EP0275280A4 - New thiophosphate ester; also polyurethane foam or prepolymer, containing tris- and bis- (2,4,6-tribromophenoxy) (thio) phosphate. - Google Patents
New thiophosphate ester; also polyurethane foam or prepolymer, containing tris- and bis- (2,4,6-tribromophenoxy) (thio) phosphate.Info
- Publication number
- EP0275280A4 EP0275280A4 EP19870904666 EP87904666A EP0275280A4 EP 0275280 A4 EP0275280 A4 EP 0275280A4 EP 19870904666 EP19870904666 EP 19870904666 EP 87904666 A EP87904666 A EP 87904666A EP 0275280 A4 EP0275280 A4 EP 0275280A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- prepolymer
- compound
- mixture
- formula
- tribromophenoxy
- 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.)
- Withdrawn
Links
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 13
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 13
- -1 thiophosphate ester Chemical class 0.000 title claims abstract description 11
- 229920001730 Moisture cure polyurethane Polymers 0.000 title claims description 5
- 229910019142 PO4 Inorganic materials 0.000 title description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title description 4
- 239000010452 phosphate Substances 0.000 title description 4
- UYYBTSWSNFBXPF-UHFFFAOYSA-N 1,3,5-tribromo-2-(2,4,6-tribromophenoxy)sulfanyloxybenzene Chemical compound BrC1=C(OSOC2=C(C=C(C=C2Br)Br)Br)C(=CC(=C1)Br)Br UYYBTSWSNFBXPF-UHFFFAOYSA-N 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005864 Sulphur Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 239000006260 foam Substances 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 12
- 150000002513 isocyanates Chemical group 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 150000007530 organic bases Chemical class 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical group 0.000 claims description 6
- 230000000979 retarding effect Effects 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000000779 smoke Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000003466 anti-cipated effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 150000005691 triesters Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000036647 reaction Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- OWNZHTHZRZVKSQ-UHFFFAOYSA-N tribromo(sulfanylidene)-$l^{5}-phosphane Chemical compound BrP(Br)(Br)=S OWNZHTHZRZVKSQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 1
- PKLRDZGLQIGNOJ-UHFFFAOYSA-N BrC1=C(C(=CC(=C1)Br)Br)O.[BrH]1C=CC=C1 Chemical compound BrC1=C(C(=CC(=C1)Br)Br)O.[BrH]1C=CC=C1 PKLRDZGLQIGNOJ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- JOCBASBOOFNAJA-UHFFFAOYSA-N N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid Chemical compound OCC(CO)(CO)NCCS(O)(=O)=O JOCBASBOOFNAJA-UHFFFAOYSA-N 0.000 description 1
- WGOGKJYRAWQHLR-UHFFFAOYSA-N P(=S)(O)(O)O.[BrH]1[BrH]CC=C1 Chemical compound P(=S)(O)(O)O.[BrH]1[BrH]CC=C1 WGOGKJYRAWQHLR-UHFFFAOYSA-N 0.000 description 1
- CFDZSJXVBSLSBV-UHFFFAOYSA-N P(=S)(O)(O)O.[BrH]1[BrH][BrH]C=C1 Chemical compound P(=S)(O)(O)O.[BrH]1[BrH][BrH]C=C1 CFDZSJXVBSLSBV-UHFFFAOYSA-N 0.000 description 1
- IUSGATWWECUUDG-UHFFFAOYSA-N P(O)(O)O.[BrH]1[BrH][BrH]C=C1 Chemical compound P(O)(O)O.[BrH]1[BrH][BrH]C=C1 IUSGATWWECUUDG-UHFFFAOYSA-N 0.000 description 1
- 206010063493 Premature ageing Diseases 0.000 description 1
- 208000032038 Premature aging Diseases 0.000 description 1
- 241000022563 Rema Species 0.000 description 1
- 235000017899 Spathodea campanulata Nutrition 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 150000001987 diarylethers Chemical class 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
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
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
-
- 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
- C08K5/5398—Phosphorus bound to sulfur
Definitions
- This invention relates to compounds, processes and products.
