.
The test ls a comparison between unwashed materlal and materlal washed ten times wlth hot water and detergent.
,.... .................................................................. .... ... .....
¦ SUBSTITUTE SHEET ! -`
. , ...
W O 91/00307 PC~r/A U90/00275 - 17 - 20~5629 Results: (AWTA test # 7-428995 fn) UnwashedWashed Result range Ignitability 0 0 0-20 Spread of flame 0 0 0-10 5 Heat evolved 0 0 0-10 Smoke developed 5 4 0-10 Number of speclmens tested ~ 6 Number of specimens ignited ~ 0 Agaln, these results sho~ that the treated material aftsr w~shlng ls still highly fire resistant.
The described compositions and meth~ds have been adv~nced merely by way of explanation and many modlflcatlons m~y be made thereto wlthout departlng from the splrlt and scope of the inventlon whlch lncludes every novel feature and comblnatlon of novel features hereln dl~closed.
~. . ~
.~ S~5BSTITUTE SHEET i
In accordance wlth another aspect of the present lnventlon, there is provided a polyol blend whlch comprlses a polyol and a fire retardant composltion as hereinbefore described, which i8 free of CFCs. Such polyol blends are generally used in the productlon of polyurethane foams where the blends are reacted with an lsocyanate to form the polymer, wlth carbon dioxlde productlon ln the reactlon belng the expandlng gas.
In yet another aspect of the inventlon, there is provided a polyol blend which comprlses a polyol, a flre retardant as herelnbefore descrlbed, and low levels of CFCs. As used hereln, the term "low levels" refer~ to 0.1% to 17% (wt/wt) of CFC ln the polyol mlx.
Conventional polyol formulation~ 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 ls advantageous. Polyol blends contalnlng low levels of CFCs may also contaln glycerol, slllcone, water, an amlne, and a tin catalyst. The polyol blend may contaln from 5 to 80% of the fire retardant 25 composltlon as hereinbefore described. ~';
Thls lnvention also relates to polyurethane foams whlch lncorporate flre retardants as descrlbed herein;
and further relates to polyurethane foams when produced by the reactlon of a polyol blend contalning a flre retardant, wlth an isocyanate containlng compound.
In accordance wlth another aspect of this lnventlon, the flre retardant compositlons described hereln may ~e ;
incorporated lnto polymeric materials such as polyvinyl , chloride (PVC), polyester, polyamide, polyimide, polypropylene, polyethylene, nylon, phenolic resin and acetal resin. Such polymeric materlals may contain from 0.1 to 50% (wt/wt) of the fire retardant compositlon of , j SUBSTITUTE SHEET j , , thls invention. The fire retardant of this invention is simply addsd 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 adversely effected.
The fire retardant of this lnvention may also be lncorporated into a pulp of cellulose or llke flbres for the productlon of paper, cardboards, etc. Such material exhlblts flre retardant propertles.
When used as a flre retardant coatlng or surface treatment, the flre retardant composition may be dlluted wlth an organlc solvent to form, for example, a mlxture contalns 1~ to 90% (wt/wt) flre retardant, and then ~prayed onto a surface whlch 19 deslred to be coated. On evaporatlon of the organlc solvent, a stable surface coatlng remalns. In the treatment of exposed tlmber products, for example, the flre retardant may be lncorporAted lnto conventlonal wood stalns to yleld a decoratlve surface. In another lnstance, for example, composltlon~ of thls lnventlon may be applled to furnishlng~, drapes, carpets, tents, screen cloths, etc to lmp~rt flre retardancy. In such cases a staln release, deodorant and the llke may be added to the mlxture. The term "deodorants" used hereln refers to any compound or number of compounds whlch have an odour reduclng effect, or whlch lmpart a pleasant smell to the human and/or anlmal nose. Deodorants or odour modlflers are descrlbed, for example, ln the Encyclopedla of Chemlcal Technology, 3rd Edltlon, Vol. 16, pp. 297-305, John Wlley & Sons, 1981.
