GB1584615A - Flame retardant compositions comprising halogen-containingorganic phosphorus compounds - Google Patents

Flame retardant compositions comprising halogen-containingorganic phosphorus compounds Download PDF

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GB1584615A
GB1584615A GB20686/77A GB2068677A GB1584615A GB 1584615 A GB1584615 A GB 1584615A GB 20686/77 A GB20686/77 A GB 20686/77A GB 2068677 A GB2068677 A GB 2068677A GB 1584615 A GB1584615 A GB 1584615A
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    • C07F9/2479—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1)
    • C07F9/2491—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1) containing the structure P(=X)n-N-N (X = O, S, Se; n = 0, 1)
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    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
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    • C07F9/40—Esters thereof
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    • C07F9/40—Esters thereof
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Description

(54) FLAME RETARDANT COMPOSITIONS COMPRISING HALOGEN CONTAINING ORGANIC PHOSPHORUS COMPOUNDS (71) I, JOHN JOSEPH WALDMANN, a citizen of the United States of America, of 6531 Monroe Road, Apartment 3, Charlotte, State of North Carolina, United States of America, do hereby declare the invention for which I pray that a Patent may be granted to me, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to compositions containing halogen-containing organic phosphorus compounds having particular utility as flame retardants. More particularly, this invention relates to compositions containing a group of halogen-containing organic phosphorus compounds having reactive functionality and which are useful as reactive flame retardants and as intermediates in the production of reactive flame retardants for use in various materials.
The use of organic compounds containing phosphorus and halogen as flame retardant additives is well known. However, many of these flame retardant additives have been found unsatisfactory for one or more of the following reasons: (1) They must be incorporated in large amounts to be effective as a flame retardant; (2) They undesirably alter the chemical or physical properties of the material to which they are added; (3) They are not permanently retained in the material. but wash out or leach out over a period of time; (4) They are not thermally stable and split off chlorine, bromine, hydrogen chloride or hydrogen bromide when heated; and (5) They are toxic.
It is also known to employ as flame retardants. halogen-containing organic phosphorus compounds having reactive functional groups therein which permit the flame retardant to react with the material to which it is added to provide for better retention in the material.
These known reactive flame retardant compounds reduce the problem of retention as compared to flame retardant additives, but generally still suffer many of the disadvantages mentioned above. Note, for example, U. S. Patent 3,840,622 and the several patents relating to reactive flame retardants which are discussed therein by way of background. See also the following more recent U. S. Patents: 3,883.620; 3,886,237; 3,888,844, and 3.920,685.
In the present invention, halogen-containing organic phosphorus compounds have been provided which overcome or reduce many of the problems above mentioned and are particularly useful as flame retardants and as intermediates in the production of flame retardants. These compounds exhibit exceptionally good flame retardant properties and thermal stability and contain reactive functional groups which allow them to readily combine chemically with the materials to which they are added.
According to one aspect thereof. the invention provides a flame retardant polymeric composition comprising a normally flammable polymer and a reactive flame retardant in the form of a halogen-containing organic phosphorus compound having the formula:
wherein n is the whole number 1 or 2; X represents chlorine or bromine; Z represents oxygen or sulfur; A represents an oxygen atom or a bivalent radical containing one or more oxy linkages; B represents a chloro, bromo, hydroxy, alkoxy, halo- alkoxy, alkenyloxy, haloalkenyloxy.
or N - (isocyanatohydrocarbyl) carbamoyloxy radical; R1 represents a chloro, bromo, hydrocarbyl, substituted hydrocarbyl. hydrocarbyloxy, substituted hydrocarbyloxy, heterocyclyl substituted heterocyclyl, heterocyclyloxy, or substituted heteroclyloxy radical; and R2 represents a radical selected from those defined for R1 or represents amino. hydrazino, or -OM where M is one equivalent of a metal selected from Na, K, Li, Zn, Mg. Ni, Ca.
Ba, Sb, Ti, V. and Sn; R, and R2 when n is 1 may together form an arylenedioxy radical.
According to another aspect, the invention provides a flame retardant composition comprising a normally flammable polymer and a reactive flame retardant in the form of a halogen-containing organic phosphorus compound having the formula:
where X and Z are as defined for Formula I. A' represents the direct P-C bond or a bivalent radical containing one or more oxy linkages and R3 represents a hydrocarbyl or hydrocarbyloxy radical.
As defined above for Formula I, R, represents a reactive functional group selected from chloro, bromo, hydrocarbyl and hydrocarbyloxy radicals. When R1 in Formula I represents a hydrocarbyl or hydrocarbyloxy radical, such radical may be aliphatic, acyl. cycloaliphatic.
aromatic, or heterocyclic. and may be substituted or unsubstituted. When R1 represents an aliphatic radical. it may be a substituted or unsubstituted alkyl. alkyl, or alkynyl which is optionally interrupted by one or more oxygen atoms. When substituted, the substituent is preferably a reactive one such as reactive chlorine or bromine, hydroxy, haloalkyl. amino.
epoxy. etc.
The radicals which R, may represent are illustrated by the following radicals: -OC2H5; , -CH3; -C2Hs; -OCH3;
-.0CH2CHCH2 (glycidol); -OCH2NCO; 0 o -OC-(polyhalo-cyclo or polycyclo-aliphatic); OCH2CH20CH2CH20CHCX3 ; OCH3CH30CHCX3 OH (CH242 O (CH2X)2 O -N > rNH -Nn,NR O O where R is H,
-(CH2)n - (hydantoin derivatives, haloalkyl derivatives, haloaryl derivatives, alkylepoxy derivatives, aryl epoxy derivatives, unsaturated epoxy derivatives, and halocycloalkyl derivatives);
-O carbohydrate such as -O (glucosane); -O Sucrose); -O Fructose); -O (Sorbitol); -O Soforose); etc.
In the foregoing radicals, X represents bromine or chlorine as defined for Formula I, R2 represents a reactive phosphor-attached functional group selected from amino and hydrazino; or represents a radical selected from those defined from R, or represents -OM.
where M is as defined in Formula I. such radical being produced by the reaction of a metal salt of the class described with a hydroxyl radical; or represents -O.Q where Q represents an epoxy ester radical of acrylic or methacrylic acid. The epoxy ester derivatives contemplated include the acrylic and methacrylic acid esters of: epoxy alkyl epoxy alkenyl, epoxy cycloalkyl. epoxy aryl. and epoxy hetero cyclic compounds. As examples of such compounds from which Q may be derived may be mentioned glycidyl acrylate and glycidyl methacrylate.
When n = 1 in Formula I. R, and R2 may optionally join together as a divalent arylenedioxy radical, such as o--phenylenedioxy.
A in Formula I is an oxygen atom or a bivalent radical containing one or more oxy linkages.
Thus A includes the oxy radical (-0-) as well as bivalent radicals derived from an alkane which is interrupted by one or more oxygen atoms. When A is the latter. such radical may be substituted or unsubstituted. Such alkane preferably contains from 1 to 6 carbon atoms.
Radicals of this class include the bivalent radicals of polyols such as ethylene glycol or diethylene glYcol. Included in this class of bivalent radical are the following: oxy (-0-).
alkyleneoxy (-RO-). oxyalkylene (-OR-). alkylenedioxy (-ORO-). oxydialkylene (-ROR-).