- this invention relates to broninated phenol esters and to their use in mixtures with prepolymers in order to improve certain characteristics of materials to be synthesized from such prepolymers.
- An additive of this invention is one compound or a mixture of compounds chosen from a group of brominated phenol esters which ha ve exhibited f ire retardent , surf actant and plasticising properties.
- a method of producing fire retardent polyurethane foam wherein the additive is mixed into either an isocyanate prepolymer or a polyol prepolymer of the polyur ⁇ thane system, and the modified prepolymer thus formed is in turn mixed with polyol prepolymer or isocyanate prepolymer respectively to produce polyurethane foam.
- the present invention provides a polyurethane foam containing a fire retarding amount of a mixture of a compound of formula XI set out in the accompanying drawings and a compound of formula XII set out in the accompanying drawings wherein X 1 and S 2 are oxygen or sulphur and RO- is 2,4,6-tribromophenoxy.
- the present invention also provides a polyurethane foam prepolymer containing a fire retarding amount, with respect to a foam which can be produced, of a mixture of a compound of formula XI set out in the accompanying drawings and a compound of fornula XII set out in the accompanying drawings wherein X 1 and X 2 are oxygen or sulphur and RO- is 2,4,6- tribromophenoxy. Preferably X 1 and X 2 are both oxygen or both sulphur.
- the foam or prepolymer may additionally include a compound of formula V set out in the accompanying drawings.
- the prepolymer may be a polyol or isocyanate. The latter is preferred.
- the prepolymer preferably comprises an organic base.
- That base is preferably selected from triethylamine, ethylene diamine, and triethano 1 amine.
- said compound of formula XI is present in said mixture as from 70 to 80%.
- said compound of formula XII is present in said mixture as from 20 to 30%. by weight.
- said compound of formula XIII is present in said mixture as from 3 to 8% by weight.
- said mixture is present in said prepolymer as from 21 ⁇ 2 to 20 preferably 8 to 10% by weight.
- said organic base is present in said mixture as from 6 to 8% by weight.
- the present invention also provides the compound of formula II set out in the accompanying drawings wherein RO- is 2,4,6 -tribromophenoxy and mixtures containing same.
- the present invention provides in a preferred aspect for use of five brominated phenol esters with compound of formulae I-V set out in the accompanying drawings.
- Compound II which is the preferred component of the additive does not seem to have been previously described.
- Compound IV as a fire retardent does not seem to have been described.
- One previous publication [Benbow & Cullis (1975), Combustion and Flame, v.24, p.217-230] describes the use of Compound III for fire retardation of flexible polyurethane foam. Its use was considered by those authors to be unsatisfactory, primarily because of poor solubility.
- the acidity introduced by either Compound II or I V partly neutralizes amine catalysts in the system resulting in a reduced rate of foaming when polyol and isocyanate are mixed.
- This ef f ect may be at l east in part reduced by addition of an organic base, severa l of which ha ve been tested successful ly.
- a t t empera tur es pr oduced b y a n exoth ermic react ion when isocyanate and polyol prepolymers are mixed, isocyanate is released to recombine immediately with hydroxyl residues to f orm the urethane l inkages.
- the diester (Compound II or I V) is not onl y ful ly solubil ized but also helps to solubilize the triesters, both phosphate (Compound I or III) and phosphite (Compound V), possibly by pi-bonding.
- the f ol lowing example provides a process f or manufacture of the additive.
- the esters were manufactured in acetone solution by esterif ication of bromol (2,4 ,6- tribromophenol) produced in situ from phenol.
- EXAMPLE In a first procedure, phenol in acetone was mixed with bromine (1:5.2 phenol/bromine w/w) to form bromol, then this mixture was mixed with phosphorus tribromide (1.05:1 pheno 1 /b romi de w/w) at a temperature betwen 15°C and 30°C, thus forming a solution of tribromol phosphite.
- the initial phenol concentration in acetone was about 80£ w/w, but this value was not critical and was sometimes varied widely according to the mechanics of mixing. This solution was stored under nitrogen until used.
