IL102190A - Fire retardant polymer compositions - Google Patents

Description

2235/92 102190/2 FIRE RETARDANT POLYMER COMPOSITIONS 2235/92 POLYMER COMPOSITIONS Field of the invention This invention relates to polymer compositions, more particularly to impact resistant polymer compositions comprising a base polymer and a polyoctenamer.

Background of the invention Polymers are often used in plastic compositions in combination with a variety of additives. These are introduced to impart or improve upon properties which are deficient in the base resin. Thus, for example, pure PVC is a rigid material to which plasticizers are commonly added to reduce brittleness. Fire retardants (FRs) may be added to decrease the flammability of the base resin. Fillers are added to stiffen some polymers and/or reduce costs for the end-user.

However, these additives too, often introduce other deleterious effects which may limit the effective range of uses, unless yet another additive can be found to overcome this deficiency. For example, PVC plasticizers may be inflammable, thereby necessitating the use of FR additives. FRs often reduce the impact resistance of polymeric substrates, necessitating the use of impact improvers. However, the latter in turn, may reduce HDT (Heat Deflection Temperature) and/or flame retardancy. As a result, the final product is often a plastic composition which contains a number of components combined to produce the optimal properties for the intended use. It would be desirable to minimize the number of materials required to achieve 2235/92 this end, for economic as well as technical reasons but this is not often possible.

It is a purpose of this invention to provide polymer compositions, based on a variety of base polymers, that have high impact resistance.

It is another purpose of the invention to provide such compositions that are satisfactory from the viewpoint of other desirable properties, e.g. fire retardation.

It is a further purpose of this invention to provide such compositions that are inexpensive and can be prepared by conventional operations and equipment.

Other purposes and advantages of the invention will appear as the description proceeds.

Summary of the invention The polymer compositions according to the invention are characterized in that they comprise at least one base polymer, at least an additive that is a fire retardant (FR) and/or a filler, and at least one polyoctenamer.

The base polymer is chosen in the classes of thermosetting or thermoplastic resins.

Preferably, the base polymer is chosen from among styrene resins, PVC, polyolefins, polycarbonates, polyacrylates, linear and 2235 92 unsaturated polyesters and epoxies; styrene resins, the polyester PBT, PVC and polyolefins being particularly preferred.

The amount of polyoctenamer in the composition is from 1 to 20%, preferably from 5 to 10%, by weight of the composition.

Other components, such as fire retardant synergists, UV stabilizers, lubricants, anti- oxidants, heat stabilizers, cross-linking agents such as peroxides and triallyl cyanurate, and pigments may be included in the composition. Examples of additives are AO, Mg stearate, stearic acid, DCUP, CC-DFB, and the like.

Polyoctenamers are unique polymers of cyclooctene (cf Rubber & Plastics News, 9.7.90, p. 14). The commercial name "Vestenamer", and occasionally its initial V, will be used hereinafter to designate polyoctenamers in general. Two types of polyoctenamers are presently commercially available (from Huels, Marl, Germany): Vestenamer 8012 and Vestenamer 6213.

The invention further provides new polymer compositions of matter, characterized in that they comprise at least one polyoctenamer, at least one fire retardant and/or filler and optionally at least one styrene polymer .

The invention further provides new masterbatch compositions of matter, characterized in that they comprise at least one polyoctenamer and at least one fire retardant and/or filler. 2235/92 The polymer compositions of matter according to the invention are characterized by high impact resistance.

Detailed description of preferred embodiments Polymer compositions comprising a base polymer and ; Vestenamer have been disclosed in the art. Thus JP 62062855 (Daicel-Huels) discloses a composition of polyamides and Vestenamer with or without additives (which include FRs). JP 62205156 (Daicel-Huels) discloses a composition of polyamides and Vestenamer with inorganic fillers and without FR. JP 62131043 (Daicel-Huels) discloses a composition of polyolefins and Vestenamer without FRs. DE 3518277 (Huels), EP 363578 (GE), EP 327677 (GE), and DE 3442273 (Huels) disclose compositions of polyphenyl ether (PPE) and Vestenamer, with the addition of other components, such as FRs, polyethylene and styrene resins.

Surprisingly, it has now been found that polyoctenamers are useful as impact improvers, without seriously detracting from other physico-mechanical properties, in styrene resins, PVC, polycarbonates, polyacrylates, polyolefins, polyesters, etc. when used, in minor amounts, in combination with FRs and/or filler type additives.

Styrene resins include high impact polystyrene (hereafter "HIPS"), ABS and other styrene copolymers. Polyolefins are represented primarily by polyethylene (PE) and polypropylene (PP). Polyesters may be unsaturated resins or linear polymers (e.g. PBT and PET) used for fibers or in engineering applications. 2235 92 The range of concentrations of the additives used varies considerably with the requirement of the use for which the polymer composition is intended. However, bromine containing FRs are commonly used in such concentrations that the Br content of the final product is from 1-30%, preferably from 10-20% by weight of the final polymer composition.

