SMOKE SUPPRESSANT POLYMER COMPOSITIONS

Abstract: A polymer composition comprises: polymeric material of which at least one third is constituted by homopolymer or copolymer of vinylchloride; five to one hundred in parts per hundred parts of total polymer of a plasticiser selected from the organic esters of formula in which R¹ is selected from the lower (meaning up to C20) alkyl groups; R² is selected from H, the lower alkyl and lower acyl groups; and R³ and R⁴ are independently selected from H, OH, lower alkyl groups, and lower acyloxy groups, such group (in every case) optionally having one or more than one substituent selected from lower alkyl groups, lower acyl groups and lower acyloxy groups; and effective amounts of at least one stabiliser and at least one smoke suppressant. The plasticisers produce a synergistic smoke suppressant effect with most commercially available smoke suppressants.

Description: Polymer Compositions This invention relates to polymer compositions containing major amounts (say at least one third of total polymer content) of homopolymers and/or copolymers of vinyl chloride, all hereinafter called 'PVC compounds' for brevity. PVC compounds frequently contain a plasticiser and a stabiliser, and in most cases a filler, and when these are suitably chosen the compounds have excellent. physical, chemical and electrical properties and are widely used for the insulation and/or sheathing of electric wires and cables; also for example floor and wall coverings, upholstery fabrics, tapes, film, belting, extruded profiles, hose and as mouldings, coatings (often applied in plastisol form) etc. The significant chlorine content of PVC gives compositions based on it a degree of flame retardance, but the results achieved vary with the formulation and are particularly sensitive to the type and amount of plasticiser (usually the most flammable major ingredient); even compositions specially formulated for high oxygen index will burn, and/or will decompose to liberate vapours that burn, if exposed to a sufficiently high temperature, for example by a fire breaking out in a building in which products containing the compositions are installed. ;en this happens dense smoke is liable to be generated and in a situation where the amount of the polymer composition present is large, this may significantly increase the danger of the fire by obscuring its location and/or hampering both escape and fire-fighting. In recent years, a number of additives that have a broad, if not universal, tendency to reduce smoke generation when added to such polymer compositions have been discovered, but further improvement is desirable. Such an additive is hereinafter called a 'smoke suppressant' which expression, for the avoidance of uncertainty, is hereby defined as a substance which, when added in a small amount to the other ingredients of the specific polymer composition being ref erred to, reduces the amount of smoke generated on burning under at least some conditions. Some smoke suppressants can be regarded as constituting a filler also. We have now discovered that the effect of known smoke suppressants can be enhanced to a surprising extent by using a plasticiser (or more than one plasticiser) of a particular kind. In accordance with the invention, a polymer composition comprises: polymeric material of which at least one third is constituted by a homopolymer or copolyme of vinyl chloride,10 - 100 parts per hundred parts of total polymeric material of plasticiser, being at least 30% of the total plasticiser present, selected from the organic esters of formula EMI3.1 in which R1 is selected from the lower (meaning up to C20 alkylgroups; R2is selected from H, the lower alkyl and lower acylgroups; and R3 and R4are independently selected from OH, lower alkoxy groups, and lower acyloxy groups, provided that not more than one of R2, R3 and R4 is included among H, OH and lower alkyl, such groups (in every case) optionally having one or more than one substituent selected from lower alkyl groups, lower acyl