- phenol in acetone was mixed with thiophosphoryl bromide in bromine solution while controlling the temperature to below 30°C.
- Reactant ratios were 1:5.2:1.05-1.09 (w/w/w phenol/bromine/bromide), this forming a mixed solution of tribromol thiophosphate (70-80% ) with the balance being dibromol thiophosphate.
- This solution was then blended with the phosphite solution from the first process (20:1 w/w phosphate/phosphite) and an amount of organic base (triethylamine) sufficient to neutralize 85-95 ⁇ of residual acidity.
- This mixture was then poured into water whereupon a white flocculated precipitate separated immediately. This precipitate was then dried to reduce water content below 5 i w/w.
- the final mixture then became Compounds I/II/V (approx. 15/5/1).
- Those other characteristics include (1 ) enhanced surfactancy of isocyanate prepolymer which tends to improve cell structure and to reduce or remove the need for silicone, (2) improved adhesion to substrate expected from lowering of silicone addition, (3) reduced need for polymerization catalysts, and (4) anticipated marked suppression of embrittlement and catastrophic failure caused by normal or premature aging.
- Compounds I and II are superior to Compounds III and IV with respect to smoke production, catalysis and solubility, but are inferior with respect to flammability, stability to aerial oxidation and cost.
- Compound V is a fire and smoke suppressant in its own right but in this application it is provided mainly as an antioxidant for mixing with either of the other compounds to confer long term stability. The effects of each ⁇ f these compounds seemed to be proportional to their content.
- Type S Bayer Desmodur 44V20 + Bayertherm 4150 (1:1 v/v)
- Type G Lackfa Lamoltan
- Type K Bayer Desmodur 44V20: Mixture A (100:16 w/w) + Bayertherm 4150 (1,1 v/v),
- fixture B performed similarly.
- Type K is the standard type S a l tered on l y by addition of the additive of this invention.
- the table represents the direct comparison of commercial ly available standard and premium grade foams with the those provided herein.
- Values for type S have been arbitrarily set at 10; optimum performance would be zero. Thus, low values are preferred.
- Both type G and type K behave markedly better than type S. With respect to fire and smoke type K is inferior to type G, but type K is so far superior to type G with respect to structural integrity that its overall performance is significantly better than type G. Type K catches fire and burns at a substantially lower temperature than the other two types.
- Type K fires are far less dramatic than those of type S, but it is anticipated that in widespread use the most significant advance of type K is to be its relatively low potential to produce those gaseous products which are proven potent killers.
- Use of polyhalogenated diaryl ethers such as those used in type G is being voluntarily restricted pending availability of satisfactory alternatives because such compounds are known or suspected precursors of di ⁇ xins.
- Additives ⁇ f the type provided herein have no inherent capacity to produce dioxins at the temperatures anticipated in any combustion possibly sustained by type K foam.
- These inventions provided herein have contributed to significant advances in the applicability of polyurethane f oam to situations currently precluded because of flammability.
- These inventions also provide materials with surfactant and plasticising properties which may be of major, rather than incidental, interest in various applications. The claims form part of the disclosure of this specification.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A polyurethane foam including prepolymer forms containing a fire wetardant mixture of formulae (XI) and (XII), wherein X1 et X2 are oxygen or sulphur and RO is 2,4,6-tribromophenoxy; and a new compound of formula (II), where RO is as previously defined.