(oxydialkylene) dioxy (-ORORO-). (aminodialkylene) dioxy. (-ORN(H)RO-). and (alkylaminodialkylene) dioxy (-ORN(R)RO-). R in the preceding illustration represents an alkyl or alkylene radical. The following radicals. in particular. are contemplated:
The radical represented by B is preferably a reactive one. Thus. B may represent chloro or bromo. or a hydroxy radical. B may also represent an alkoxy or alkenyloxy radical. When B is an alkoxy or alkenyloxy radical. such radical is preferably substituted with one or more halogen atoms especially chloro or bromo.
The following halogen-substituted alkoxy or alkenylox! radicals. in particular. are contemplated for B: -OCH2CX3; -OCH2CHXCH2X;
When B represents a N-(isocvanatohvdrocarbvl)carbamovloxv radical. the hvdrocarkxl moiety may be alkyl cycloalkyl. aryl. or polyaryl. An illustrative exampleof such a radical is uriedotoluylisocyanate
The compounds of this invention, as represented by Formulas I and II all include, as a characteristic feature thereof, the group -CHCX3, B which appears at least once. This group is derived from chloral or bromal used as a material in producing the compound. This group provides for separation of the -CX3 from the phosphorus atom, resulting in good heat and UV stability and good resistance to hydrolytic reaction.
The compounds of Formula I may be further defined according to structure. Thus, one class of compounds contemplated in accordance with Formula I may be more particularly represented by the formula:
wherein A, B, R1, X, and Z are as defined above for Formula I.
Especially useful are those compounds in accordance with Formula III wherein
(ii): B is-C1, -Br, -OH or -OCH2CHXCH2X (iii): A is as defined in (i) and B is as defined in (ii).
Also particularly useful are those compounds in accordance with Formula III where R, is C, to C4 alkoxy and B is selected from hydroxy, chloro, and bromo.
Also contemplated are compounds in accordance with Formula III in which R is
(u is 1 or 2) and B is chlorine or bromine; or R, is
(u is I or 2) and B is halogen-substituted alkoxy.
Very desirable, both as a reactive flame retardant itself and as an intermediate in the synthesis of other reactive flame retardants are the following tetrahaloalkyl phosphorodihalidate or phosphothiodihalidate compounds under Formula III:
where A, X, and Z are as defined above for Formula I, and Y, independently of X, also represents chlorine and bromine. Also useful are the corresponding tetrahaloalkyl acids of Formula IV where Y represents OH.
Also contemplated. and particularly useful as a flame retardant in urethanes, are compounds under Formula I where R, = R2 = a uriedohydrocarbyl isocyanate derivative and B is a N-(isocyanatohydrocarbyl)carbamoyloxy radical.
Another class of compounds contemplated in accordance with the above Formula (I) may be more particularly represented by the formula
wherein A, B, R1, X and Z are as defined in Formula I, and R, represents chloro, bromo, amino, hydrazino, or -OM, where M is as defined for Formula I.
Compounds of particular interest this class are those under Formula V in which A is oxy and B is chlorine or bromine. Another preferred class of compounds under Formula V are those where R4 is selected from chloro, bromo, amino and hydrazino.
Still another class of compounds within Formula I may be more particularly represented by the formula
where A, B, R1, X and Z are as defined above for Formula I.
Of particular interest are those compounds under Formula VI in which A is oxy or the bivalent radical of glycol or diethylene glycol.
Also within the present invention are compositions containing halogen-containing organic phosphorus compounds in accordance with Formula II
wherein X and Z are as defined for Formula I, A' represents the direct P-C bond or a bivalent radical containing one or more oxy linkages, and R3 represents a hydrocarbyl or hydrocarbyloxy radical.
Preferred compounds of this class are phosphinic acids under Formula II where R3 represents C1 - C4 alkoxy, and A' represents the direct P-C bond or a
linkage.
In the compounds of formula I, the presence of at least one oxy linkage in the bivalent radical A gives very desirable heat and UV stability and resistance to hydrolytic reaction by providing for separation of the halogen from the phosphorus atom. These compounds exhibit stability and resistance to hydrolysis not found in organic phosphorus compounds of similar structure but where the chloral or bromal is attached directly to the phosphorus atom.
Monoalkyl phosphorous acid esters, however, when reacted with chloral or bromal to give the compounds of Formula II. result in products which have very acceptable resistance to heat, UV. and hydrolytic reaction, even though the chloral or bromal may be attached directly to the phosphorus atom.
The compounds for use in the compositions of this invention are produced by various methods. all involving reacting chloral or bromal with certain organic and/or inorganic phosphorus compounds. The production of a number of such compounds for example, involves reacting chloral or bromal with PC15 or PBrS. which is then treated with water or
sodium hydroxide or H2S: CX3CHO + PY5 [NaOH/H2O or triethylamine/H2O or H2S] mti 1)OCHCx3 (VIII) y/ I y where X and Y are Br or Cl, Z is O or S.
This product (VIII) is used directly or may be further reacted with various reactive compounds (which themselves may be derived from bromal or chloral) to produce other highly reactive polyhalogenated organic phosphorus compounds.
R* = a reactive functional product Other compounds for use in the compositions of this invention are produced by reacting chloral or bromal with mono or dialkyl phosphites, which in turn, may be further reacted with bromal or chloral, and/or with other reactive compounds, such as aryl diisocyanates, for example:
The compounds for use in the compositions of the present invention exhibit exceptionally good flame retardant properties and thermal stability, and are particularly valuable as flame retardants for a variety of natural and synthetic polymeric materials including acrylics, polyacetals, polyurethanes, polyolefins, polycarbonates, ABS resins, polyesters, polyamides, woods, proteins, natural and synthetic cellulosic polymers, and rubber. The compounds may either be mixed with the material during polymerization, or in the melt, or may be applied topically, as in the case of natural polymers or natural and synthetic textile fibers. The compounds may also be used with cellulosic fibers such as cotton and rayon and with natural or synthetic silk or wool fibers.
The compounds are reactive and readily combine chemically with the materials to which they are added. They are further characterized by a relatively high ratio of phosphorus and halogen to alkylene linkages, to which at least in part, may be attributed the desirable flame retardancy and low toxicity properties, and the ability of the compounds to combine with the material without adversely affecting the physical properties thereof. Most of the compounds are also -characterized by being substantially neutral, i.e. no free acid.
The compounds can be used in any proportion which is effective to provide the desired level of flame retardancy, and without adversely affecting the desired properties of the material to which they are added. Exact ranges vary depending upon the phosphorus and halogan content of the particular compound and the level of flame retardancy desired.
A more complete understanding of this invention will be obtained from the following Examples, which are provided for purposes of illustration. It will be understood that the invention is not limited to these Examples but that various modifications will be recognised by one of ordinary skill in the art. Examples 1 to 34 (Example 9 being for comparative purposes) relate to the preparation of halogen-containing organic phosphorus compounds, and Examples 35 to 50 relate to the incorporation of such compounds in resins and other materials. Examples 51 and 52 are examples of the use of compositions according to the invention for rendering polyurethane and timber fire resistant.
EXAMPLE 1.
'Preparation of ethyl p p-trichloro- -trichloro-a-hydroxyethyl-phosphinate.
A three necked glass flask equipped with a reflux condenser open at the top, a mechanical stirrer, a thermometer, a cryostat-thermostat temperature control and dropping funnel with a drying tube to protect the reaction mixture from atmospheric moisture is charged with 1 Mole monoethyl phosphite
(Prepared from diethyl phosphate and sodium metal or hydroxide under reflux in an inert solvent).
