Improvements in or relating to red phosphorus

Abstract: Evolution of phosphine from red phosphorus is reduced by means of acyclic, aliphatic compounds having at least one carbon-to-carbon double bond, in the alpha-position relative to an electron-withdrawing group. A preferred example of such a compound is trans -cinnamaldehyde.

Description: This invention relates to red phosphorus and in particular to a method for reducing the emission of phosphine therefrom. The present invention also relates to red phosphorus treated by the said method, to masterbatches comprising treated red phosphorus or including red phosphorus and compounds of the invention, and to polymeric compositions containing flame-retardant quantities of red phosphorus (generally 1-20%), either as pretreated red phosphorus, or with masterbatches, or by the addition of compounds of the invention during processing. Red phosphorus is well known per se as a flame retardant for polymeric materials. However, red phosphorus, even at ambient temperatures, tends to decompose slowly, with the emission of phosphine. At the temperatures at which many polymeric materials are processed, even more phosphine will be evolved. Atmospheric oxidation of red phosphorus tends to give phosphorus acids, hydrogen and phosphine as decomposition products, of which phosphine is the most hazardous (having a TLV of 0.3 ppm in the USA). Attempts have been described to reduce the emission of phosphine from red phosphorus by treating the phosphorus with carbonyl compounds. Reactions of phosphorus with compounds containing unsaturated carbon-to-carbon bonds are also known but require the additional use of a free-radical initiator before effective combination with the phosphine can be achieved. This use of a free-radical initiator would lead to cross-linking and degradation of polymers during processing. Masterbatches, comprising red phosphorus and a polymeric material, are widely used in the electrical industry, especially for further processing (eg, as sheathing for cable). The masterbatches are supplied in bulk and stored until ready for use. It is therefore important, both for economic and for environmental reasons, that the evolution of phosphine from the red phosphorus contained in the masterbatches is kept to a minimum. We have unexpectedly found that acyclic, aliphatic compounds containing at least one carbon-to-carbon double bond in the alpha - position relative to at least one electron-withdrawing group, are effective in minimising the evolution of phosphine from red phosphorus. Accordingly, the present invention provides a method of reducing the emission of phosphine from red phosphorus, the method comprising adding to the red phosphorus an acyclic, aliphatic compound having one or more carbon-to-carbon double bonds, at least one of said double bonds being in the alpha - position relative to an electron - withdrawing group. The present invention also provides red phosptorus treated by the method described in the immediately - preceding paragraph. The present invention further provides phosphine-suppressed flame-retardant compositions comprising red phosphorus treated according to the aforesaid method and polymeric materials. The present invention yet further provides a method of making flame-retardant compositions as herein described. According to the present invention, the electron - withdrawing group may be a carbonyl group or a thio group, for example aldehyde, thioaldehyde, ketone, thioketone, carboxylic acid, thioacid, carboxylic acid anhydride, thioacid anhydride, carboxylic ester or thioester. Alternatively the electron - withdrawing group may be halogen, nitrile, nitro, ether or thioether. As stated hereinabove, the compound used for the treatment of red phosphorus has at least one carbon-to-carbon double bond in the alpha - position relative to an electron - withdrawing group and a particularly preferred example of such a compound is trans - cinnamaldehyde. Suitably, the compound used to treat the red phosphorus is added to the red phosphorus in an amount of from 0.1% to 100% by weight, preferably 5% by weight. Masterbatches according to the present invention may suitably comprise a polymer containing 20% to 80% by weight of red phosphorus, preferably 50% by weight. Suitable polymeric materials include thermoplastics and thermosetting materials. Suitable thermoplastics materials include polyethylene, polypropylene, polystyrene, high-impact polystyrene, acrylonitrile/butadiene/styrene terpolymers, styrene/butadiene/styrene terpolymers and styrene/butadiene copolymers. Alternatively, polyamides, polyesters, acrylates and vinylic polymers may be used as the thermoplastics materials. Suitable thermosetting materials include epoxies, phenolics, polyurethanes, urea-formaldehyde polymers and polyureas. Preferred embodiments of the present invention will be illustrated by way of the following Examples. Example 1 - Phosphine Suppression of Red Phosphorus Powder In each case, 1g of red phosphorus was mixed with 1g of suppressant. The mixture was sealed in a 250-ml conical flask fitted with a gas-sampling septum. Humidity was controlled to about 70% in the flask by the inclusion of a test-tube containing a saturated mixed-salt solution of ammonium chloride and potassium nitrate. The phosphine level in the flask was measured after 14 days by gas head-space analysis on a Gas Chromatograph fitted with a Flame Photometric Detector. Calibration was against a cylinder of a known concentration of phosphine in nitrogen. Ex. No. Description Relative Phosphine (%) 1.1 Red Phosphorus Control 100 1.2 1.1 + CROTONALDEHYDE 0 1.3 1.1 + METHYL METHACRYLATE 54.9 1.4 1.1 + alpha-CHLOROCINNAMALDEHYDE 0 1.5 1.1 + CINNAMOYL CHLORIDE 5.8 1.6 1.1 + CINNAMAMIDE 64.7 1.7 1.1 + CINNAMONITRILE 19.6 1.8 1.1 + 2-NITROCINNAMALDEHYDE 1.8 1.9 1.1 + CITRAL 1.4 1.10 1.1 + alpha-AMYLCINNAMALDEHYDE 4.5 1.11 1.1 + alpha-METHYL-trans-CINNAMALDEHYDE 3.6 1.12 1.1 + 2,4-HEXADIENAL 0.06 1.13 1.1 + 3-METHYL-2-BUTENAL 0.34 1.14 1.1 + trans, trans-DIBENZYLIDENEACETONE 14.6 1.15 1.1 + 2-ETHYL-trans-2-BUTENAL 0.44 1.16 1.1 + CINNAMYL CHLORIDE 0.56 1.17 1.1 + 4-PHENYL-3-BUTEN-2-ONE 9.0 1.18 1.1 + trans-3-PENTEN-2-ONE 4.4 1.19 1.1 + trans-2-METHYL-2-BUTENAL 0.56 1.20 1.1 + trans-CINNAMALYDEHYDE 0.22 Example 2 - Phosphine Suppression of Red Phosphorus Masterbatch 7.5g of suppressant was added to 150g of red phosphorus and mixed thoroughly. 150g of low density polyethylene (LDPE); (mfi = 7); was added. The mixture was stirred and extruded through a 25/25 single-screw extruder fitted with a cavity transfer mixer. The masterbatch was pelletised and phosphine was monitored by placing 1g of masterbatch in a 250-ml flask as in Example 1 above. Relative Phosphine (%) 2.1 Red Phosphorus Control 100 2.2 2.1 + trans-CINNAMALDEHYDE 3.7 Example 3 - Phosphine Suppression of Flame Retardant Polymeric Composition 160g of masterbatch as in Example 2 above was added to 840g of LDPE (mfi = 7) and injection-moulded to give test specimen bars, each about 8.4g in weight. A bar was cut in half and placed in a 250-ml flask for phosphine monitoring as in Example 1 above. Relative Phosphine (%) 3.1 Red Phosphorus Control 100 3.2 3.1 + trans-CINNAMALDEHYDE 8.3 Example 4 - Phosphine Suppression using a Carrier for the Suppressant 2.5g of trans-CINNAMALDEHYDE was dissolved in 10g of acetone and soaked into 5g of carbon black. Acetone was evaporated off. The treated carbon black was then processed into low-density polyethylene (MFI=7) and tested for phosphine as in Examples 2 and 3 above. Relative Phosphine (%) 2.1 Red Phosphorus Control - Masterbatch 100 4.1 trans-CINNAMALDEHYDE/Carbon Black Masterbatch 7.4 3.1 Red Phosphorus Control - Polymeric Composition 100 4.2 trans-CINNAMALDEHYDE/Carbon Black Flame Retardant Polymeric Composition 8.3