Description
NEW THIOPHOSPHATE ESTER; ALSO POLYURETHANE FOAM OR PREPOLYMER, CONTAINING TRIS- AND BIS- (2,4,6-TRIBROMOPHENOXY) (THIO) Titl .PHOSPHATE This invention relates to compounds, processes and products. In a particular aspect this invention relates to broninated phenol esters and to their use in mixtures with prepolymers in order to improve certain characteristics of materials to be synthesized from such prepolymers. An additive of this invention is one compound or a mixture of compounds chosen from a group of brominated phenol esters which ha ve exhibited f ire retardent , surf actant and plasticising properties. In a particular aspect of the present invention there is provided a method of producing fire retardent polyurethane foam wherein the additive is mixed into either an isocyanate prepolymer or a polyol prepolymer of the polyurβthane system, and the modified prepolymer thus formed is in turn mixed with polyol prepolymer or isocyanate prepolymer respectively to produce polyurethane foam. The present invention provides a polyurethane foam containing a fire retarding amount of a mixture of a compound of formula XI set out in the accompanying drawings and a compound of formula XII set out in the accompanying drawings wherein X1 and S2 are oxygen or sulphur and RO- is 2,4,6-tribromophenoxy. The present invention also provides a polyurethane foam prepolymer containing a fire retarding amount, with respect to a foam which can be produced, of a mixture of a compound of formula XI set out in the accompanying drawings and a compound of fornula XII set out in the accompanying drawings wherein X1 and X2 are oxygen or sulphur and RO- is 2,4,6- tribromophenoxy. Preferably X1 and X2 are both oxygen or both sulphur. The foam or prepolymer may additionally include a compound of formula V set out in the accompanying drawings. The prepolymer may be a polyol or isocyanate. The latter is preferred. The prepolymer preferably comprises an organic base. That base is preferably selected from triethylamine,
ethylene diamine, and triethano 1 amine. Preferably said compound of formula XI is present in said mixture as from 70 to 80%. Preferably said compound of formula XII is present in said mixture as from 20 to 30%. by weight. Preferably said compound of formula XIII is present in said mixture as from 3 to 8% by weight. Preferably said mixture is present in said prepolymer as from 2½ to 20 preferably 8 to 10% by weight. Preferably said organic base is present in said mixture as from 6 to 8% by weight. The present invention also provides the compound of formula II set out in the accompanying drawings wherein RO- is 2,4,6 -tribromophenoxy and mixtures containing same. Various particularly preferred aspects of this invention will now be described. The present invention provides in a preferred aspect for use of five brominated phenol esters with compound of formulae I-V set out in the accompanying drawings. Compound II, which is the preferred component of the additive does not seem to have been previously described. The use of Compound IV as a fire retardent does not seem to have been described. One previous publication [Benbow & Cullis (1975), Combustion and Flame, v.24, p.217-230] describes the use of Compound III for fire retardation of flexible polyurethane foam. Its use was considered by those authors to be unsatisfactory, primarily because of poor solubility. Use of Compounds I, III, and V for fire retardation of various f lammable materials has been described, but always in applications and combinations distinctly different from those described herein. The widespread sale of urethane prepolymers rather than the finished polymer requires the manufacture of prepolymers with high stability during protracted storage. This imposes strict limitations upon the choice of additives including f ire retardents, primarily because of precipitation and/or neutralization of catalysts during storage. The solubility of purified preparations of
Compounds III and V in either type of prepolymer is limited? C ompound I h as much g reater so l ub i l it y , but a t h i gh concentrations it stil l tends to precipitate at temperatures below 20°C. However, incompletely esterified preparations of Compound I, that is those which contain some Compound II , are very much more soluble in each prepol ymer. Similarl y, incompletely esterified preparations of Compound III which contain some Compound IV, are very much more soluble in each prepolymer. Either of these preparations alone or when mixed intimately with Conpound V yields easi ly a true solution which seems to be stable indefinitely. The acidity introduced by either Compound II or I V partly neutralizes amine catalysts in the system resulting in a reduced rate of foaming when polyol and isocyanate are mixed. This ef f ect may be at l east in part reduced by addition of an organic base, severa l of which ha ve been tested successful ly. The rema rkab l e ef f ecti v eness of the dies t ers (Compounds I I and I V ) upon th e so l ub i l i ti es o f their corresponding triesters in isocyanate