The dropping funnel contains 1 Mole chloral. This is added slowly while maintaining the temperature of the reaction mass below 600C under a nitrogen blanket. The mixture is stirred an additional 20 ininutes and maintained at 50 C.
The reaction mass is treated with an inert solvent at 350C. and then purified. This product is analysed as follows: C4H8Cl303P Calculated in the final product: Cl/P = 3.44 Found by analysis: Cl/P = 3.40 EXAMPLE 2 Prepa'ration of ethyl -tribromo-a-hydroxyethyl phosphinate.
The procedure is similar to Example 1 except that 1.0 Mole bromal is used in place of chloral.
The product is analyzed as follows: C4H8Br303P Calculated in the final product: Br/P = 7.74 Found by analysis: Br/P = 7.69 EXAMPLE 3 Preparation of 0.0-diethyl-a-(ppp-trichloroethylene-ocy-o'-hydroxy-ppp- trichloroethylene)-phosphonate
An apparatus;similar to the one described in Example l is charged with l Mole of -tricllloro-α-hydroxyethyl (or hydroxymethyl) phosphonic acid diethylester (material A). 150 ml of dioxane and 0.08% of a strongly acid cation exchange resin such as Ion Exchanger I. availablefrdm E. M. Laboratores. Inc. of Elmsford. New York. The percentage refers to parts by weight of material A. Material A is prepared by reacting diethyl phosphite with chloral following the procedure of Example 1. The dropping funnel contains 1 Mole chloral which is added slowly while maintaining the temperature of the reaction mass below 60 C. preferably at 50 C. A nitrogen blanket is used. The mixture is maintained an additional 20 min. at 50 C. after the exothermic reaction is complete. The product is cooled at room temperature. filtered and is purified by the same procedure as shown in Example I . The product is analyzed as follows: C8H13Cl6O5P Calculated in the final product: Cl/P = 6.87 Found by analysis: = Cl/P = 6.80 EXAMPLE 4 Preparation of O-ethyl'-o-pPP-trichloroethylene-oxy-a'-hydroxy-ppp- trichldroethylene-phosphonate.
The procedure of Example 3 is followed. substituting material A with I Mole O-ethyl- -trichloro-α-hydroxy-ethyl-phosphonic acid.
The product is analyzed as follows: C6H9Cl6O4P Calculated in the final product: Cl/P = 6.87 Found by analysis: Cl/P = 6.80 EXAMPLE 5 Preparation of O,O-diethyl-a-PP P-tribromoethylene-oxy- a'-hydroxy-PP P, tribromoethvlene-phosphonate.
The procedure of Example 3 is repeated substituting 1 Mole bromal for the chloral used in that example.
The product is analyzed as follows: CsHi 3Br6O SP Calculated in the final product: Br/P = 15.48 Found by analysis: Br/P = 15.39 EXAMPLE 6 Preparation of tetrachloroethylene-phosphoro-dichloridate.
An apparatus similar to the one described in Example 1 is charged with an inert solvent of a low freezing point (300 mls) and 2.80 to 7 Moles preferably 3 Moles Pal5. The dropping funnel contains 0.97 to 2.40 Moles of chloral/or chloral hydrate, preferably 1 Mole which is added at such a rate that the reaction temperature is maintained below 40"C. The resulting mass is filtered to give tetrachloroethylene-phosphoro-tetrachloride:
The resulting solution is cooled off to 5"C to 0 C.
A concentrated solution of sodium hydroxide, 39g in 39g water, is added dropwise at such a rate that the temperature does not exceed 5"C. The additional time is 1.10 hours and the reaction mixture is stirred 20 to 40 minutes, preferably 30 minutes more at 12" to 250C.
The reaction is illustrated by the equation:
the salt is then filtered and the solution dried over Na2SO4. The drying agent is filtered out and washed with 45 ml methylene-dichloride. The methylene dichloride is distilled out at atmospheric pressure resulting in almost total yield of tetrachloroethylene-phosphorodichloridate, a clear straw colored liquid:
EXAMPLE 7 Preparation of tetrachloroethylene-phosphate-bis (methoxyisocyanate).
Where X = Cl.Br Tetrachloroethylene-phosphorodichloride (Example 6) or tetrahaloethylenechlorophosphate- a'-chloroethyl-phosphorodichloride with the structure:
prepared from tetrachloroethylene-phosphorodichloride (Example 6) and vinyl phosphonic acid dichloride), 254g and paraformaldehyde, 127g are heated together to 30 - i45oC in an autoclave, preferably 138"C for 160 minutes. After cooling and purification have been completed, the following products are the result:
50.8g of the tetrachloroethylene-bis (dichloromethyl)-phosphate or tricloro ethylenea-chloromethyl-bis(dichloromethyl) -phosphate are added to 381 mls of dry benzene which contain 111.76g of a Group I metal cyanate (such as sodium cyanate) at such a rate that the reaction temperature is maintained below 30O - 350The reaction mass is refluxed for 160 minutes and then cooled and filtered. The C6 H6 is distilled off resulting in di- and triisocyanate phosphates.
Calculated in the final product: Cl/P = 4.57 Found by analysis: Cl/P = 4.33 EXAMPLE 8 Preparation of tetrachloroethylene phosphothio dichloridate.
Example 6 is repeated substituting 2 Moles of H2S for the 2 Moles of sodium hydroxide.
EXAMPLE 9 (For purpose of comparison) Preparation of tetrachloroethylene phosphoric acid or tetrachloroethylenethio phosphoric acid.
Examples 6 and 8 are repeated substituting 4 Moles of sodium hydroxide or 4 Moles of H2S for the 2 Moles used in those examples.
EXAMPLE 10 Preparation of tetrabromoethvlene phosphorodibromidate.
Example 6 is repeated substituting l Mole PBr5 and 1 Mole bromal for the Pals and chloral used in that example. The corresponding acid and thio derivatives are prepared following the procedures of Examples 8 and 9.
EXAMPLE 11 Preparation of ppp-trichloro-o-bromo-ethylene -phosphorodibromidate
Example 6 is repeated using 1 Mole PBrs and 1 Mole chloral. The corresponding acid and thio derivatives are prepared following the procedure of Examples 8 and 9.
EXAMPLE 12 Preparation of 2.2' - bis (p p p-trichloroethylene-methoxy pp p-trichloroethylene α-oxy)-tetrachloroethylene-phosphate
An apparatus similar to the one described in Example 1 is charged with 150 ml benzene and 1 Mole of pp p-trichloroethylene- a- hydroxy- a '-methoxy-p pp -trichloroethane (prepared from reacting chloral and 222-trichloroethanol). This mixture is cooled to about 10 C.
The dropping funnel contains 0.2 Mole of tetrachloroethylene-phosphorodichloridate (from Example 6), 50 ml benzene and 50 ml triethylamine; this is added slowly with stirring so as to maintain the temperature of the reaction-mass below room temperature.
After the addition, the solution is stirred for an additional 80 mintues at 20 - 300C. The benzene solution is washed to neutral, filtered, and the solvent is stripped under vacuum.
The resultant product is: C10H7 Cll604P Calculated in the final product: Cl/P = 18.31 Found by analysis: Cl/P = 16.89 EXAMPLE 13 Preparation of bis (pp p-trichloro-ethylene-methoxy -ppp-trichloroethylene-a-oxy) -2-chloroethyl-phosphonate
Procedure of Example 12 is used with 1 Mole of 2'-chloroethylrphosphorodichloride replacing tetrachloroethylene-phosphorodichloridate.