Claims: A method for reducing the emission of phosphine from red phosphorus, characterised by reacting the red phosphorus with an acyclic, aliphatic compound having one or more carbon-to-carbon double bonds, at least one of said double bonds being in the alpha - position relative to an electron - withdrawing group. A method according to Claim 1, characterised in that the electron withdrawing group is a carbonyl group or a thio group, for example, aldehyde, thioaldehyde, ketone, thioketone, carboxylic acid, thioacid, carboxylic acid anhydride, thioacid anhydride, carboxylic ester or thioester. A method according to Claim 1, characterised in that the electron - withdrawing group is halogen, nitrile, nitro, ether or thioether. A method according to Claim 1 or characterised in that the acyclic, aliphatic compound is trans - cinnamaldehyde. A method according to any one of Claims 1 to 4, characterised in that the acyclic, aliphatic compound is added to the red phosphorus in an amount of from 0.1% to 100% by weight, for example, about 5% by weight. A phosphine-suppressed flame-retardant composition, characterised by a polymeric material and red phosphorus treated according to the method of any one of Claims 1 to 5. A composition according to Claim 6, characterised by from 20% to 80% by weight red phosphorus and correspondingly from 80% to 20% by weight of the polymeric material. A composition according to Claim 7, characterised by 50 parts by weight of the polymeric material and 50 parts by weight of red phosphorus. A composition according to Claim 6, 7 or 8 characterised in that the polymeric material is polyethylene, polypropylene, polystyrene, high-impact polystyrene, an acrylonitrile/butadiene/styrene terpolymer, a styrene/butadiene/styrene terpolymer or a styrene/butadiene co-polymer. A composition according to Claim 6, 7 or 8 characterised in that the polymeric material is a polyamide, a polyester, an acrylate or a vinylic polymer. A composition according to Claim 6, 7 or 8 characterised in that the polymeric material is an epoxy -, a phenolic -, a polyurethane or a urea/formaldehyde - resin or a polyurea.

Inventors: CHILLES COLIN ANDREW, DUTTON TOM, OAKLEY JOHN SIMON, ZAKIKHANI MOHSEN, CHILLES, COLIN ANDREW, DUTTON, TOM, OAKLEY, JOHN SIMON, ZAKIKHANI, MOHSEN
Applicants: ALBRIGHT & WILSON, ALBRIGHT & WILSON LIMITED
Application year: 1992
Main classification: C01B25
IPC codes: C08K3, C09K21, C01B25