prepolymer is believed to be due to the reversable combination of isocyanate, residues with monophosphoric acid residues possib ly as suggested as Reaction 1 in the accompanying drawings wherein R 1 represents an organic functional group. The forward reaction is favoured at low temperatures, but the balance begins to shift significantly towards the b ack rea ction a t temperatures abo v e 40 ° C. Thus , a t t empera tur es pr oduced b y a n exoth ermic react ion when isocyanate and polyol prepolymers are mixed, isocyanate is released to recombine immediately with hydroxyl residues to f orm the urethane l inkages. In its esterif ied f orm, the diester (Compound II or I V) is not onl y ful ly solubil ized but also helps to solubilize the triesters, both phosphate (Compound I or III) and phosphite (Compound V), possibly by pi-bonding. An important e f f ect of the p os sib l e chemica l combination of isocyanate with diester and its association with triester, then their re-release during the foaming
reaction, is that the uniform dispersion of the esters is thereby promoted. This overcomes one of the main problems with fire retardents in polyurethane prepolymers, namely uneven dispersion and therefore uneven protection against fire. The f ol lowing example provides a process f or manufacture of the additive. The esters were manufactured in acetone solution by esterif ication of bromol (2,4 ,6- tribromophenol) produced in situ from phenol. EXAMPLE In a first procedure, phenol in acetone was mixed with bromine (1:5.2 phenol/bromine w/w) to form bromol, then this mixture was mixed with phosphorus tribromide (1.05:1 pheno 1 /b romi de w/w) at a temperature betwen 15°C and 30°C, thus forming a solution of tribromol phosphite. The initial phenol concentration in acetone was about 80£ w/w, but this value was not critical and was sometimes varied widely according to the mechanics of mixing. This solution was stored under nitrogen until used. In a second procedure, phenol in acetone was mixed with thiophosphoryl bromide in bromine solution while controlling the temperature to below 30°C. Reactant ratios were 1:5.2:1.05-1.09 (w/w/w phenol/bromine/bromide), this forming a mixed solution of tribromol thiophosphate (70-80% ) with the balance being dibromol thiophosphate. This solution was then blended with the phosphite solution from the first process (20:1 w/w phosphate/phosphite) and an amount of organic base (triethylamine) sufficient to neutralize 85-95} of residual acidity. This mixture was then poured into water whereupon a white flocculated precipitate separated immediately. This precipitate was then dried to reduce water content below 5 i w/w. The final mixture then became Compounds I/II/V (approx. 15/5/1). In an al ternative to the second procedure thiophosphoryl bromide was replaced by phosphoryl bromide. Reactant ratios were then 1:5.2:0.94-0.97. The final mixture then became Compounds III/IV/V (approx. 15/5/1). The preferred additive is Itixture A comprised of
Compounds I, II and V (approx. 15/5/1). Compound V may be 3- 12% of the mixture; about 5% is considered optimum. Triethylamine is the preferred neutralizing base despite its high flammability; in practice, it evaporates out of foam within 1-2 days. Idhen added to isocyanate prepolymer as provided herein mixture A confers the maximum benefits yet found from use of any of the Compounds I-V. This is illustrated in the following table which lists a consensus of opinions of those persons who have studied the burning of polyurethane foams subject of this invention. Although these assessments are subjective, the inventor regards them as the best current indicators of performance because of a lack of objective measures for some characteristics important for performance. A similar mixture, flixture B, was formed containing compounds III, IV and V in similar proportions. The three types αf foam subject of the following table have no remarkable physical differences. The choice of composition of additive for type K foam depends on the relative importance of cost, fire retardency, smoke suppression, and some other physical characteristics conferred upon the foam by the additive. Those other characteristics include (1 ) enhanced surfactancy of isocyanate prepolymer which tends to improve cell structure and to reduce or remove the need for silicone, (2) improved adhesion to substrate expected from lowering of silicone addition, (3) reduced need for polymerization catalysts, and (4) anticipated marked suppression of embrittlement and catastrophic failure caused by normal or premature aging. Compounds I and II are superior to Compounds III and IV with respect to smoke production, catalysis and solubility, but are inferior with respect to flammability, stability to aerial oxidation and cost. Compound V is a fire and smoke suppressant in its own right but in this application it is provided mainly as an antioxidant for mixing with either of the other compounds to confer long term stability. The effects of each αf these compounds seemed to be proportional
to their content.