The product is analyzed as follows: C10H10Cl13O5P Calculated in the final product: Cl/P = 14.88 Found by analysis: Cl/P = 14.82 EXAMPLE 14 Preparation of tetrachloroethylene-bis ( -trichloroethylene-α-chloropropyl) -phosphonate.
where X = Cl,Br An apparatus similar to the one described in Example 1 is charged with 250 ml of benzene.
0.65 Mole of tetrachloroethylene-phosphorodichloridate (Example 6) and 11.81 g anhydrous aluminum chloride.
The dropping funnel contains 2 Moles of ppp-trihalo-1,2-epoxy-alkyl (Cl to C6) or cycloalkyl such as -trichloro-1,2-epoxy-propane. This is added slowly to the mixture at such a rate that the temperature of the reactants is maintained to about 50 - 60 C. When the exothermic reaction ceases, heat is applied and the temperature is raised to 700C. when 0.35 Mole of tetrachloroethylene phosphorodichloridate is added.
The product is purified by the procedure shown in Example I. The solvent is stripped under vacuum at 60 C/12 mmHg.
The resulting product is: C8H7 Cll204P Calculated in the final product: Cl/P = 13.73 Found by analysis: Cl/P = 13.68 EXAMPLE 15 Preparation of 5,5-bis-(chloromethyl)-a- tetrachloroethylene-oxy-a'-chloro - 1-hydantoin- phosphonate.
An apparatus similar to the one described in Example 1 is charged with 250 ml toluene, 1 Mole triethylamine and 2 Moles -5,5-bis (chloromethyl)-hydantoin (made from 1,3 dichloroacetone and sodium/or potassium cyanate).
The dropping funnel contains tetracloroethylene-phosphorodichloridate (Example 6) in minimal amount of toluene. This is added slowly to the mixture at such a rate that the internal temperature is maintained at about 55" - 60 . The procedure of Example 14 is followed.
After filtration, the solvent is stripped under vacuum at 95"C/lo mmHg.
The resulting product is: C7 H6 C17 N204P Calculated in the final product: Cl/P = 8.01 Found by analysis: Cl/P = 7.80 EXAMPLE 16 .Preparation of'bis (-ppp-trichloroethylene -a-hydroxy-p -oxy-pp p -trichloroethylene-a' -hydroxy-bis(methyl)- 1,2- pyrocatechol-phosphate.
An apparatus similar to the one described in Example 1 is charged with 250 ml benzene, 100 ml triethylamine, l Mole -ssssss- trichloroethylene-a-hydroxy-p -oxy-a'-hydroxy-trichloroethylene (made from reaction of chloral with chloral hydrate) and 5g MgC12. The reactor is washed with N2. Then 1 Mole l-chloroethyl-1,2-pyrocatechol phosphate is added at room temperature at such a rate that the temperature of the reactants is maintained at about 55" - 60 C. When the exothermic reaction ceases, heat is applied and the temperature is raised to 65 0C and kept for an additional 2 hours. The reaction mass is cooled to room temperature a
'Ihe product is analyzed as follows: Cl2HllCl3Br3 06P Calculated in the final product: Br/P = 7.74 Found by analysis: Br/P = 7.71 EXAMPLE 18 Preparation of bis (ppp-trihalo-a-hydroxyethylene -ss'-oxy-diethyleneglycol- tetrachloroethvlene phosphate.
where X = Cl, Br The apparatus described in Example 1 is charged with 10 Moles tetrachloroethylene phosphorodichloridate and 200 ml benzene. The dropping funel contains 2 Moles of (ssssss-tribromo-ss-hydroxyethane)-ss'-oxy.2,2-oxydiethanol, 150 ml benzene and 210g triethylamine is added at a temperature below 18"C. When the exothermic reaction ceases the solution is heated at 30 C and kept for 30 min.
The salt is filtered and the resulting solution is heated under N2 and purified by vacuum at 55 C, 18 mmHg.
The product is analyzed as follows: C14H21Cl4 Br6 OioP Calculated in the final product: Br/P = 15.48 Fqund by analysis: Br/P = 15.38 EXAMPLE 19 Preparation of -ssssss-trihalo-α-hydroxyethylene-ss'- oxy-diethyleneglycol-2tetrachloroethylene-aminophosphate .
where X = CI,Br Into a solution of 0.1 Mole of -ssssss-trichloro-α-hydroxyethylene-ss'-oxy- diethyleneglycol-2-tetrachloroethylene-chlorophosphate (prepared according to Example 18 but with the reactants in a ratio of 1:1) and 200 ml CCl4, ammonia gas is passed while stirring at 20 - 35"C. When an exothermic reaction is no longer observed the ammonia is stopped. The mass of the reaction is then treated, while stirring, with 80 ml of water to dissolve the by-product ammonium-chloride. The resulting mixture is stirred into chloroform, filtered and is distilled off at 50 C/ 12 mmHg to give: C8H13Br3 C14 N P6 P Calculated in the final product: Br/P = 7.74 Found by analysis: Br/P = 7.67 EXAMPLE 20 Preparation of -p pp-trihalo-a-hydroxyethylene-a'-oxy -diethyleneglycol-2- tetrachloroethylene-hydrazinophosphate.
wnere X = t:l Hr The procedure of Example 19 is repeated substituting the ammonia and 1 Mole of hydrazinehydrate.
After the purification the following product is obtained: C8H,4Cl7 N2 6 P Calculated in the final product: Cl/P = 8.01 Found by analysis: Cl/P = 7.92 EXAMPLE 21 Preparation of a-tetrachloro-ethylene- ss-chloropropionamide -phosphorochloridate.
where X = Cl,Br The apparatus described in Example 1 is charged with 1 Mole acrylamide or derivatives and 600 m. dioxane. The dropping funnel contains 1 Mole tetrachloroethylenephosphorodichloride added slowly so that the temperature of the mixture remains below 30"C. The resulting mixture is stirred an additional 10 minutes at 300 - 350 C and 35 - 40 minutes at 450C. The product is purified under N2 by vacuum at 450C/15 mmHg.
The product is analyzed as follows: C5H6 Cl6 N O3P Calculated in the final: Cl/P = 6.86 Found by analysis: Cl/P = 6.82 EXAMPLE 22 Preparation of poly(halo-propane) - a-oxy- p pp-trihaloethylene-a'bis (B'-halo-methyl-propanol) -phosphate.
R = H,Br where X = Cl,Br An apparatus described in Example 1 is charged with 1 Mole a,p-dibromo-propanol/or a,a,p,p'-tetrabromo-propanol under N2. The temperature is raised to 450 - 550C when 1 Mole bromal/or chloral is added slowly. The resulting mass reaction is cooled below 10 C when 1 Mole of P2O5 is added, keeping the temperature of the solution below 15 0C. After the exothermic reaction has ceased heat is applied to 450 - 50"C when over 4 Moles epichlorohydrin/or epibromohydrin are added slowly. The temperature is maintained below 70"C. The solution is purified and cooled at room temperature.
The product is identified as: C17H27C17 Br2 O9P Calculated in the final product: Br/P = 5.16 Found by analysis: Br/P = 5.10 EXAMPLE 23 Preparation of bis (2,3-dibromo-2-propene - 1 -oxy-p p p-tribromo-ethylene -a-oxy)phosphate-bis(p-chloromethyl-propaneglycol)
The procedure of Example 22 is repeated in presence of 2,3--dibromo-2-propene-l-oxy- ppp-tribromo-cY-hydroxyethylene.