groups and lower acyloxy groups; and effective amounts of at least one stabiliser and at least one smoke suppressant. (Parts herein are by Preferred copolymers of vinyl chloride are those (including graft copolymers) in which the copolymerisable monomer is ethylene, propylene, vinylidene chloride, acrylic and methacrylic acids and their esters, and vinyl acetate. The compositions need not contain any other polymer1 but when there is another polymer present it may be any that is compatible with the other ingredients; in particular it may be a chlorine-containing polymer or it may be a polymer not containing chlorine. An exampleis a copolymer of ethylene with 5 - 60% vinyl acetate (EVA). More than one plasticiser may be used,though the total plasticiser content should not normally exceed 100 parts; in the case of flexible PVC compounds at least one must be a primary plasticiser, but one or more may be a secondary plasticiser (sometimes called an extender) that would not be effective as a plasticiser in the absence of the other plasticiser or plasticisers (the plasticiser defined above as a characteristic of the invention may be either primary or secondary). Preferably, however, a single plasticiser, or more than one plasticiser selected from the group defined, is used. One preferred group of plasticisers has the formula EMI4.1 in which R5 and R6 are selected from the same groups as R3 and R4, and R7 fran the same groups as R1, all listed above, provided that no more than two of R3, R4 R5, and R6 is included among H, OH and lower alkyl. More specifically we prefer plasticisers of either of the formulae specified in which R1 and R7 (if present)are unsubstituted alkyl groups; R2 (if present) is an unsubstituted acyl group, and R3, R4, R5 and R6 (to the extent present) are unsubstituted acyloxy groups. Preferably all the R groups have at least 3 carbon atoms. Most preferred are the fatty acid hexa-esters of dipentaerythritoland in particular the mixed butyratecaprylate hexa-esters commercially available under the trademarks Bisoflex OBC and Hercoflex707, and the corresponding esters of pentaerythritol. For most of the plasticisers, and most of the applications, contemplated, the total plasticiser content will bein the range 30 - 90 parts per hundred parts of total polymer. The stabiliser may be conventional and does not require description, naturally the amount required will depend upon the type selected and upon the end-use. The benefits of the invention appear to be obtained with all known classes of smoke suppressant additives but more especially with those that affect pyrolytic mechanisms. in the condensed phase rather than combustion processes in the flame zone. At present we prefer to select from: (i) Smoke suppressant molybdenum compounds especiall.y (but not exclusively3 (a) of a kind described by F. W. Moore in a paper entitled "Advances in the Use of Molybdenum Additives as Smoke Suppressants for PVC and Results of Mechanism Studies" presented at the Polymer Conference in Detroit, Michigan,. USA on 24th May, 1977 (see also US Patent 3870679), for example molybdic oxide (b) the proprietary materials sold under the trade mark Kemgard as Kemgard 911A and Kemgard 911C, which are believed to be of the kind described and claimed in British Patent 1551472, and (c)ammonium dodecaphosphomolybdate. (ii) metal oxide solid solutions of the kinds described in British Patent 1521531 and British Patent Application - 2032908A, for example the product sold as "Ongard II" which is believed to be a solid solution of.the oxides of zinc, magnesium and calcium. (iii) metal salts of the kind described in British Patent 1490233, for example the commercial hydrated zinc borate sold under the designations "ZB-2335" and FirebrakeZB. (iv) magnesium compounds, especially the hydroxide basic carbonate and carbonate and the proprietary compound sold under the designation "Reomol DV243". These smoke suppressants can be used at customary levels. Naturally these vary from material to material, but in most cases in the range 0.01 - 70 parts per hundred total polymer (or more in the case of smoke suppressants that are also fillers). 