Intumescent fire retardants (IFR), such as ammonium polyphosphate and melamine phosphate, and metal oxide hydrates such as Mg(OH)2, when used as FRs, are often present in amounts of about 20-80%, preferably from 30-70% by wt of the final polymer composition. Fillers, such as CaC03, when used e.g. in PVC, are used at levels of 20-80%, and preferably 50-70% by wt of the final polymer composition.

The polyoctenamers are used in the compositions claimed by us in minor amounts, i.e. to an extent of about 30-40 % with respect to Br-containing FRs and 2-10% by wt with respect to fillers and the intumescent and hydrated FRs.

Typical Br-containing FRs are TBS (tribromostyrene) (FR-803), PBB-MA (p entab romob enzyl acrylate ) (FR-1 025 M) , and tribromophenylmaleimide (FR-1033), etc., which represent the reactive type of FR. Additive type FRs, such as poly- tribromostyrene, Deca, TBBA, brominated epoxy resins, etc., can also be used. Typical hydrated FRs are: Mg(OH)2 and aluminum trihydrate (ATH). Typical IFRs are ammonium phosphates and polyphosphates and melamine phosphates, often used in combination with polyhydric compounds such as pentaerythritol. 2235 92 Other additives may also be present, such as pigments, stabilizers, processing aids, lubricants, etc.

Surprisingly, the compositions according to the invention, besides having enhanced impact resistance and good fire retardant properties, exhibit good thermal processing properties. They possess, therefore, a combination of useful properties that the polymer compositions of the prior art do not possess.

The three basic components of the compositions according to the invention, i.e. resin, FR (or filler) and the polyoctenamer, can be co-blended (with or without other additives) and the final plastic composition produced in a single fabrication operation (such as extrusion, injection, molding, etc.); or the polyoctenamer may be first combined with the second additive (the FR or filler) to produce masterbatches, and this combination, may be mixed and fabricated with the resin (with or without other additives) in a separate step. The latter type of operation has been found to be advantageous in some cases, such as in styrene polymers, because it permits to reduce the FR load. The blending and fabrication temperatures vary depending primarily upon the nature of the resin being processed. The following temperature ranges are indicative, but not limiting: 240°C - 270°C ABS 230°C - 280°C HIPS 210°C - 250°C PP A number of non-limitative examples of the invention will now be described. The formulations and masterbatches (hereafter "MBs") of 2235/92 the examples were prepared on a Brabender PLE 651 twin-screw extruder using a temperature profile of 120°C, 180°C, 230°C and 220°C, a Buss Cokneader or a Papenmeier mixer, and the final formulations subsequently injection molded to test specimens on an Arburg Allrounder Model 221-75-350 injection molding machine at a temperature profile of 180°C, 240°C, 240°C, 235°C. Other fabrication techniques are not excluded: such techniques include e..g. cast molding, extrusion, vacuum forming, press molding, and rotational molding.

The following operating conditions prevailed in the injection operation: Injection speed 2 Cycle time 20 seconds Injection pressure 70 bar Hold pressure 50 bar Back pressure 25 bar 2235 92 Example 1 Masterbatches (MB) comprising a polyoctenamer and FRs Tafrle 1 Compositions comprising ABS, a polvoctenamer and FRs. formed from masterbatches "Masterbatches 1A and 1C", below, designate the masterbatches of Example 1. 2235 92 Taftle2 Example 3 Compositions comprising HIPS, a polyoctenamer and FRs. formed from masterbatches Table The properties of the compositions according to the invention are illustrated by the following comparison of 1.6 mm VO (Rating Standard UL-94) ABS and NR (Non-rated) ABS. 2235/92 Table 4 - eat e ecton emperature- 64 Flammability- UL-94 dSudden stop of injection molding machine for 5 min., after which continued successful molding was possible or impossible.