Table. Relative performance of three compositions of polyurethane foam.
characteristic type S type G type K
1 ) fire retardency -initial flare 10) 3) 5)
)20 )4 )8
-sustained burning 10) 1 ) 3)
2) smoke from burn -carbonaceous 10) 2) 3)
)20 )3 )6
-irritating 10) 1 ) 3)
3) integrity after burn -cell structure 10) 7) 2) -collapse, cracks )20 )20 )a and delaminating 10) 13) 6)
= = == = = = == =
Total 60 27 22
Type S: Bayer Desmodur 44V20 + Bayertherm 4150 (1:1 v/v) Type G: Lackfa Lamoltan Type K: Bayer Desmodur 44V20: Mixture A (100:16 w/w) + Bayertherm 4150 (1,1 v/v),
Subject to the above, fixture B performed similarly.
The table summarizes observations made after use and combustion of polyurethane foams of various manufacture, all of which contain additives designed to reduce flammability and smoke evo lution. Such f oams are most dif f icult with respect to minimizing the eff ects of combustion. Their g r e a t e s t a t t r i b u t e , n a m e l y h e a t i n s u l a t i o n , i s simul taneously responsib l e for their greatest drawback , namel y f lammability, primari ly because their superlati ve insulating capacity ensures very high point temperatures when subjected to heat. Type S foam is a standard, commonly sol d type of pouring f oam. It contains tris(chl oroethyl ) p ho spha t e , a t yp e of f i re ret a rdent common l y used in po l yurethane f oam. Typ e G i s a p r emium qua l ity f oam containing a dif f erent type of fire retardent with much greater efficacy than that of type S, namely polybromophenyl ether. Type K is the standard type S a l tered on l y by addition of the additive of this invention. Thus, the table represents the direct comparison of commercial ly available standard and premium grade foams with the those provided herein. Values for type S have been arbitrarily set at 10; optimum performance would be zero. Thus, low values are preferred. Both type G and type K behave markedly better than type S. With respect to fire and smoke type K is inferior to type G, but type K is so far superior to type G with respect to structural integrity that its overall performance is significantly better than type G. Type K catches fire and burns at a substantially lower temperature than the other two types. This is by design for good reasons: the low burning temperature (1 ) renders extinguishing of burning foam relatively easy, (2) minimizes the rate of spread of fire and the risk of creation of an explosive fireball, and (3) minimizes the production of carbon monoxide which is the major cause of death in polyurethane and other polymer fires. Type K fires are far less dramatic than those of type S, but it is anticipated that in widespread use the most significant advance of type K is to be its relatively low potential to produce those
gaseous products which are proven potent killers. Use of polyhalogenated diaryl ethers such as those used in type G is being voluntarily restricted pending availability of satisfactory alternatives because such compounds are known or suspected precursors of diαxins. Additives αf the type provided herein have no inherent capacity to produce dioxins at the temperatures anticipated in any combustion possibly sustained by type K foam. These inventions provided herein have contributed to significant advances in the applicability of polyurethane f oam to situations currently precluded because of flammability. These inventions also provide materials with surfactant and plasticising properties which may be of major, rather than incidental, interest in various applications. The claims form part of the disclosure of this specification.
Claims
THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:- 1. A polyurethane foam containing a fire retarding amount of a mixture of a compound of formula XI
XI
and a compound of formula XII
XII
wherein X1 and X2 are oxygen or sulphur and RO-is 2,4,6 - tribromophenoxy. 2. A foam as claimed in claim 1 , wherein X1 and X2 are both oxygen or sulphur. 3. A foam as claimed in claim 2, wherein X 1 and X2 are both sulphur. 4. A foam as claimed in claim 2, wherein X1 and X2 are both oxygen. 5. A foam as claimed in any preceding claim and additionally including a compound of formula V.