In the case of surface treatments of textiles, yarns and fabrlcs lt is generally preferred to use an aqueous fire retardant. Thls is formed by the combination of the compound with a commercial emulsifying agent (such as ICI
.', i SUeSTlTUTE SHEE~J
: ' ., ~
WO91/00307 PCT/AU90/0027~
~ 7 ~ 20A5629 Teric 200), which is then diluted with water and applied to the fabric or textiles. Application may be by immerslon and nip roller to achieve pick up weights of between 20 -90i~. Usually a high temperature treatment (CUch as about 100C-250C) of the fabric followY
application of the compound to stabilise both the compound and the fabric. The resultant cloth exhibits a high degree of flre retardancy. (See Example ).
Partlcular advantages associated wlth the use of the flre retardant compositlons in relation to fabrlc appllcatlons of the lnventlon are;
1. A good "hand" of feel of the fabrlc. Many flre retardants effect the feel of fabrlcs causlng them to eel stlff or "woody".
2. Good llght-fastness, the treated fabrlc exhlblts uv stablllty well in excess of requlred standards. ''~' 3. A hlgh level of wash retentlon, agaln well ln excess of standards.
4. Ease of applicatlon, that ls requlring a single treatment.
In accordance wlth another aspect of thls lnventlon, ;~, there 18 provlded a flre retard~nt composltlon as deflned heroln, whlch addltlonally comprlses one or mor~ of the "
~ollowlng:
(1) a deodorant:
~11) staln release compound; ;;
(ill) wood staln or palnt;
(lv) volatlle organlc solvent and/or lnorganlc solvent; and/or (v) emulslfylng agent.
In accordance wlth a further aspect of this lnventlon, there 19 provlded textiles; yarns; fabrlcs;
tlmber; wood-contalnlng products; or articles such as carpets, screen cloths, drapes or furnlshlngs; which have been treated wlth a flre retardant composltion as described hereln. By the term "treatment" is meant , "'", ; ~ ' ;'' ~ ' ;.~i! ., - .; ,' " ~ ; ' ' ' ~ ' ;
W O 91/00307 PC~r/AU90/0027~
appllcatlon by spraying, dipping, painting and other methods well known in the art for the application of fire retardants.
A number of embodiments of the present invention will now be further described, with reference to the followlng, non-llmlting example. It is to be understood that the followlng examples ln no way restrict the inventlon to those compounds, composltlons and methods speciflcally exempllfled, whlch are detalled ~y way of representative example only.
E~ 1 .
preDar~ on of Fire Retardant ComDositions:
Reagents:
(i) Trichloropropyl phosphate (TCPP) and trlchloroethyl phosphate (TCEP) were obtalned commerclally from Akzo Chemicals under the trade names FYROL Pcf and FYROL Cef respectively. Both TCPP and TCEP
are llqulds at amblent temperatures.
(il) Trls 2,4,6 tribromophenol and Bls 2,4,6 Tribromophenol (TBP) were obtalned from elther Great Lake~ Chemlcal Company, West Lafyette, Indlana, U.S.A. or from ~romlne Compounds Llmlted, Beersheva, Israel. These compounds are flaky sollds at amblent temperatures.
Flre retardant composltlons were prepared by mlxlng the bromlnated phenol wlth one or both of chlorlnated phosphates, untll all the bromlnated phenol 19 dlssolved thereln. Warmlng the chlorlnated phosphate, for example to 70-C, promotes solubllity of the brominated compound.
Where TCPP and TCEP are used ln combinatlon, the weight ratlo ls usually 1:1 however thls may vary.
A range of flre retardant composition were prepared wherein the welght ratlo of chlorlnated phosphates (TCPP
and TCEP) to bromlnated phenols was from 1:0.45 to 1 35 1:1.25. For Examples 2 to 6 listed below a near saturated solutlon of fire retardant was prepared by dlssolvlng 80g of TBP in lOOg o~ TCPP.