0.1 - 20 Parts (and more especially 2 - 10) can considered a preferred range. be In most cases the polymer compositions df the invention will include at least one filler; a wide range may be used but (setting aside the smoke suppressant fillers already discussed) we prefer to use fillers that enhance flame retardance and/or inhibit emission of hydrogen chloride on combustion. More particularly, we prefer to use one or more of alumina trihydrate calcium carbonate dolomite especially in grades of small particle size (of the order of 0.1 micrometres and below for the carbonates when acidbinding properties are desired, and in other cases 10 micrometres or below). When a high degree of resistance to flame propagation is desired, preferably the compositions also include a flame-retardant additive, preferably antimony trioxide. Among other ingredients that may be included if desired are lubricants, (e.g. calcium stearate), crosslinking agents, crosslinking promoters, radiation sensitisers, colourants, antioxidants, U.V. stabilisers, blowing-agents, and anti-static agents, all in customary amounts. In appropriate cases the compositions can be cross-linked by electron or gamma radiation, or by other known techniques. The invention is illustrated by the following tabulated examples (including comparison examples, indicated by letters to distinguish them immediately from numbered examples of the invention). In all the examples, the polymer composition comprises 100 parts of the same suspension-grade vinyl chloride homopolymer of K-value 71 (calculated from relative viscosity data obtained by the method in ISO R 174), 50 parts of the filler specified, 8 parts of a proprietary stabiliser paste (of which 2 parts is a conventional plasticiser), 50 parts total plasticiser (excluding that in the stabiliser paste), 1 part calcium stearate (lubricant) and varying amounts (or none) of smoke suppressant. The various formulations were compounded on a 2-roll mill and pressed at 160 degrees C into sheets of appropriate thickness. Samples, cut from a sheet 1.0 + 0.1 mm thick were tested for smoke generation according to ASTM E662-79 in the flaming mode using an N.B.S.smoke chamber supplied by American Instrument Co. (Aminco) (results quoted as Dmcorr, the maximum specific optical density measured and corrected for smoke deposition on the optical detection system and as percentage transmittance). Samples cut from a sheet 3 mm thick were tested for oxygen index according to BS2782: Part 1: 1978, Method 141D (results as % oxygen). Tables 1- 3 identify materials (plasticisers, smoke suppressants and fillers) used in the examples that follow. Table Plasticisers Designation Herein Chemical type Trade mark Supplier DOP di(2-ethyl hexyl) phthalate - Various (commercial dioctyl phthalate) 530 a trialkyl (straight chain Monoplas 530 Scott-Bader C7 - C9) trimellitate Ltd. G62 epoxidised soyabean oil Paraplex G62 Rohm & Haas Co. DOA di(2-ethyl hexyl) adipate Bisoflex DOA) ) ) 107 a mixed ester based on C4 - C6 Bisoflex 107) linear dibasic acids (mainly ) aliphatic with very small ) BP Chemicals proportions of phthalate) ) Ltd. OBC mixed butyrate-caprylate Bisoflex OBC) hexa-ester of dipentaerythritol DHC dipentaerythritol hexacaprylate DPHC LP3 Pentaerythritol tetra pelar- Reolube LP3600) gonate) ) LP5 Mixed acid (C5 to C7 tetra Reolube LP504 ) Ciba-Geigy ester of pentaerythritol) Ltd ) LP6 Mixed acid (C5 to C8') tetra Reolube LP602 ester of pentaerythritol SR2 Pentaerythritol tetra-acrylate Ancomer SR295) ) Ancomer Ltd SR3 Dipentaerythritol penta-acrylate Ancomer SR399) Table 2 Smoke Suppressants Designation Herein Chemical type Trade Mark Supplier MoO3 molybdic oxide MFR Climax Molybdenum Ongard believed to be a solid solution Ongard II Anzon Ltd. comprising oxides of zinc, magnesium and calcium ZB-2335 hydrated zinc borate ZB-2335 Borax Corp. 911A a complex molybdate carried on Xemgard 911A) Sherwin