V
wherein RO - is 2,4,6-tribromophenoxy. 6. A polyurethane foam prepolymer containing a fire retarding amount, with respect to a foam which can be produced, of a mixture of a compound of formula XI
χι
and a compound of formula XII
XII
RO
wherein X1 and X2 are oxygen or sulphur and RO-is 2,4,6 - tribromophenoxy.
7. A prepolymer as claimed in claim 6, wherein X1 and X2 are both oxygen or sulphur.
8. A prepolymer as claimed in claim 7, wherein X 1 and X2 are both sulphur.
9. A prepolyner as claimed in claim 7, wherein X1 and X2 are both oxygen.
10. A prepolyner as claimed in any one αf claims 6-9 and additionally including a compound of formula V.
wherein RO - is 2,4,6-tribromophenoxy.
11. A prepolymer as claimed in any one of claims 6-10, wherein said prepolymer is an isocyanate.
12. A prepolymer as claimed in any one of claims 6-11 , wherein said prepolymer is a polyol.
13. A prepolymer as claimed in any one of claims 6-12, and including an organic base.
14. A prepolymer as claimed in claim 13, wherein the organic bass is selected from triethylamine, ethylene diamine, and trlethanolamine.
15. A prepolymer as claimed in any one of claims 6-14, wherein said compound of formula XI is present in said mixture as from 70 to 80% by weight.
16. A prepolymer as claimed in any one of claims 6-14, wherein said compound of formula XII is present in said mixture as from 20 to 30 % by weight.
17. A prepolymer as claimed in claim 10, wherein said compound of fornula XIII is present in said mixture as from 3 to 8 % by weight.
18. A prepolymer as claimed in any one of claims 6-17, wherein said mixture is present in said prepolymer as from 2£ to 20 preferably 8 to 10% by weight. 19. A prepolymer as claimed in claim 13, wherein said organic base is present in said mixture as from 6 to 8% by weight. 20. A compound of formula II
wherein RO- is 2,4,6- tribromophenoxy. 21. A mixture comprising a compound of formula XI set out in claim 1 and a compound of formula XII set out in claim 1. 22. A mixture as claimed in claim 21 and additional ly containing a compound of formula V set out in claim 5. 23. A f oam , prepol ymer or mixture substantia l l y as hereinbef ore described with ref erence to any one the examples. 24. The articles, things, parts, elements, steps, features, methods, processes, compounds and compositions referred to or indicated in the specification and/or claims of the application individually or collectively, and any and all combinations of any two or more of such.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU6810/86 | 1986-07-09 | ||
AUPH681086 | 1986-07-09 | ||
AUPI093887 | 1987-03-17 | ||
AU938/87 | 1987-03-17 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0275280A1 EP0275280A1 (en) | 1988-07-27 |
EP0275280A4 true EP0275280A4 (en) | 1988-11-16 |
Family
ID=25643124
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19870904666 Withdrawn EP0275280A4 (en) | 1986-07-09 | 1987-07-09 | New thiophosphate ester; also polyurethane foam or prepolymer, containing tris- and bis- (2,4,6-tribromophenoxy) (thio) phosphate. |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0275280A4 (en) |
JP (1) | JPH01500908A (en) |
KR (1) | KR880701725A (en) |
DK (1) | DK128088D0 (en) |
ES (1) | ES2004771A6 (en) |
GR (1) | GR871082B (en) |
PT (1) | PT85297B (en) |