.;
j SU6STITUTE SHE~T I ~ :
., E$AMPLE 2 Polyol Blends ( stability of blends containing fire retardant):
The followlng components were mixed together in a standard commerclal mixer, or beaker, to give a common polyol blend:
- 31.5g Polyol - Daltolac 140 (trademark of ICI
Chemlcal Industrles Llmited) '~
- 2.29g Glycerol - 0.67g Slllcon - Dow Cornlng DC 193 - 0.44g Amlne - Dabco 33LV (33~ trlmethyl amlne) - 0.4g Water - 0.04g Tln - Dabco T12 catalyst (Dibutyl tin -dllaurate) - 14.57g CFC - Dupont Freon 11 ;
- 53.00g Flre retardant composltlon of Example 1.
Polyol blends contalning no CFCs were prepared by deletlng the CFC component ln the above mlx, and ralsing the amount of water to 2.44 g.
The above formulations contain 50.5% (wt/wt) fire r-tardant. Formulations the same as above (in the pre~ence and absence of CFC) were prepared which contain from 5 to 63~ (wt/wt) fire retardant.
The above polyol formulations were stable, and could bo stored for at leaQt 60 days at elevated temperatures of 60-C without any noticeable deleterious effects.
Parameters checked lnclude changes in both the vlscoslty and the colour of the blend and, when reacted wlth an lsocyanate, changes in the reaction time proflles of, Cream, Rlse & Gel times (as descrlbed in the Polyurethane Handbook, Hansen Publishers, New York, 1985, Ed. ~unter Oertel), when compared wlth fresh blends of the same formulatlon. No notlceable changes were observed.
. . ,, ;;
t 35 ,1 , ~ , ,,~ ' .
i ,~ ~ ' ;' . -- . .
W091/~307 PCT/AU90/00275 - lo - 2045629 E~AMPLE 3 A Standard Polyurethane Blend wlth Varying Levels of Fire Retnrdant (E~ample 1) Compared to a Commonly UsQd Fire Rstardant (FYrol Pcf):
Polyurethane foams are prepared by reacting a hydroxyl-containlng polymer (polyol) with a polyfunctional isocyanate as shown in Scheme A, where (1) 19 polyfunctlonal lsocyanate, ~2) a polyol, and (3) a polyurethane Scheme A:
O O
OCN - R - NCO ~ HO - R ' - OH C - NH - R - HNC - OR ' - O
(1) (2) (3) whsreln R and R' are alkyl, alkoxy or the llke optionally subqtltuted wlth one or more substltuents.
A detailed revlew of polyurethanes 18 to be found in Polyureth~ne Elastomers, by C. Hepburn, Applled Science Publlshers, 1982, whlch ls lncorporated herein by reference.
Polyurethane foams were produced by mixlng the polyol formulations with a polyisocyanate, SUPRASEC 5005 (a dilsocyanato-diphenylmethane), obtained from ICI
Australia Operations Llmlted. The amount of lsocyanate used to react wlth the polyol was calculat~d by determining the total equivalents of hydroxyl groups ln the polyol formulation, according to methods well known ln the ~rt, 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.
Thus, the polyol blend of Example 2 would be mixed in a commercial mixer with 56 g of lsocyanate. (Suprasec 5005) The following formulations were produced:
3a 3b 3c 3d Daltolc 140 31.5~ 31.50 31.50 31.50 Glycerol 2.29 2.29 2.29 2.29 Sllicone 0.67 0.67 0.67 0.67 ~, ; SU~STITUTE SHEET j . - , -WOgl/00307 PCTtAU90/0027i ~' ' - 11 - 2045629 . .
