A flame-retardant composition

Abstract: A flame-retardant composition useful in rendering polymers flame-retardant by copolymerizing with the starting monomers, which composition comprises a halogenated, phosphorus-containing polyester obtainable by reacting a polyhydroxyphosphonic compound (A) with a halogenated polycarboxylic compound (B) in such a ratio as to provide two or more hydroxyl groups in the resulting polyester, optionally followed by the reaction thereof with a multifunctional organic compound (C), which compound (C) is reactive towards the hydroxyl groups of said halogenated, phosphorus-containing polyester.

Description: The present invention relates to a flame-retardant composition useful in rendering polymers flame-retardant by copolymerizing with the starting monomers. Moreover, the invention relates to polymer compositions which are rendered flame-retardant by having added an effective amount of an flame-retardant composition to the reaction mixture at the time that the polymer is prepared, as well as to polymer articles containing polymer compositions which are rendered flame-retardant in accordance with the present invention. Since polymers are used more and more in day-to-day appliances, fire requirements have become more stringent. As a result, the interest in compounds or compositions that render said appliances (i.e., the polymers which have been used to make the same) more flame-retardant has increased. German Offenlegungsschrift No. 1923937 discloses ester-containing polyols with flame resistant properties resulting from incorporating into the polyol chain, phosphorus from acids or (unsubstituted) oxides, a halogen-containing acid anhydride, and an alkylene oxide to reduce the resulting polyol acid number. To render polyurethane foam (suitable for i . a . insulation purposes) more flame-retardant, US Patent Specification No. 4,343,914 teaches to add an effective amount of a certain polyhydroxyphosphonic compound, i.e., an alkyl bis(3-hydroxypropyl)phosphine-oxide to the resin composition prior to the reaction of the polyol with the diisocyanate. Under these conditions, the polyhydroxyphosphonic compound reacts with the diisocyanate and becomes a part of the polyurethane chain. The merits that according to said US reference may be attributed to the polyhydroxyphosphonic compound include non-corrosiveness, high ultraviolet stability, non-toxicity and minimal adverse change in the physical properties of the polyurethane. In order to render the prepared polyurethane foam even more flame-retardant, said polyhydroxyphosphonic compound is advantageously used in combination with an halogenated organic compound. European Patent Specification No. 66171 A proposes the use of such phosphine oxides, with or without a halogen-containing compound, in rendering epoxy resins flame-retardant through combination with the epoxy monomer or with a known amine or anhdyride hardener used for curing the resin. The present invention seeks to provide a flame-retardant composition which may be built into the polymer which is to be rendered flame-retardant, and which composition has an even greater efficiency than those known hitherto. Moreover, said composition should have no appreciable detrimental effect on either the stability of the - to be rendered flame-retardant - polymer or on any of its other properties. Accordingly, the present invention provides a flame-retardant composition useful in rendering polymers flame-retardant by copolymerizing with the starting monomers, which composition comprises a halogenated, phosphorus-containing polyester, obtainable by reacting a phosphine-oxide containing at least two hydroxyalkyl groups (A) with a halogenated polycarboxylic compound (B) in such a ratio as to provide two or more hydroxyl groups in the resulting polyester, optionally followed by the reaction thereof with a multifunctional organic compound (C), which compound (C) is reactive towards the hydroxyl groups of said halogenated, phosphoruscontaining polyester. The prefix "poly" is used herein in respect of hydroxy and carboxylic groups to denote "two or more". An alkyl group is a straight chain or branched chain group suitably having up to 10 carbon atoms. Halogen is fluorine, chlorine, bromine or iodine. The flame-retardant composition of the invention may suitably be used directly in the form of the reaction product of the compounds (A) and (B), and optionally, (C); as such it will usually contain more than one product. It is within the gist of the invention to separate and purify the individual reaction products having flame retardant properties, and to use the latter as flame-retardants. Compound (A) is a phosphine-oxide containing at least two hydroxyalkyl groups. As such, preference is given to phosphine-oxides disclosed in US Patent