The product is analyzed as follows: C16H19Cl2 Bur1008 P Calculated in the final product: Br/P = 25.88 Found by analysis: Br/P = 25.79 EXAMPLE 24 Preparation of bis (pp p-trichloroethylene- 1,1 '-carboxyaminophenyl-isocyanate) phosphono-2-oxy-P p p-trichloroethylene- a-carboxyaminophenyl-isocyanate
An apparatus similar to the one described in Example 1 is charged with 1 Mole bis(ppp trichloroethylene- 1,1 '-hydroxy)-phosphono-oxy- a-hydroxy-p ssss-trichloroethylene (prepared by reacting bromal or chloral, or chloral hydrate with Me(I,II,III) (phosphide), such as
The dropping funnel contains 3 Moles alkyl or aryl or polyaryl-diisocyanate, such as toluene diisocyanate (80/20); this is added slowly while maintaining the temperature of the reaction mass below 80 C under the nitrogen blanket. The mixture is maintained and stirred an additional 90 minutes.
5.58 Moles of additional toluene diisocyanates with 25So NCO groups (prepared by heating TDI or other aryl polyisocyanates with lithium acetate) are added. The product is a pale yellow liquid containing the structure as follows: C33H24Cl9 N6 OllP Calculated in the final product: Cl/P = 10.30 Found by analysis: Cl/P = 10.26 EXAMPLE 25 Preparation of ssssss-trichloropropane-α-carboxy-amino-isocyanate -phosphono-bis (trichloroethylene-oxy- a' -carboxy- amino-isocyanate).
The procedure of Example 24 is followed substituting the material with bis(a-hydroxy pp p-trichloroethylene)-phosphono-p p p-trichloro- α-hydroxy-propane (made from a-hydroxy-methyl -phosphonic acid HO-CH2P-OH and chloral) OH
The resulting product is a pale yellow liquid containing the structure as follows: C34H26C19 N6 O11P Calculated in the final product: Cl/P = 10.30 Found by analysis: Cl/P = 9.90 EXAMPLE 26 Preparation of 1 -bis(p p p-trihaloethylene -a-urylene-phenyl-isocyanate) oxydiethyleneglycol-2-tetrachloroethylene-phosphate
The apparatus described in Example 1 is charged with 1 Mole tetrachloroethylene phosphorodichloridate (Example 6) and 2 Mole of diethylene glycol under the nitrogen blanket.
The temperature of the mixture is raised to 50"C and 2 Mole of triethylamine is added. After purification the resulting solution is treated with 2 Mole of chloral at 500C and is maintained for 40 minutes. 2 Mole of toluene diisocyanate with 25% NCO groups is added at 90"C.
where it is maintained an additional 25 to 35 minutes. The product is pale yellow liquid containing the structure C32H 13Cl loN40 s2P Calculated in the final product: Cl/P = 11.44 Found by analysis: Cl/P = 11.36 EXAMPLE 27 Preparation of a-tetrahalo-ethylene-ce'- polyhalo phenyl-M-phosphate and a-tetrahalo-ethylene- a' -polyhalo cycloalkyl-M-phosphate.
Where: X = Cl, Br M = Na. K, Li, Zn, Mg, Ni, Ca. Ba Sb, Ti, V, Sn salts An apparatus similar to the one described in Example 1 is charged with 0.2 Mole of tetrachloroethylene-phosphorodichloridate or phosphorothiochloridate (Examples 6 and 8) and 0.2 Mole of polyhalo cycloalkyl or polyhalo aryl-alcohol, such as 2,4 6-tribromophenol and 100 ml of dried benzene. The dropping funnel contains 0.2 Mol triethylamine and is added at such a rate that the temperature never exceeds 25"C-30"C. The mixture is stirred for 2 hrs. at 50"C. The reaction mass is filtered and washed with benzene. The resulting solution is warmed at 400 - 500 C in presence of triethylamine when is added 18g H2O in 12 minutes after purification. resulting in:
(product B) To the resulting solution is added 0.5g potassium salt and heated to 500 C for 20 minutes.
The unreacted product is distilled off to give: Ce H3 Br3 Cl4 O4 P K Calculated in the final product: Br/P = 7.74 Found by analysis: Br/P = 7.64 EXAMPLE 28 Preparation of a-tetrahalo-ethylene-ct'-phosphato-(metha) acrylate:
where X = Cl, Br Q = H, or alkyl, alkylenyl, cycloalkyl, aryl and heterocyclic epoxy ester derivatives of acrylic and methacrylic acid.
The procedure of Example 27 is repeated substituting tetrachloro cyclohexanol for 2,4,6tribromophenol and substituting the metal salts with 1 Mole of appropriate epoxyacrylate or methacrylate derivates (such as cycloalkyl/or aryl/or heterocyclic such as hydantoins derivatives).
The methyacrylate at 50"C in presence of TMAC as catalyst and heated for 10 to 120 minutes at 60 C. The unreacted product is distilled off to give:
Calculated in the final product: Cl/P = 9.15 Found by analysis: Cl/P = 9.09 EXAMPLE 29 Preparation of a-tetra-halo-ethylene- a' -bis(polyhalocyclohexane) -phosphate
Where X = Cl, Br An apparatus similar to the one described in Example 1 is charged with 0.2 Mole of tetrachloro-ethylene-phosphoro dichloride (Example 6) or phosphorothio-chloridate (Example 8) and 0.4 Mole of polyhalo-cyclohexanol such as tetrachlorocyclohexanol (or isomers) or polyhalo-aryl- alcohol and 100 ml of dried benzene under N2. The dropping funnel contains 0.6 Mole triethylamine and is added at such a rate that the temperature never exceeds 25 - 30"C. The mixture is stirred for 2 hrs at 500C under N2. The product is purified following the same procedure as in Example.
The product is analyzed as follows: Cl4Hl3C1,204P Calculated in the final product: Cl/P = 6.87 Found by analysis: Cl/P = 6.80 EXAMPLE 30 Preparation of poly(halo-hydroxy-phosphato) -carbohydrate.
The apparatus described in Example 1 is charged with 41.13 grams carbohydrate (sucrose, fructose, glucose, sorbitol, soforose) such as glucosane, 165 ml dioxane and 40 grams triethylamine. The mixture is warmed at 650C under N2 and then 52 grams of tetrachloroethylene-phosphoro dichloride is added and maintained 1.1/2 hr at this temperature. The reaction mass is cooled to room temperature and filtered. The resulting product contains the following structure:
where R is the radical polymer carbohydrate. The reaction mass is heated to 500C for 20 minutes and 171 grams epichlorhydrin is added at such a rate that the temperature never exceeds 80" - 90"C. the resulting solution is heated at 800 - 900C for additional 360 minutes. The unreacted compounds are recovered at 800C/8mm to give a viscous polymeric material.
C30H36C1180 ,8P3 Calculated in the final product: Cl/P = 6.87 Found by analysis: Cl/P = 6.77 EXAMPLE 31 Preparation of bis-(p p p-trihalo- a- hydroxyethylene-oxy-ethan aminoethoxy-2-bis (polyhalo-propane) -phosphate.