3a 3b 3c 3d (cont) (cont) (cont) (cont) Amlne 0.44 0.44 0.44 0-4 Tln 0.04 0.04 0.04 0.04 Water 0.44 0.44 0.44 0.44 CFC (Fll)14.57 14.57 14.57 14.57 Example 1 0 0 5.60 0 Fyrol Pcf 0 5.60 0 21.00 Isocyanate56.00 56.00 56.00 56.00 1 0 "' 3e 3f 3g 3h Daltolc 140 31.50 31.50 31.50 31.50 Glycerol 2.29 2.29 2.29 2.29 Slllcone 0.67 0.67 0.67 0.67 Amlne 0.44 0.44 0.44 0.44 Tln 0.04 0.04 0.04 0.04 Water 0.44 0.44 0.44 0.44 CFC (Rll)14.57 14.57 14.57 14.57 Example 121.00 0 31.00 53.00 Fyrol Pcf 0 31.00 0 0 Isocyanate56.00 56.00 56.00 56.00 * All quantlties are ln grams.
Formulatlon 3a contalns no flre retardant.
Formulatlon~ 3c, 3e, 3g and 3h contaln lncreaslng amounts of tho flre retardant composltlon of thls lnventlon.
Formulatlons 3b, 3d and 3f contaln lncreaslng amounts of tho commerclally avallable flre retardant Fyrol Pcf (trlchloropropyl phosph~te).
On reactlon the varlous formulatlons gave rlse to polyurethane foams.
Limited O ygen Index ANSI/ASTM D 2863-77:
~hls test, ls an Australian and Internatlonal Standard of flammability (see Polvurethane Hand~ook, Ed.
Gunter Oertel, 11985, Carl Hanser Verlag, pp. 495-496).
'~
13~
~, ' .
~ ;t~83~7 P(~/A'~
, 3aslcally, the test measures the % of oxygen that will support candlelight combustion. The lower the ~ oxygen index the more flammable is a material.
R0sults:
~ Oxygen Index Blend 3a, (no fire retardant) 19.5 Blend 3b ~5.6g)(Conventlonal formulatlon) 22.5 Blend 3c (5.6g) 23.0 10 Blend 3d (21g)(unstable foam) 23.5 Blend 3e (21g) 24.6 Blend 3f (31g)(unusable foam) 25.0 Blend 3g (31g) 27.5 Blend 3h (53g) 28.5 These results show that foams produced uslng conventional flre retardants have a lower percentage oxygen lndex, and thus are more flammable than those foams produced utllislng the flre retardant compositlon of thl~ lnventlon. It ls to be noted that small lncreases in the percentage in oxygen lndex correspond to slgnlflcant increases ln flre retardancy. For example, a dlfference of 0.5 ~n the percentage oxygen lndex between formulatlon 3b (contalnlng a conventlonal flre retardant) and formulatlon 3c ~contalnlng the flre retardant compo~ltlon of this lnventlon) 18 lndlcative of a slgnl1cant decrease ln flammablllty of the foam produced by composltlon 3c.
The lncrease ln flre retardancy observed ln foams contalnlng the flre retardant composltlon of Example 1 ls belleved to result from a synerglstlc interactlon between the components of the flre retardant, namely TCPP and ;
TBP. ;~
~he foam produced from blends 3b, 3d and 3f, was ;
inferlor when compared to foams produced using the same level of the flre retardant of the lnventlon, insofar as flammablllty and stablllty are concerned.
Formulations according to blends 3b, 3d and 3f were ''' ' ''~:
:, , ! SUBSTITUTE SHEET ! : :~ ~
~ ,., .. ~
WO91/00307 PCT/AU~/00275 ~ -also produced, where the fire retardant Fyrol Pcf was replaced with halogenated phosphates, trichloroethyl phosphate (TCEP), and dimethylmono phosphate (DMMP), and wlth trlbromophenol (TBP). The percentage oxygen lndex of the foams produced uslng halogenated phosphates generally corresponded to those obtalned uslng the flre retardant Fyrol Pcf (TCPP). The 4Oams produced uslng T8P
were of very poor quallty and possessed a very low percentage oxygen index, below about 19.