particles of calcium carbonate ) Williams Co. 911C a complex molybdate carried on Kemgard 911C) particles of talc. DV243 a magnesium compound Reomol DV243 Ciba-Geigy Ltd. ADPM ammonium dodecaphospho- - Various molybdate Table 3 Fillers Designation Chemical type Particle size Trade mark Supplier Herein 7Mt calcium carbonate 95% below Snowcal 7ML Blue Circle 10 micrometres Ltd. 710 hydrated alumina below Hydral 710 Alcoa Ltd. (alumina trihydrate) 2 micrometres DLMC magnesium 2 - 7 Darlington The Chemical basic carbonate micrometres & Insulating Co. Ltd. Table 4 illustrates the synergistic effect of using a plasticiser of the kind described (specifically OBC) in combination with a smoke suppressant (specifically MoO3) in in contrast with the much smaller effect of using the same smoke suppressant with other aliphatic and aromatic plasticisers: Table 4 E Composition NBS smoke chamber test x Corrected a maximum. m Plasticiser Filler Smoke. optical Transmit- Oxygen Compare P Suppressant density tance Index with 1 (parts by Dmcorr T(%) Example(s) e weight) A DOP 7ML none. 310 0.45 23.0 - B DOP 7ML MoO3 (10) 170 5.1 27.2 A C DOA 7ML none 330 0.31 22.1 D DOA 7ML MoO3 (10) 170 5.1 26.3 C E 107 7ML none 310 0.45 22.5 F 107 7ML MoO3 (10) 180 4.3 27.2 E G OBC 7ML none 300 0.53 22.6 A,C,E 1 OBC 7ML. MOO3 (10) 80 24 24.8 .B,D,F,G Table 5 illustrates how broadly similar results are obtained. with a variety of different known smoke suppressants. Table 5 E Composition NBS smoke chamber test x Corrected a maximum m Plasticiser Filler Smoke optical Transmit- Oxygen Compare p Suppressant density tance Index with 1 (parts by D corr T(%) Example(s) c weight) m H DOP 7ML Ongard (10) 200 3.0 24.8 A 2 OBC 7ML Ongard (10) 140 8.7 26.3 A, H J DOP 7ML ZB2335 (10) 250 1.2 26.1 A 3 OBC 7ML ZB2335 (10) 150 7.3 25.2 A, J 4 OBC 7ML 911A (10) 110 14 25.9. A, G 5 OBC 7ML 911C (10) 120 12 24.6 A, G 6 OBC 7ML Dv243 (10) 130 10 24.2 A, A, G 7 OBC 7ML ADPM (5) i40 8.7 23.7 A, A, G 8 OBC 7ML MoO3 (5) 90 20 26.1 A, A, G, j +ZB2335 (5) 1, 3 Table 6 illustrates the invention in the field of reactive (flame retardant and smoke suppressant) fillers. Table 6 Composition NBS smoke chamber test x Smoke Additional Corrected a Suppress- Smoke maximum m Plasticiser ant Suppressant optical Transmit- Oxygen Compare p Filler (parts by density tance Index with 1 weight) Dmcorr T(%) Example(s) e X DOP 710 none 310 0.45 24.8 A 9 OBC 710 none 200 3.0 27.5. G L DOP DLMC none 300 0.53 25.7 A 10 OBC DLMC none 230 1.8 28.7 G M DOP 710 MoO3 (10) 180 4.3 30.5 K 11 OBC 710 Mo03 (10) 80 24 32.5 9, M M DOP 710 Ongard (15) 230 1.8 30.0 K 12 OBC 710 Ongard (15) 160 6.1 31.1 9, @ 13 OBC 710 ZB2335 (10) 110 14 29.3 9, 11, 12 P DOP DLMC none 300 0.53 25.7 A, K Q DOP DLMC MoO3 (10) 290 0.63 27.8 P 14 OBC DLMC MoO3 (10) 110 14 34.1 P, Q, 10 R DOP DLMC Ongard (15) 240 1.5 28.3 P 15 OBC DLMC Ongard (15) 190 3.6 36.1 P, Q, R In an additional example to illustrate compatibility with antimony trioxide (Example 16), the formulation of Example 1 was modified by reducing the content of MoO3 to 5 parts and adding 5 parts antimony trioxide. Dmcorr was increased only to 230 (transmittance 1.8#) and an oxygen index of 29.3 was achieved. In a similar example (Example S) using DOP, the value of Dmcorr was 360 (transmittance 0.18%), which is higher than in Example A with the same plasticiser and filler and no smoke suppressant nor antimony trioxide. Table 7 illustrates modifications to the formulation of Example 1 by replacing part of the OBC with an equal weight of DOP, and shows that a worthwhile advantage can be obtained (at reduced cost) using the plasticisers defined in combination with a conventional plasticiser. Table 7 E Composition tTBS smoke chamber test x Corrected a maximum m Plasticiser Filler Smoke optical Transmit- Oxygen Compare P Suppressant density tance Index with l (parts by Dmcorr T(%) Example(s) e weight) A DOP 7ML one 310 0.45 23.0 B DOP 7ML Mo03 (10) L70 5.1 27.2 A G OBC 7ML None 300 0.53 22.6 A,C,b? 1 OBC 7ML Mo03 30 24 24.8 3',D,F,G 17 40 OBC +10DOP 7ML MoO3 (10) 100 17 - G,1 18 30 OBC +20DOP 7ML MoO3 (10) 110 14 27.2 G,1,17 Table 8 illustrates the use of various esters of pentaerythritol and di-pentaerythritol (including some outside the scope of the invention). Since not all are primary plasticisers, a proportion of nop was used in all cases: Table 8 E Composition NBS smoke chamber test x Other Smoke Corrected Transmit- Compare a Plasti- Suppre- maximum ance with m DOP ciser Filler ssant optical T(%) examples(s) p (parts (parts density 1 by . by weight) Dmcorr e weight) -17 10 OBC (40) 7ML MoO3 (11) 100 . 