Where X = Cl,Br X'= H.Br An apparatus described in Example I is charged with 0.37 Mole of triethanol amine in 100 ml of 1. 1-dichloroethylene and 102 g triethylamine. 0.123 Mole bis (a,p-dibromo-propane)- phosphoro-chloridate/or bis (cz,a',sssss'- tetrabromo-propane)- phosphoro-chloridate is placed in the dropping funnel with 50 ml 1,l-dichloroethylene. This solution is added slowly to the mixture in the reactor so that the reaction temperature does not rise above 15"C 20"C. The reaction mixture is allowed to warm at room temperature for about 10 hours. The solution is evaporated in a vacuum to yield a viscous oil residue which is then dried over Na2So4 (if necessary) and filtered. The resultant materials are represented by the chemical formula:
A neutral sample l Mole (product A or B) as prepared above is heated to 400 - 450C under a nitrogen blanket. The dropping funnel contains 2 Moles of chloral/or bromal/or ppp3 trihalo-l,2-epoxypropane (Chloral is used to obtain the structure illustrated above). This solution is added slowly over a period of 30 - 40 minutes to the reactor. When the exothermic reaction ceases, the mass is warmed at 500 - 60 C for 80 minutes.
The product is identified as the structure above.
Calculated in the final product: Br/P = 10.32 (A) Br/P = 20.64 (B) Found by analysis: Br/P = 10.28 (q) Br/P = 20.61(B) EXAMPLE 32 Preparation of bis (tetrachloroethylene-phosphorochloride -p-chloropropyon -c- hydroxymethy)-ss- methoxy-imine)
An apparatus described in Example 1 is charged with 2 Moles of tetrachloroethylenephosphorochloride-p-chloropropyonamide, 100 g dioxane and 15.75 g p-toluene sulfonic acid and heated at 40 C. The dropping funnel is charged with 4.75 Moles of formaldehyde.
The solution is added slowly while maintaining the temperature of the solution below 65"C.
The resulting mixture is stirred an additional 80 minutes at 65 "C and then it is cooled to room temperature. the product is purified following the same procedure as in Example 1.
The product is analyzed as follows: Cl4H,8Cll2N2 Og P2 Calculated in the final product: Cl/P = 6.87 Found by analysis: Cl/P = 6.79 EXAMPLE 33 Tetrahaloethylene- B-chlorophosphate- B '-hydrogen -oxymethyl-phosphite:
Where X = Cl.Br An apparatus similar to the one described in Example 1 is charged with 0.1 Mole of tetrachloroethylene-phosphorodichloride (Example 6) or tetrachloroethylene-phospho thiodi-chloride (Example 8),102 mls of triethylamine and 100 mls of inert solvent. The dropping funnel contains 0.1 Mole of monoalkyl/or cycloalkyl/or aryl hydrogen phosphite such as p-oxymethyl-hydrogen-phosphite.
is added at such a rate that the temperature never exceeds 10 C. The mixture is stirred 30 minutes at room temperature and then gently heated to the boiling point of the solvent for 20 - 120 minutes, preferably 40 minutes. The product is filtered and the solvent distilled off.
The product is analyzed as follows: C3 H C15 O5 P2 Calculated in the final product: Cl/P = 2.86 Found by analysis: Cl/P = 2.77 EXAMPLE 34 Preparation of tetrahaloethylene-p-chlorophosphate- 1.4.5.6.7.7-hexachlorobicyclo -(2,2.1 )-5-heptane-2.3- carboxy-p'-cyclohexanol.
An apparatus similar to the one described in Example 1 is charged with 1 Mole of 1,4,5,6,7,7-hexachlorobicyclo- (2,2,1)-5-heptane-2,3-acid anhydride, 200 mls benzene and 1 ml (n-benzyl-diemethylamine. This is mixed at 45" - 55"C preferably 45"C under N2 until dissolved. Then 1 Mole ( + 10%excess) of cyclohexene oxide is added dropwise within 40-60 minutes at the same temperature.
102 g of triethylamine is slowly added. The dropping funnel contains 1 Mole tetrachloroethylene-phosphorodichloride (Example 6). [Tetrahaloethylene-p- chloro phosphate-ex'-chloro-ethyl-phosphoro -dichloride (Example 7), or tetrahaloethylenep h o s p h o r thiodichloride (Example 8) may be used instead. This is added at such a rate that the temperature never exceeds 5 to 150C preferably 10"C.
The mixture is stirred 30 to 80 minutes, preferably 30 minutes, and then gently heated to the boiling point of the solvent for 20-120 minutes. preferably 40 minutes. The product is filtered and concentrated.
The product is analyzed as follows: C17H12Cl11O7 P Calculated in the final product: Cl/P = 12.59 Found by analysis: Cl/P = 12.47 EXAMPLE 35 Thermoplastic-Thermoset Acrylic. A suitable reaction vessel equipped with stirrer, temperature control, condenser and dropping funnel with a drying tube is charged with: pyrophosphoric acid, such as chloropyrophosphoric acid Cl(OH)(O)POP(O)(OH)2 21.84 pbw urea (or urea derivatives) 58.84.pbw The mixture is heated to 500C for 20 min. to 2 hours and then cooled to room temperature and 8 pbw urea and 18 pbw FR of Example 4 is added. The dropping funnel contains acrylic alkyl ester or metha (acrylic) alkyl-ester such as methylmethacrylate 50.80 pbw and vinylnitrile derivatives such as acrylonitrile 127 pbw. These are added and stirred until the solution becomes almost clear.
The resulting solution could be polymerized by UV, electron beam or redox system.
To the above solution is added 1% pbw of organic peroxide such as 2,4-dichlorobenzoylperoxide and N,N-di(2-hydroxyethyl)-p-toluidine. The solution is allowed to heat at 40"C under N2 until it becomes very viscous and the reaction appears to be practically complete. The bulk casting is then baked several hours at about 70"C to assure complete polymerization. resulting in a thermoplastic fire resistant product. If the product is heated until 200"C for 35-40 minutes the acrylic copolymer becomes thermoset and flame resistant.
EXAMPLE 36 The procedure of Example 35 is repeated in presence of vinylamide derivatives such as acrylamide 25.40 pbw and metal oxalic complex such as K2[Ti O(C2 04)2]2H20. The resulting (co)-polymer is a flame resistant product.
EXAMPLE 37 The procedure of Example 35 is repeated in presence of: methacrylic acid 58.42 pbw methacrylonitrile 68.58 pbw urea 8.89 pbw 4-amino-2,5-imino-amido -s-triazine 0.8 pbw a-tetrachloroethylene -p-chloropropionamide- phosphorochloridate (Example 21) 15 pbw A I Z B N initiator (azoisobutyronitrile sold under the trade name VIZO by DuPont) 0.8 pbw These materials are heated 48 hours at 500C under N2 and then 4-10 minutes at 90 C. The resulting moldable thermoplastic (co) polymer is flame resistant.
EXAMPLE 38 In a suitable apparatus described in Example 35, is charged with methylmethacrylate monomer and/or other acrylic or vinyl monomers (as described composition in US Patents 3,847,865; 3,843,612; 2,750,320 and 2,367,661) such as: methylmethacrylate 49 pbw methacrylic acid 21 pbw 3,4-epoxycyclohexylcarbinyl -3.4-epoxycyclohexanecarboxylate 29.4 pbw 2(2' - hydroxy-50' -methyl -phenyl)benzotriazole 0.1 pbw 0.4-NaOH ' 0.4 pbw 75% solution of t-butylperoxy -pivalate 2 pbw O-ethyl-a-(ppp-'trichloroethylene-oxy - a '-hydroxy- pp ss-trichloroethylene phosphonate (as described in Example 4) 17 pbw hydrafobe silica 6% pbw in MMA basis ZnC12 0.1% pbw in MMA basis The procedure is carried out the same way as described in US Patent 3,843,612, The resulting polymer is flame resistant.