These results show that the combination of a halogenated phosphate and a phenol substltuted with one or more halogen atoms interact synergistlcally to produce foams havlng decreased flammabillty, when compared to foams produced uslng elther of the components alone.
These results are surprlsing and unexpected.
The formulation of Example 1 was advantageous as ~table foams could be produced in the presence of large quantltles of 1re retardant (see blends 3g and 3h). In contra~t, formulatlons contalnlng more than 21 g of Fyrol Pcf or other halogenated phosphates were physlcally infsrlor ~poor dlmenslonal stabllity and low closed cell count) and gave rlse to unstable foams. Foams produced uslng the flre retardant TBP were of very poor quallty and were generally unstable regardless of the amount of T~P used.
The improved stabllity of foams produced uslng the flre retardant composition of Example 1 was unexpected, partlcul~rly as the independent components of the flre retardant of Example 1 dld not glve rlse to stable foams when large quantities were used (blends 3d and 3f).
Large quantities of the fire retardants of this invention may be incorporated into polyurethane foams without disturbing their structure. This is advantageous as foams which are highly flame resistant may be 35 produced. ;
, . ~ , .
SUe~TlTUTE SHEET i ., .
E~AMPLE 4 Soluble Fire Retardants:
The fire retardant composltlon of Example 1 was dlluted ln methanol to glve 20% (w/w) flre retardant composltlon. Thls material was sprayed onto needled polypropylene (a rlbbed wall coverlng manufactured by Melded Fabrlcs Pty Ltd of Melbourne) and allowed to dry.
Dry pick up welght was 15.7%
The materlal was then washed 10 times wlth hot water contalnlng a detergent.
The treated materlal exhlblts excellent fire retardancy as measured by ASTM method FMVSS 302, a horlzontal burn test ~see - Internatlonal Plastlcs Flammabillty Handbook, Author Jurgen Troltzsch, publlshed by Hanser Publlshers ISBN 3-446-13571-5, Section 8.3.1.2). In thls test, a slab of materlal 8 lnchQs x 3 lnCheJ wa8 held horlzontally ln a flame ~nd the rate of burn back mea~ured. Results classlfy samples ln this test a~ "8elf Extlnguishlng". ~he treated materlal dld not burn.
In contrast, non-treated materlal was completely consumed by flame, which rapldly spread down the strlp of material.
Needled polypropylene treated ln the same manner 25 (includlng washlng) as above, wlth equlvalent amounts of ;~
TCPP, TCEP, DMMP or T3P shows slgnlflcant burn back ;~
(about 83 mm/mlnute) and consumptlon of material.
.;' ',,: ',',':
~AMPLe 5 Flre ~etard~nt Co~tina For Timber:
ln thls example samples of 6mm Plywood (200mm by 200mm) were thoroughly drled by placlng 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 wlth a mixture comprising 20 parts of Example 1 and 80 parts of l,l,l,trichloroethane (solvent) and allowed to dry.
Other samples were also made at the same tlme and in a . ,:'"'",;,'~
';~
_ , .
, SUBSTITUTE SH~ET ~
. .. . . .
- 15 - ~0456Z9 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 50 that the sample size is 6mm by 10mm by 200mm wlth approxlmately one half of the sample (10 by 100mm) having a coatlng of flre retardant. The samples were then held downwards at an angle of 45 Deg wlth the untreated end in the lower acpect. The untreated end of each sample was llt. ~urning i8 observed as the flame travels upward.
~n the case of those samples treated wlth the flre retardant of Example 1, burnlng ceased upon the flame reaching the treated area. In all the other samples tested, complete burnlng took place wlth the sample~
belng consumed.
E~AMPLE 6 As ~ Sur~ce Trentment for Te~tlles:
In one example a mlxture is formsd with 85% of the flre retardant compound (Example 1) and 15% Terlc 200 (IC~). The Terlc 200 is heated to 50 Deg C to llqulfy it and the flre retardant 15 910wly added whllst the temperature ls kept at 50 dec C. Thl~ ls then allowed to cool. Thls mlxture ls further added to water at the rate of 200 grams per lltre, wlth constant agltatlon.