Specification No. 4,343,914, i.e., phosphine-oxides having the formula (HO-CH 2 CR'HCH 2 ) 2 P(=O)R, wherein both radicals R' may be the same or different radicals selected from the group consisting of hydrogen atoms and methyl radicals, and R is an alkyl radical of having from 2 to 8 carbon atoms. In addition, alkoxylation products (i.e. upon reaction with ethylene oxide, propylene oxide and/or other alkylene oxides) may also be used. The most preferred compound (A) is the phosphine-oxide having the formula (HO-CH 2 CR'HCH 2 ) 2 P(=O)R, wherein each R' is a hydrogen atom, and R is an alkyl radical having 4 carbon atoms, e.g., isobutyl-bis(3-hydroxylpropyl)phosphine-oxide. The halogenated, polycarboxylic compound (B) may be an aromatic, aliphatic, or olefinic compound bearing at least one halogen atom, preferably chlorine or bromine (fluorine-, or iodine-substituted compounds are considered less suitable), and bearing at least two carboxylic acid groups or derivatives thereof (eg., carboxylate; acid chloride; ester; or anhydride). Compound (B) suitably is a halogenated, aromatic compound containing an anhydride group; most suitably the compound is a substituted benzene. Preferably, compound (B) is a chlorinated or brominated phthalic anhydride; tetrabromophthalic anhydride being most preferred. The flame-retardant composition may be prepared using conditions well known from esterification reactions described in the art. However, to prevent the preparation of a very viscous (or even an insoluble solid) composition, preference is given to reaction schemes whereby the halogenated, polycarboxylic compound (B) is added to suitably an excess of the compound (A). A suitable reaction scheme (although leading to a different type of flame-retardant, i.e. suitable for application on instead of application in a polymer) is found in US Patent Specification No. 4,178,399. The ratio of halogenated, polycarboxylic compound (B) versus polyhydroxyphosphonic compound (A) depends on the functionality of both said compounds. Thus, when employing for instance tetrabromophthalic anhydride (TBPA) and isobutyl-bis(3-hydroxylpropyl) phosphine-oxide (available from FMC Corporation under the designation FR-D), i.e., the most preferred embodiment leading to tetrabromophthalic-acid-bis(isobutyl-3-hydroxypropylphosphine-oxide) propyl ester (TBPDPE), the molar (and equivalent) amount of said phosphine oxide is preferably twice that of the anhydride. Conveniently, the reaction is carried out in the presence of a hygroscopic material, for example anhydrous sodium acetate. The reaction of compound (A) with compound (B) is suitably carried out at elevated temperature, preferably at a temperature in the range of from 100 to 200°C. The reaction time is conveniently from 2 to 3 hours using a temperature regime starting at, for example, 120°C and rising to 170 to 180°C for the bulk of the reaction period. The so-obtained halogenated, phosphorus-containing polyester may be further modified by reaction with a multifunctional organic compound (C), which compound (C) is reactive towards the hydroxyl groups of said halogenated, phosphorus-containing polyester. Thus, a wide range of copolymerizable flame-retardant compositions can be obtained. Suitably, said compound (C) is an alkylene oxide having from 2 to 4 carbon atoms, modifying the polyester by mild alkoxylation (yielding again a hydroxyl-terminated polyester, however with a different reactivity and/or viscosity), a polyisocyanate suitably as a conventional diisocyanate, for example methylene diphenyl diisocyanate or toluene diisocyanate, (yielding an isocyanate-terminated flame-retarding polyester), or an (alkyl)acrylic acid or derivative thereof (yielding a flame-retarding polyester containing terminal ethylenic unsaturation). However, it is appreciated that other possibilities (to adapt the flame-retarding polyester to a specific polymerisation process) may be followed without departing from the gist of the invention. It is noted that for certain applications the viscosity may be still too high. Then, the flame-retardant composition may be diluted with a reactive, and/or a non-reactive viscosity-lowering diluent. The diluent may be, for example another flame retardant. For instance, suitably in the use of a hydroxy-functional, flame-retardant composition in preparing a polyurethane foam, the composition may be diluted with a glycol derivative, or other hydroxy-functional diluents, but also alternatively with an alkyl or haloalkyl phosphonate or phosphate, suitably a C 1-6 alkyl or halo C 1-6 alkyl phosphonate or phosphate, preferably dimethylmethylphosphonate, trichloropropylphosphonate, or - and preferred - with triethylphosphate. In use the flame retardant composition of the invention is added to the polymer starting materials prior to