EXAMPLE 39 in a suitable apparatus described in Example 35 is charged one of the compositions as described in US Patent 3,843,594, such as: methylmethacrylate 435 pbw glycidol methacrylate 266 pbw methacrylonitrile 159 pbw hydrofobe silica 0.8% pbw of MMA 5 ,5-bis(chloromethyl)- a-oxy- -tetrachloroethylene-a'-chloro-l- hydantoin phosphonate (Example 15) 20 pbw p p,p-trichloro- a-hydroxyethyl- p-ethoxy- -phosphonate (Example 1) 5 pbw MoO3-Cu2O 5% pbw of MMa The resulting thermoset molding powder is fire resistant.
EXAMPLE 40 In a suitable apparatus described in Example 35 is charged with one of the compositions described in US Patent 3,033,813; 3,104.154 or 3,736,241, such as: To 100g of a 50% aq. ZnCl2 there are added 5g homopolymeric acrylonitrile and 1g polypyrolidone (following the procedure of USP#3,033.813), and bis(2,3-dibromo-2propene- l-oxy-p pp- tribromo-ethylene-a-oxy)- phosphate-bis (p-chloromethyl- propaneglycol) as described in Example 23. The resulting acrylic fiber is flame resistant.
EXAMPLE 41 The following mixture: polypropylene powder (Melt index 10) 90 pbw a-tetrachloroethylene bis( a'- -polychloro cyclohexane)- -phosphate (Example 29) 10 pbw bis-(p-chloromethyl)-vinyl phosphate-Zn (Salt) 0.5% pbw of PP UV Stabilizer Tinuvin P (Ciba-Geigy), ("TINUVIN" being a Registered Trade Mark 0.08% pbw of PP is made homogeneous by tumbling. A sample is rolled between 100" - 135 C and pressed between aluminum sheets at 1700 - 200"C on a hot press for one minute. The polypropylene film is flame resistant.
EXAMPLE 42 A mixture is made of: polypropylene powder (Melt index 10) 90 pbw a-tetrachloroethylene-bis[ -poly (halocyclohexane)] -phosphate (Example 29) 7 pbw -tetrachloroethylene-a'-2,4,6- -tribromophenol-K-phosphate (Example 27) 3 pbw Cadmium-ss-chloroethylvinylphosphate 0.05% pbw of PP Tinuvin P 0.01%pbw of PP A sample is rolled between 110 - 135 C and pressed between aluminum sheets at 1700 to 200 C on a hot press for one minute.
The polypropylene film is flame resistant.
EXAMPLE 43 A mixture if made of: polypropylene powder (Melt index 10) 90 pbw a-tetrachloroethylene-bis [ -a'-poly(halocyclohexane) ] -phosphate (Example 29) 7 pbw ZnCl2.2DMF 0.5 to 5 pbw Sb203 2.7 pbw A sample is rolled between 100" - 135 C and pressed between aluminum sheets at 1700 to 200 C on a hot press for one minute.
The polypropylene film is flame resistant.
EXAMPLE 44 A mixture is made of: Pliovic (Registered Trade Mark) S-51 *(a PVC resin supplied by Goodyear Rubber Co.) 90 pbw a-tetrachloroethylene-a'-2,4,6- -tribromophenol-K-phosphate (Example 27) 7 pbw A sample is rolled between 80" - 125" C and pressed between aluminium sheets at 1200C for 15-25 minutes.
The PVC is dyeable and flame resistant.
*(The example could be repeated in presence of ETHYL Co. PVC resin SM-250) EXAMPLE 45 A polyester panel is made by mixing the following ingredients and pressing them (hot).
Hetron (Registered Trade Mark) 23925 (polyestcr supplied by Hooker Chemical Co.) 90 pbw o-tetrachloroethylene-a'-2,4,6-tri- -bromophenoxy-p-a-hydroxy-ethyl- -metha-acrylate (Deriv. Example 28) 8 pbw
Benzoylperoxide 1.2% pbw of resin Sb203 1.68 pbw The process is similar to Example 44 resulting in a flame resistant and dyeable product.
EXAMPLE 46 A polyester panel is made by mixing the following ingredients and pressing them (hot).
Unsaturated polyester as described in USP 3,372,176 (by Diamond Shamrock Co.) 90 pbw bis(2,3,.dibromo-2-propene- 1-oxy -ppp-tribromoethylene-a-oxy-phosphate- -bis(p-ch'loromethyl-propane glycol (Example 23) 5 pbw ZnCl2.2 DMF, 0.5 to 2 pbw benzoylperoxide 1.06% pbw of resin The process is similar to Example 44 resulting in a dyeable and flame resistant product.
EXAMPLE 47 A polyester panel is made by mixing the following ingredients and pressing them (hot).
PBT VERSEL-1200 (polyester by Allied Chem. Co.) 90 pbw O-ethyl-bis(a'-hydroxy-ethyl ppp-trichloro)-phosphate (Example 4) 8 pbw Zn C12.2DMF 0.5 to 5 pbw Sb203 1.5 pbw The process is similar to Example 44 resulting in a flame resistant product.
EXAMPLE 48 A polyester panel is made by mixing: PBT-VERSEL-1100 (Polyester by Allied Chem. Co.) 90 pbw a-tetrachloroe'thylene-p-chloro- -propionamide-phosphorochloridate (As in Example 22) 8 pbw SbC13 DMF (or ZnCl22DMF) 2 pbw The ingredients are mixed and pressed (hot) according to the condition described in a flame resistant and dyeable 'product.
EXAMPLE 49 Polyurethane foam was prepared using methods, known to those skilled in the art, by reacting the following compounds: Starch glucoside polyalkylene ether (with-OH 450 to 560) 8.89g is blended with 4.40 g of bis (pp p-tricloro- a-hydroxyethylene) p'-oxy-diethyleneglycol-2-tetra- chloroethylene phosphate (as in Example 19) and 8.89g toluene diisocyanate [or 50 to 70% (TDI blended with bis (pp p-trihalo- a- urylene-phenylisocyanate -ss'-oxy-diethyleneglycol- tetrachloro ethylene phosphate) as in Example 26)] and heated 110 minutes. A non ionic vegetable oil emulsifier (0.50g) and 0.5g H2O containing 0. 17g triethylene diamine are added slowly with stirring 20 to 30 sec. The reaction mixture is poured into a waxed box for foam at room temperature to give a flame resistant polyurethane foam.
EXAMPLE 50 The procedure is similar to Example 49 where 2.00g tetrachloro-ethylene-phosphate bis(methoxy isocyanate) are used as in Example 7 and 6.8g silicon tetra-(methoxy isocyanate)- in place of 8.89g of TDI.
The resulting foam is UV and flame resistant.
EXAMPLE 51 In the following examples is employed a formula (A): N-ethylmorpholine 0.12 pbw Silcon oil [Dow-Corning (Registered Trade Mark) -50] 0.03 pbw Dibutyltin 0.08 pbw Water 0.46 pbw Polyol as in Example 31 such as bis(ppp-tribromo-a-hydroxyethylene)-oxy-ethane -amino-ethoxy-2-bis (tetrabromopropane)- phosphate, 139 pbw is mixed with 8.89 pbw of polypropylene glycol. Upon addition of 3.33g -bis(ppp-trihaloethylene-a- urylene-phenyl isocyanate)-oxy- diethyleneglycol -2-tetrachloro ethylene-phosphate, (as in Example 26), 4,57g of toluene diisocyanate is added. The resulting polyurethane foam is flame resistant.