17 18 20 OBC (30) 7ML MoO3 (10) 110 14 S 20 LP3 (30) 7ML none 300 0.53 19 20 LP3 (30) 7ML MoO3 (10) 140 8.7 18,S T 20 SR2 (30) 7ML none 230 1.8 S U 20 SR2 (30) 7ML MoO3 (10) 210 2.5 19 V 15 LP6 (35) 7ML none 300 0.53 S 20 15 LP6 (35) 7ML Mo03 (10) 130 10 17/18,V w 15 LPS (35) 7ML MoO3 (10j 290 0.63 21 15 LP5 (35) 7ML MoO3 (10) 120 12 X 20 SR3 (30) 7ML none 270 0.9 S Y 20 SR3 (30) 7ML MoO3 (10) 160 6.1 19 Z 20 DPB (30) 7ML none 280 0.75 S 22 20 DPH (30) 7ML MoO3 (10) 110 14 19 23 10 DPrI (40) 7ML MoO3 (10) 110 14 19,21

Claims: Claims: 1. A polymer composition comprising: polymeric material of which at least one third is constituted by a homopolymer or copolymer of vinylchloride; ten to one hundred parts per hundredparts of total polymeric material of plasticiser, being at least 30% of the total plasticiser present, selected from the organic esters of formula EMI16.1 in which R1 is selected from the lower (meaning up to C20) alkyl groups; Rz is selected from H, the lower alkyl and lower acyl groups; and R3 and R4, are independently selected from OH, lower. alkoxy groups, and lower acyloxy groups, provided that not more than one of R2, R3 and R4 is included among H, OH and lower alkyl, such group (in every case) optionally having one or more than one substituent selected from lower alkyl groups, lower acyl groups and lower acyloxy groups; and effective amounts of at least one stabiliser and at least one smoke suppressant. 2. A polymer composition comprising: polymeric material of which at least one third is constituted by a homopolymer or copolymer of vinyl chloride; ten to one hundred parts per hundred parts of total polymeric material of plasticiser-,being at least 30% of the total plasticiser presentselected from the organic esters of formula EMI17.1 in which R1 and R7 are selected from the lower (meaning up to C2.0) alkyl groups and R3, R4, R5 and R6 are independently selected from OH, lower alkoxy groups, and lower acyloxy groups, provided that not more than one of R3 R4t. R5 and R6 is included among H, OH and lower alkyl, such group (in every case) optionally having one or more than ona substituent selected from lower alkyl groups, lower acyl groups and lower acyloxy groups; and effective amounts of at least one stabiliser and at least one smoke suppressant. 3cA composition as claimed in Claim 1 or Claim 2 in which R1 and R7 (if present) are unsubstituted alkyl groups. 4. composition as claimed in any one of the preceding Claims in which R2 is an unsubstituted acyl group. 5.A composition as claimed in any one of the preceding Claimsin which R31 R41 R5 and R6(to the extent present) are unsubstituted acyloxy groups. 6.A composition as claimed in any one of the preceding Claims in which all the R groups have at least three carbon atoms. 7.A composition as claimed in Claim 1 or Claim 2 in which the. plasticiser is a fatty acid hexa-ester of dipentaerythritol. 8.A composition as claimed in Claim 1 or Claim 2 in which the plasticiser is a fatty acid tetra-ester of pentaerythritol. 9. A composition as claimed in Claim 1 or Claim 2 in which the plasticiser is a mixed butyrate-caprylate hexa-ester of dipentaerythritol. 10. A composition as claimed in Claim 1 and Claim 2 in which the plasticiser is a mixed butyrate-caprylate tetraester of pentaerythritol.

Inventors: NESS, DIANE ELIZABETH MARJORIE, WALKER, RICHARD THOMAS
Applicants: BICC PUBLIC LIMITED COMPANY
Application year: 1981
Main classification: C08L27
IPC codes: C08K5