The fabrlc to be treated 19 lmmersed ln the solutlon and run through nlp roller~ to glve a plck up welght of between 40 to 100% (usually 70%). In some lnstances a st~ln relea~e, deodorant, uv stablllser or other treatment m~y be added to the mlxture. The wet fabric ls i 30 then stretched and exposed to hot alr at between 120 and 160-C for several mlnutes.
TESTS
Austral~an Standard 1530 (parts 2 & 3) TESTS FOR
FLAMMABILITY OF MATERIALS AND SIMULTANEOUS DETERMINATION
OF IGNITION, FLAME PROPAGATION, HEAT RELEASED AND SMOKE
IND B
Thls is an Australlan standard test (for a detailed .. . .
'VBSTITUTE SHEE~r i ., ~i reference, see International Plastics Flammabillty Handbook, Author Jurgen Troitzsch, published by Hanser Publlshers ISBN 3-446-13571-5 Section 8.2.16 which is incorporated hereln by reference) and in the~e examples testlng was carried out at the Australlan Wool Testlng Authorlty Ltd. North Melbourne, Vlctoria, Australia.
In one sample tested agalnst the AS 1530 part 2 test (a vertlcal burn test, flame applied to the bottom of a strlp of materlal) ths followlng test results were obtalned:
Sample: Woven fabrlc comprlslng 65% polyester and 35%
cotton havlng a nomlnal mass of 220 grams per square metre, colour navy.
Dry plck up welght of flre retardant actlve ~;;
lngredlents as per Example 6 was 10.8%
Reeults: (AWTA test # 7-428445-fn) Treated Untreated Result ranae ;~
Speed Factor 0 44 0-60 20 Sproad Factor 0 23 0-40 ~;
Heat Index 1 12 0-Upwards Flammablllty Index 1 85 0-lOO
In these tests, hlgh values reflect undeslrable i~
r-sults. It ls cl~ar from the above data that treatment wlth the flre retardant ls most advantageous. ;
In another sample tested agalnst the AS 1530 part 3 tost (~ample moved towards a radiant heat source) the followlng test results were obtalned: ~' Sample: Woven fabric comprisiny 100% wool having a nominal mass of 388 grams per square metre and a thlckness of 1.3 mm.
Dry pick up weight of fire retardant active ingredients as per Example 6 was 11.3%.
The test ls a comparison between unwashed materlal and materlal washed ten times wlth hot water and detergent.
,.... .................................................................. .... ... .....
¦ SUBSTITUTE SHEET ! -`
. , ...
W O 91/00307 PC~r/A U90/00275 - 17 - 20~5629 Results: (AWTA test # 7-428995 fn) UnwashedWashed Result range Ignitability 0 0 0-20 Spread of flame 0 0 0-10 5 Heat evolved 0 0 0-10 Smoke developed 5 4 0-10 Number of speclmens tested ~ 6 Number of specimens ignited ~ 0 Agaln, these results sho~ that the treated material aftsr w~shlng ls still highly fire resistant.
The described compositions and meth~ds have been adv~nced merely by way of explanation and many modlflcatlons m~y be made thereto wlthout departlng from the splrlt and scope of the inventlon whlch lncludes every novel feature and comblnatlon of novel features hereln dl~closed.
~. . ~
.~ S~5BSTITUTE SHEET i
Claims (24)
original claims 1, 2, 4 and 5 amended; other claims unchanged (1 page)]
THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:-
1. (Amended) A fire retardant composition which comprises:
(i) at least one halogenated phosphate; and (ii) at least one mono-phenol substituted with one or more halogen atoms.
(i) at least one halogenated phosphate; and (ii) at least one mono-phenol substituted with one or more halogen atoms.