EXAMPLE 52 A solid wood such as Douglass fir or chips, redwood, white fir, western hemlock, western pine, southern pine species of lumber, lawn-faced Douglass fir, southern pine plywood or carton is used. A 1/8" screen is impregnated with PPP-trichloro-a-hydroxy ethyl-pa ethoxy-phosphonate (Example 1) or 0,0-dimethyl-bis (a-oxy- a'- hydroxyethyl-PPPd trichloro) -phosphonate (As Example 3) 70 to 80%pbw, tris(haloaliphatic)-phosphites such as tri-(p-chloropropyl-phosphite 30 to 20%pbw which are diluted with methylenechloride or chloroethylene derivatives bp.less than 100" C at 15 to 70% pbw of the materials. At the room temperature the materials are impregnated between 2.5 to 50 atm. for 80 to 100 minutes and then under the heat the solvent is removed resulting in flame resistant wood, chips, or carton without alteration of physical properties, and with moisture resistance.
WHAT I CLAIM IS: 1. A flame retardant polymeric composition comprising a normally flammable polynier and a reactive flame retardant in the form of a halogen-containing organic phosphorus compound having the formula:
wherein n is the whole number 1 or 2; X represents chlorine or bromine; Z represents oxygen or sulfur; A represents an oxygen atom or a bivalent radical containing one or more oxy linkages; B represents a chloro, bromo, hydroxy, alkoxy, halo-alkoxy, alkenyloxy, haloalkenyloxy, or N-(isocyanatohydrocarbyl)carbamoyloxy radical; R, represents a bromo, chloro, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, heterocyclyl, substituted heterocyclyl, heterocycloxy, or substituted heterocycloxy radical; and R2 represents a radical selected from those defined from R, or represents amino, hyd razino, or -OM where M is one equivalent of a metal selected from Na, K, Li, Zn, Mg, Ni, Ca. Ba, Sb. Ti, V and Sn; R, and R2 when n = 1, together represent a divalent arylenedioxy radical.
2. A composition according to Claim I, wherein the reactive flame retardant has the formula
3. A composition according to Claim 2. wherein R, is C1 to C4 alkoxy and B is selected from chloro, and bromo.
4. A composition according to Claim 2. wherein R, is
where u = l or 2. and B is selected from chloro and bromo.
5. A composition according to Claim 2, wherein R, is
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (16)

**WARNING** start of CLMS field may overlap end of DESC **. The resulting foam is UV and flame resistant. EXAMPLE 51 In the following examples is employed a formula (A): N-ethylmorpholine 0.12 pbw Silcon oil [Dow-Corning (Registered Trade Mark) -50] 0.03 pbw Dibutyltin 0.08 pbw Water 0.46 pbw Polyol as in Example 31 such as bis(ppp-tribromo-a-hydroxyethylene)-oxy-ethane -amino-ethoxy-2-bis (tetrabromopropane)- phosphate, 139 pbw is mixed with 8.89 pbw of polypropylene glycol. Upon addition of 3.33g -bis(ppp-trihaloethylene-a- urylene-phenyl isocyanate)-oxy- diethyleneglycol -2-tetrachloro ethylene-phosphate, (as in Example 26), 4,57g of toluene diisocyanate is added. The resulting polyurethane foam is flame resistant. EXAMPLE 52 A solid wood such as Douglass fir or chips, redwood, white fir, western hemlock, western pine, southern pine species of lumber, lawn-faced Douglass fir, southern pine plywood or carton is used. A 1/8" screen is impregnated with PPP-trichloro-a-hydroxy ethyl-pa ethoxy-phosphonate (Example 1) or 0,0-dimethyl-bis (a-oxy- a'- hydroxyethyl-PPPd trichloro) -phosphonate (As Example 3) 70 to 80%pbw, tris(haloaliphatic)-phosphites such as tri-(p-chloropropyl-phosphite 30 to 20%pbw which are diluted with methylenechloride or chloroethylene derivatives bp.less than 100" C at 15 to 70% pbw of the materials. At the room temperature the materials are impregnated between 2.5 to 50 atm. for 80 to 100 minutes and then under the heat the solvent is removed resulting in flame resistant wood, chips, or carton without alteration of physical properties, and with moisture resistance. WHAT I CLAIM IS:
1. A flame retardant polymeric composition comprising a normally flammable polynier and a reactive flame retardant in the form of a halogen-containing organic phosphorus compound having the formula:
wherein n is the whole number 1 or 2; X represents chlorine or bromine; Z represents oxygen or sulfur; A represents an oxygen atom or a bivalent radical containing one or more oxy linkages; B represents a chloro, bromo, hydroxy, alkoxy, halo-alkoxy, alkenyloxy, haloalkenyloxy, or N-(isocyanatohydrocarbyl)carbamoyloxy radical; R, represents a bromo, chloro, hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy, substituted hydrocarbyloxy, heterocyclyl, substituted heterocyclyl, heterocycloxy, or substituted heterocycloxy radical; and R2 represents a radical selected from those defined from R, or represents amino, hyd razino, or -OM where M is one equivalent of a metal selected from Na, K, Li, Zn, Mg, Ni, Ca. Ba, Sb. Ti, V and Sn; R, and R2 when n = 1, together represent a divalent arylenedioxy radical.
2. A composition according to Claim I, wherein the reactive flame retardant has the formula
3. A composition according to Claim 2. wherein R, is C1 to C4 alkoxy and B is selected from chloro, and bromo.
4. A composition according to Claim 2. wherein R, is
where u = l or 2. and B is selected from chloro and bromo.
5. A composition according to Claim 2, wherein R, is
where u = 1 or 2 and B is halogen-substituted alkoxy.
6. A composition to Claim 2, wherein R1 is and B is
7. A composition according to Claim 2, wherein the reactive flame retardant has the formula
where Y, independently of X, also represents chlorine or bromine.
8. A composition according to Claim 1, wherein the reactive flame retardant has the formula
9. A composition according to Claim 1, wherein the reactive flame retardant has the formula
10. A composition according to Claim 1. wherein the reactive flame retardant has the formula
where R4 represents chloro, bromo, amino, hydrazino. or -OM. where M is as defined in Claim 1.
11. A composition according to Claim 10. wherein R4 is selected from chloro, bromo.
amino, and hydrazino.
12. A composition according to Claim 10 wherein A is oxy and B is chlorine or bromine.
13. A flame retardant composition comprising a normally flammable polymer and a reactive flame retardant in the form of a halogen-containing organic phosphorus compound having the formula:
wherein X represents chlorine or bromine Z represents oxygen or sulfur A' represents the direct P-C bond or a bivalent radical containing one or more oxy linkages, R3 represents a hydrocarbyl or hydrocarbyloxy radical.
14. A composition according to claim 13, wherein R3 represents C, to C4 alkoxy and A' is selected from
and the direct P-C bond.
15. Flame retardant polymeric compositions substantially as hereinbefore described with reference to any one of Examples 1 to 8 and 10 to 34.
16. The use of flame retardant compositions substantially as hereinbefore described with reference to any one of Examples 35 to 52.
GB20686/77A 1976-05-28 1977-05-17 Flame retardant compositions comprising halogen-containingorganic phosphorus compounds Expired GB1584615A (en)

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