polymerisation. In the case of polyurethane preparation, the polyester composition is suitably preblended with the starting polyol. The present invention extends to a polyol composition which incorporates a flame retardant composition of the present invention. The amount of flame retardant composition of the invention used may be, for example, in the range of from 10 to 60 parts per hundred parts by weight of polyol, suitably from 10 to 40, most suitably from 10 to 30. If a diluent is also used, suitably it is incorporated into the flame retardant composition in a ratio in the range of from 1:4 to 1:8 by weight, preferably in a weight ratio of 1:4. The invention is illustrated by the examples below. From said examples it may be seen that foams thus prepared, compare favourably (less flame-retardant is required to obtain the same effect) with foams prepared using conventional flame-retardants. It will be appreciated that said examples should not be construed to form a limitation of the scope of the invention. In the examples below, the notation "pbw" means parts by weight, and the following compounds (trademarks marked with an *) have been used:- FR-D isobutyl-bis(3-hydroxypropyl)phosphine-oxide, sold by the FMC Corporation PHT 4 tetrabromophthalic anhydride (TBPA), sold by Great Lakes Chemicals BR E 5100 30/70 TCPP/tetrabromophthalate diol, sold by Great Lakes Chemicals DMMP dimethylmethylphosphonate, sold by Ciba-Geigy TCPP trichloropropylphosphonate, sold by Tenneco Organics Ltd. TEP triethylphosphate, sold by Aldrich Chemicals IXOL* B 251 a flame-retardant, sold by Solvay FOX-O-POL* VD 280S a flame-retardant, sold by Resina CARADOL* 585-8 (C585-8) a laminating-type polyol, sold by Shell CARADOL* MD 944 (MD944) a laminating-type polyol, sold by Shell CARADOL* MD 946 (MD946) a laminating-type polyol, sold by Shell CARADATE* 30 (MDI) polymeric diphenylmethane diisocyanate, sold by BSI DABCO* DC-193 silicon oil, sold by Air Products DIME*-6 dimethylcyclohexylamine, sold by BASF TCFM-11 fluorotrichloromethane, sold by Hoechst NaAc anhydrous sodium acetate (purity > 99%), sold by Merck MethylPROXITOL* a glycol ether, sold by Shell Preparation of tetrabromophthalic acid-bis(isobutyl-3-hydroxypropylphosphine-oxide) propyl ester (TBPDPE) Two moles (446 pbw) of FR-D were placed in a two litre glass reactor and heated under stirring to 130°C. During all the operation the mixture was flushed with a strong nitrogen stream in order to free it from atmospheric oxygen and to remove the water created during the reaction. At 130°C the required amount of TBPA (one mole, 464 pbw) was added, and the temperature decreased to 120°C. NaAc (1 pbw) was added at 130°C and the mixture was heated to 170 - 175°C over a period of approximately one hour and maintained at this temperature for a further period of 1.5 hours. After this time, the acid value was found to be 2 mg KOH/g or less. The product was used without purification or isolation of the TBPDPE. Preparation of tetrachlorophthalic acid-bis(isobutyl-3-hydroxypropylphosphine-oxide) propyl ester (TCPDPE) The above procedure was repeated, however, now using tetrachlorophthalic anhydride instead of TBPA. Foam preparation Foam samples were made in an open polyethylene bag of dimensions 170 mm x 430 mm. The reactivity targets were set on a fibre time of 45 +/- 5 seconds. The foams were prepared by (a) preblending the polyol, foam additives, silicone oil, water, flame-retardant, and TCFM-11; (b) mixing (2500 to 3000 rpm) the blend of step (a), while (c) adjusting for TCFM-11 loss; (d) adding the catalyst to the blend of step (c), while stirring for 5 seconds (2500 to 3000 rpm); (e) quickly adding the organic isocyanate (CARADATE 30) to the blend of step (d); (f) stirring the mixture for a further 10 seconds; and (g) pouring the mixture into the bag. Preparation details, and some properties of the reaction batches made are presented in the Tables. The amounts of the components utilised are given in parts per hundred parts by weight of polyol. Results Table 1 discloses 10 examples, of which numbers 1, 4, and 7 are comparative examples. From Table 1 it can be seen that the present flame-retardant composition enhances the fire-retardance of the polymer, without detrimentally influencing other process parameters. Moreover, it can be seen that there is a substantial advantage to be gained when using a diluent (possibly even a synergistic effect). Tables 2 and 3 show the advantageous use of TBPDPE diluted by an amount of 20 % (wt/wt) of TEP in both partly and fully water-blown systems when compared with commercial reactive flame-retardants. From the tables it can be clearly derived that said commercially available products are less effective and that more is required to obtain the same efficiency as compared to the use of the present