2. (Amended) A fire retardant composition according to claim 1, wherein the halogenated phosphate is selected from 2-chloroethenol phosphate; 1-3-dichloro-2-propanol-phosphate; 1-chloro-2-propanol phosphate; 2-3-di-bromo-1-propanol phosphate; trichloroethyl phosphate; or trichloropropyl-phosphate.
3. A fire retardant composition according to claim 1, wherein the halogenated phosphate is selected from trichloroethyl phosphate or trichloropropyl phosphate.
4. (Amended) A fire retardant composition according to claim 1, wherein the mono-phenol substituted with one or more halogen atoms is substituted with one or more bromine atoms.
5. (Amended) A fire retardant composition according to claim 4, wherein the mono-phenol substituted with one or more halogen atoms is 2,4,6,tribromophenol.
6. A fire retardant composition according to claim 1 which is a substantially saturated solution.
7. A fire retardant composition according to any one of claims 1 to 6 which additionally comprises one or more of the group selected from a deodorant, stain release compound, wood-stain, paint, volatile organic solvent and smulsifying agent.
8. A polyol blend which comprises a hydroxyl containing polymer (polyol) and a fire retardant composition according to any one of claims 1 to 6.
9. A polyol blend according to claim 8 which additionally comprises one or more basic compounds.
10. A polyol blend according to claim 9 which the basic compound is an amine.
11. A polymeric blend according to any one of claims 8 to 12 which is free of chlorofluorocarbons (CFCs).
12. A polyol blend according to any one of claims 8 to 12 which additionally comprises 0.1% to 17%
chlorofluorocarbons.
chlorofluorocarbons.
13. A polyurethane foam which incorporates a fire retardant according to any one of claims 1 to 6.
14. A polyurethane foam when produced by reacting a polyol blend according to any one of claims 8 to 12 with an isocyanate compound, in the presence of water and one or more catalysts.
15. A polymeric material which incorporates a fire retardant composition according to any one of claims 1 to 6.
16. A polymeric material according to claim 15 selected from a polyurethane, epoxy resin and thermoset thermoplastic material.
17. A polymeric material according to claim 11 wherein the polymeric material is a polyvinyl chloride, polyester, polyimide, polypropylene, polyethylene, nylon, phenolic resin or acetal resin.
18. Textiles, yarns and fabrics treated with a fire retardant composition according to any one of claims 1 to 6.
19. Timber and wood-containing products treated with a fire retardant composition according to any one of claims 1 to 6.
20. A pulp of cellulose or like fibres which contains a fire retardant according to any one of claims 1 to 6.
21. Paper or cardboard which contains a fire retardant according to any one of claims 1 to 6.
22. An article treated with a fire retardant according to any one of claims 1 to 6, which article is a carpet, tent, screen cloth, drape or furnishing.
23. A process for treating an article with a fire retardant composition, which process comprises mixing the fire retardant composition of any one of claims 1 to 6 with an emulsifying agent, and thereafter applying the thus formed composition to the article.