WO (1) | WO1988000199A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2917089A (en) * | 1988-01-04 | 1989-08-01 | Richard John Maerschel | Compounds or mixtures formed by reaction of 2,4,6-tribromophenyl(thio)phosphate esters with boric acid orborates and use as fire retardant |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2857308A (en) * | 1956-11-15 | 1958-10-21 | Monsanto Chemicals | Method of destroying nematodes employing phosphorodithioates |
US4021406A (en) * | 1973-05-21 | 1977-05-03 | M & T Chemicals Inc. | Flame retardant compositions |
US4059655A (en) * | 1975-11-24 | 1977-11-22 | Ppg Industries, Inc. | Process for preparing halogenated diaryl hydrogen phosphates |
DE2809773A1 (en) * | 1977-03-30 | 1978-10-05 | Teijin Ltd | FULLY AROMATIC POLYAMIDE FIBERS AND THE PROCESS FOR THEIR PRODUCTION |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1401863A (en) * | 1972-11-02 | 1975-08-06 | Gen Electric | Flame retardant polyester resin compositions |
US4258169A (en) * | 1980-03-26 | 1981-03-24 | The Upjohn Company | Polyisocyanate compositions containing in-situ formed pyrophosphate mold release agent and process of making |
DE3127914A1 (en) * | 1981-07-15 | 1983-02-03 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING FLAME-RESISTANT POLYUTHERANE AND / OR POLYISOCYANURATE GROUPS CONTAINING |
NL8301569A (en) * | 1983-05-04 | 1984-12-03 | Gen Electric | POLYMER MIXTURE WITH FLAME-RESISTANT PROPERTIES, SUITABLE FOR WIRE COAT EXTRUSION, BASED ON POLYPHENYLENE OXIDE AND ELECTRICALLY CONDUCTIVE WIRE. |
US4477600A (en) * | 1983-09-23 | 1984-10-16 | Stauffer Chemical Company | Polyurethane foams having low scorch discoloration |
JPH0629313B2 (en) * | 1984-12-07 | 1994-04-20 | 武田薬品工業株式会社 | Method for manufacturing flame-retardant flexible urethane foam |
US4616044A (en) * | 1985-01-25 | 1986-10-07 | Stauffer Chemical Company | Heat laminatable polyether urethane foam |
-
1987
- 1987-07-09 ES ES8702232A patent/ES2004771A6/en not_active Expired
- 1987-07-09 EP EP19870904666 patent/EP0275280A4/en not_active Withdrawn
- 1987-07-09 GR GR871082A patent/GR871082B/en unknown
- 1987-07-09 WO PCT/AU1987/000212 patent/WO1988000199A1/en not_active Application Discontinuation
- 1987-07-09 PT PT85297A patent/PT85297B/en unknown
- 1987-07-09 JP JP62504329A patent/JPH01500908A/en active Pending
- 1987-07-09 KR KR1019880700260A patent/KR880701725A/en not_active Application Discontinuation
-
1988
- 1988-03-09 DK DK128088A patent/DK128088D0/en not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2857308A (en) * | 1956-11-15 | 1958-10-21 | Monsanto Chemicals | Method of destroying nematodes employing phosphorodithioates |
US4021406A (en) * | 1973-05-21 | 1977-05-03 | M & T Chemicals Inc. | Flame retardant compositions |
US4059655A (en) * | 1975-11-24 | 1977-11-22 | Ppg Industries, Inc. | Process for preparing halogenated diaryl hydrogen phosphates |
DE2809773A1 (en) * | 1977-03-30 | 1978-10-05 | Teijin Ltd | FULLY AROMATIC POLYAMIDE FIBERS AND THE PROCESS FOR THEIR PRODUCTION |
Non-Patent Citations (2)
Title |
---|
CHEMICAL ABSTRACTS, vol. 93, no. 26, 29th December 1980, page 96, abstract no. 241255n, Columbus, Ohio, US; A.L. LABUTIN et al.: "Fire-resistant polyurethane sealant", & KAUCH. REZINA 1980, (8), 29-31 * |
See also references of WO8800199A1 * |
Also Published As
Publication number | Publication date |
---|---|
KR880701725A (en) | 1988-11-04 |
WO1988000199A1 (en) | 1988-01-14 |
PT85297A (en) | 1987-08-01 |
DK128088A (en) | 1988-03-09 |
GR871082B (en) | 1987-11-12 |
JPH01500908A (en) | 1989-03-30 |
PT85297B (en) | 1989-10-12 |
ES2004771A6 (en) | 1989-02-01 |
EP0275280A1 (en) | 1988-07-27 |
DK128088D0 (en) | 1988-03-09 |
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