flame-retardant. Table 4 discloses the (slightly greater) efficiency of the brominated, flame-retardant composition over the chlorinated, flame-retardant composition. Example 11 12 13 14 15 16 C 585-8 100 100 100 100 100 100 DABCO DC-193 1 1 1 1 1 1 Catalyst (DIME-6) 1.8 1.2 0.9 0.8 0.6 0.7 Water 2.6 3.7 2.9 4.2 6.5 4.8 CFC-11 12.8 21.7 15.1 0 0 0 MDI 195.6 291.1 206.7 221.5 336 239.8 TBPDPE/TEP 4:1 (wt/wt) - - 30 - - 30 FR-D - 60 - - 60 - Cream time (sec.) < 20 23 22 24 24 22 Fibre time (sec.) 45 45 53 48 48 51 Tack-free time (sec.) 54 47 65 63 57 62 Density (kg/m 3 ) 33.6 34.0 33.4 33.3 31.9 32.9 Flame retardance (cm) (DIN 4201; B2) > 25 13 13.0 > 25 14.5 13 Example 27 28 29 30 31 32 MD 946 100 100 100 100 100 100 DABCO DC-193 1 1 1 1 1 1 Catalyst (DIME-6) 0.3 0.2 0.3 0.3 - 0.1 Water 2.6 2.7 2.6 2.7 4.5 4.5 CFC-11 12.8 13.6 12.9 13.7 0 0 MDI 175.3 178.9 180.3 185.3 214.0 213.7 TBPDPE/TEP 4:1 (wt/wt) 20 30 - - 30 - TCPDPE/TEP 4:1 (wt/wt) - - 20 30 - 30 Cream time (sec.) 20 < 20 20 18 < 20 18 Fibre time (sec.) 44 42 45 41 40 36 Tack-free time (sec.) 55 53 60 53 48 42 Density (kg/m 3 ) 34.0 34.5 34.5 34.0 34.9 33.1 Flame retardance (cm) (DIN 4201; B2) 15 13 16 14 13 17

Claims: A flame-retardant composition useful in rendering polymers flame-retardant by copolymerizing with the starting monomers, which composition comprises a halogenated, phosphorus-containing polyester obtainable by reacting a phosphine-oxide containing at least two hydroxyalkyl groups (A) with a halogenated polycarboxylic compound (B) in such a ratio as to provide two or more hydroxyl groups in the resulting polyester, optionally followed by the reaction thereof with a multifunctional organic compound (C), which compound (C) is reactive towards the hydroxyl groups of said halogenated, phosphorus-containing polyester. A flame-retardant composition as claimed in claim 1, wherein (A) is a phosphine-oxide containing at least two 3-hydroxypropyl groups having the formula (HO-CH 2 CR'HCH 2 ) 2 P(=O)R, wherein R' may be the same or different radicals selected from the group consisting of hydrogen atoms and methyl radicals, and R is an alkyl radical of from 2 to 8 carbon atoms. A flame-retardant composition as claimed in claim 1 or claim 2, wherein (B) is a halogenated, aromatic compound containing an anhydride group. A flame retardant composition as claimed in any one of claims 1 to 3, which also contains a viscosity-lowering diluent. A flame retardant composition as claimed in claim 4, in which the diluent is selected from glycol derivatives, alkyl phosphonates, haloalkyl phosphonates, alkyl phosphates and haloalkylphosphates. A flame-retardant composition as claimed in any one of claims 2, 3, and 5, wherein (A) is a phosphine-oxide containing at least two 3-hydroxypropyl groups having the formula (HO-CH 2 CR'HCH 2 ) 2 P(=O)R, wherein R' is a hydrogen atom, and R is an alkyl radical of 4 carbon atoms and (B) is tetrabromophthalic anhydride, and which also contains triethylphosphate. A flame-retardant composition as claimed in any one of claims 1 to 6, wherein (C) is an alkylene oxide containing 2 to 4 carbon atoms, an optionally alkyl-substituted acrylic acid or a derivative thereof, or an organic diisocyanate. A process for the preparation of a flame retardant composition as claimed in claim 1, which comprises reacting a phosphine-oxide containing at least two hydroxyalkyl groups (A) with a halogenated polycarboxylic compound (B) in such a ratio as to provide two or more hydroxyl groups in the resulting polyester, optionally followed by reaction with a multifunctional organic compound (C) as specified in claim 1. A polymer composition rendered flame-retardant by having added an effective amount of a flame-retardant composition as claimed in any one of claims 1 to 7, to the reaction mixture at the time that the polymer is prepared. The composition of claim 9, wherein said polymer composition is a polyurethane composition. The composition of claim 10, wherein said polyurethane composition is a water-blown and/or rigid polyurethane foam. Polymer articles containing polymer compositions as claimed in any one of claims 9 to 11. A polyol composition for use in the preparation of a polyurethane according to claim 10 or claim 11, which incorporates a flame retardant composition as claimed in any one of claims 1 to 7. Tetrabromophthalic acid-bis(isobutyl-3-hydroxy-propylphosphine-oxide) propyl ester or its chloro analogue, tetrachlorophthalic acid-bis(isobutyl-3-hydroxypropylphosphine-oxide) propyl ester.

Inventors: SCHENDZIELORZ MICHAEL CHRISTOP, SLABBINCK MARIJKE DANIEL FLORI, SCHENDZIELORZ, MICHAEL CHRISTOPH, SLABBINCK, MARIJKE DANIEL FLORIDA
Applicants: SHELL INT RESEARCH, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1992
Main classification: C08G63
IPC codes: C08J9, C08G63, C07F9, C08G18