24. A process for treating an article with a fire retardant, which process comprises mixing a fire retardant according to any one of claims 1 to 6 with an organic solvent and thereafter applying the mixture to the article desired to be treated.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPJ499689 | 1989-06-29 | ||
| AUPJ4996/89 | 1989-06-29 | ||
| AUPJ603289 | 1989-08-29 | ||
| AUPJ6032/89 | 1989-08-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2045629A1 true CA2045629A1 (en) | 1990-12-30 |
Family
ID=25643709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002045629A Abandoned CA2045629A1 (en) | 1989-06-29 | 1990-06-28 | Fire retardants |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0479829A1 (en) |
| KR (1) | KR920702699A (en) |
| CA (1) | CA2045629A1 (en) |
| HU (1) | HUT59168A (en) |
| WO (1) | WO1991000307A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2521588C2 (en) * | 2012-10-10 | 2014-06-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Саратовский государственный технический университет имени Гагарина Ю.А." | Epoxy compound |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9309151D0 (en) * | 1993-05-04 | 1993-06-16 | Zeneca Ltd | Syringes and syringe pumps |
| US5882338A (en) * | 1993-05-04 | 1999-03-16 | Zeneca Limited | Syringes and syringe pumps |
| GB9422082D0 (en) * | 1994-11-02 | 1994-12-21 | Zeneca Ltd | Reservoirs and delivery devices |
| US6985870B2 (en) | 2002-01-11 | 2006-01-10 | Baxter International Inc. | Medication delivery system |
| WO2009057104A2 (en) * | 2007-11-01 | 2009-05-07 | E.M.A.T. Technologies Ltd. | Polymer-based fire-retarding formulations |
| FI127667B (en) | 2017-03-09 | 2018-11-30 | Palonot Oy | Composition and method of manufacturing the same |
| RU2738111C1 (en) * | 2020-04-23 | 2020-12-08 | Федеральное государственное бюджетное образовательное учреж-дение высшего образования "Волгоградский государственный технический университет" (ВолгГТУ) | Fire-retardant intumescent material |
| RU2738116C1 (en) * | 2020-04-23 | 2020-12-08 | Федеральное государственное бюджетное образовательное учреж-дение высшего образования "Волгоградский государственный технический университет" (ВолгГТУ) | Fire-retardant intumescent material |
| RU2738367C1 (en) * | 2020-04-23 | 2020-12-11 | Федеральное государственное бюджетное образовательное учреж-дение высшего образования "Волгоградский государственный технический университет" (ВолгГТУ) | Fire-retardant intumescent material |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1079984A (en) * | 1965-09-01 | 1967-08-16 | Berk Ltd | Improvements in or relating to flexible polyurethane materials |
| GB1241542A (en) * | 1967-07-20 | 1971-08-04 | Bakelite Xylonite Ltd | Fire retardants |
| US3598733A (en) * | 1968-06-07 | 1971-08-10 | Hooker Chemical Corp | Fire retardant polymer compositions |
| US3715310A (en) * | 1968-07-17 | 1973-02-06 | Bakelite Xylonite Ltd | Fire-retardant compositions |
| BE756046A (en) * | 1969-09-12 | 1971-03-11 | Monsanto Co | COMBUSTION RETARDANT COMPOSITION |
| AU8671075A (en) * | 1974-12-06 | 1977-05-26 | Gen Electric | Flame retardant, non-dripping composition of polyphenylene ether and acrylonitrile - butadiene-styrene |
| GB2089350A (en) * | 1980-12-17 | 1982-06-23 | Ciba Geigy Ag | Flame retardant polymer compositions |
| EP0083796A1 (en) * | 1982-01-11 | 1983-07-20 | Bayer Ag | Flame-resistant moulding masses based on polyethylene terephthalate, process for its preparation and its use in the production of articles |
| DE3444868A1 (en) * | 1984-12-08 | 1986-06-12 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC MOLDS WITH FLAME-RESISTANT PROPERTIES |
-
1990
- 1990-06-28 KR KR1019910702004A patent/KR920702699A/en not_active Application Discontinuation
- 1990-06-28 EP EP90909570A patent/EP0479829A1/en not_active Withdrawn
- 1990-06-28 CA CA002045629A patent/CA2045629A1/en not_active Abandoned
- 1990-06-28 WO PCT/AU1990/000275 patent/WO1991000307A1/en not_active Application Discontinuation
- 1990-06-28 HU HU905458A patent/HUT59168A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2521588C2 (en) * | 2012-10-10 | 2014-06-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Саратовский государственный технический университет имени Гагарина Ю.А." | Epoxy compound |
Also Published As
| Publication number | Publication date |
|---|---|
| KR920702699A (en) | 1992-10-06 |
| EP0479829A4 (en) | 1992-01-07 |
| HUT59168A (en) | 1992-04-28 |
| WO1991000307A1 (en) | 1991-01-10 |
| EP0479829A1 (en) | 1992-04-15 |
| HU905458D0 (en) | 1992-03-30 |
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