The following table provides a comparison between 3.2 mm VO HIPS and NR HIPS. 2235/92 Table 5 Example 4 Comparison of Properties of Compositions Comprising ABS. V and FR Formed by Direct Compounding and via masterbatches. 2235/92 Table 6 Comrx>unding Technique Direct Via MB Compounding Components Form. Form Form. Form. Form. Form. 4 4A 2 2* . 2A 2B ABS Novodur P2H-AT ex Bayer % 71.2 71.1 71.2 71.2 71.2 71.2 FR-803 ex BCL % 17.1 17.1 17.1a 17.1b 17.1c 17.1d AO Blue Star "RG" % 4.2 4.2 4.2a 4.2b 4.2C 4.2d ex CAMPINE Vestenamer 8012 % 6.4 6.4 6.4a 6.4C 6.4d ex Huels 6213 -- 6.4b -- -- Additives % 1.1 1.1 l.la 1.1b l.lc 1.1* CC-DFB ex Peroxide % 0.1 ... -. 0.03c -- Chemie DCUP exAkzo 0.03d Bromine % 12.0 12.0 12.0 12.0 12.0 12.0 Properties6 Flammability (1.6 mm) UL 94 Rating V2 NA VO NA . NA NA HDT (1.82 MpA 50°C h) °C 69.0 NA 68.0 63.0 NA NA Izod Notched Impact J/M 90.0 67.0 130.0 130.0 92.0 44.0 aMasterbatch 1A bMasterbatch 1C cMasterbatch ID dMasterbatch IE eTest methods: Izod Notched Impact ASTM D256 HDT - Heat Deflection Temperature- ASTM D648 Flammability- UL-94 The improvement of the overall properties with respect to those of the parallel experiments in Table 4 is readily apparent. 223592 Example 5 Comparison of Properties of Compositions comprising HIPS. V and FR formed bv direct compounding and via masterbatches.

Table 7 Compounding Technique Direct Compounding Via Masterbatch Components Form5 Form.3 Form. 3' Hips Vestyron 638 ex Huels % 78.0 78.3 78.3 FR % 12.9 12.9a 12.9 AO Blue Star "RG" ex Campine % 3.5 3.2a 3.2b 8012 % 4.8 4.8a Vestenamer ex Huels 6213 % -- 4.8b Additives % 0.8 0.8a i 0.8b Bromine % 9.0 9.0 9.0 Properties0 Flammability (1.6 mm) UL-94 V2 VO^ NA Rating HDT (1.82 MPa 50°C/h) °C 65.0 65.0 64.0 Izod Notched Impact J/M 61.0 86.0 100.0 aMasterbatch 1A bMasterbatch 1C cTest methods: Izod Notched Impact - ASTM D256 HDT - Heat Deflection Temperature- ASTM D648 Flammabilitv- \Kr94 2235/92 The improvement of the overall properties with respect to those of the parallel experiments in Table 5 is readily apparent.

Example 6 Masterbatch comprising V and MgfOHD The following MB was prepared in a Papenmeier mixer with a residence time of 5 minutes, wherein the temperature rose to 65°C.

Table 8 The product was labeled MB 1H.

Example 7 Properties of Compositions Comprising' Polypropylene. V and MgCOrD,.

These compositions were prepared in a Buss Cokneader at 210-220°C with a residence time of 3 minutes. The Mg(OH)2 and V were introduced via the MB 1H of Example 6. 2235/92 Table9 Formulation 6A 6B 6C PP Lacqtene MNl 3120 ex Atochem % 30.6 33.8 98.8 Mg(OH)2 HD-12 ex Periclase % 65.0a 65.0 -- Vestenamer 8012 ex Huels % 3.2a -- -- Additives 5 % 1.2 1.2 1.2 Properties0 Flammability (3.2 mm)UL-94 VO VO NR Rating HDT (1.82 MPa 50°C h) °C 60.0 NA 54.0 Izod Notched Impact J/M 17.0 2.0 25.0 Color vs. Absolute White DE 25.0 NA NA aMasterbatch 1H b Additives Irganox B-255 ex. Ciba-Geigy 10.6% Loxiol UL-100 ex Henkel 57.0% Stearic acid ex Witco 32.4% cTest methods: Izod Notched Impact - ASTM D256 HDT - Heat Deflection Temperature- ASTM D648 Flammability- UL-94 Color [DE] Cie-Lab L*a*b* List of Abbreviations TBS Tribromostyrene PTBS Polytribromostyrene DECA/FR-1210 Decabromodiphenyl Ether OCTA/FR-1208 Octabromodiphenyl Ether ABS Acrylonitrile, Butadiene, Styrene Resin HIPS High Impact Polystyrene PBT Polybutylene Terephthalate PET Polyethylene Terephthalate V Vestenamer/Polyoctenamer MB Masterbatch masterbatch - a premixture of some of the components to be used subsequently with other components in the formation of the final composition (cf. eg. H. Mark, Encyc. of Polymer Science and Technology, Vol. 2, p. 700) DCUP Dicumyl Peroxide CC-DFB 2,3-Dimethyl-2,3-Diphenylbutane CG Ciba-Geigy BCL Bromine Compounds Ltd.

NA Not Available Pyrochek 68 Brominated Polystyrene Ex Ferro While a number of illustrative examples have been given, it is understood that the invention is not limited thereto and may be carried out by persons skilled in the art with many modifications, variations and adaptations, without departing from its spirit or exceeding the scope of the claims. 102190/3 -17-

Claims (16)

1. - Polymer composition, characterized in that in comprises at least one base polymer selected from among styrene resins, PVC, polyolefins, polycarbonates, poly aery late s, linear and unsaturated polyesters and epoxies, at least one additive chosen from among fire retardants and/or fillers, and at least one polyoctenamer.

2. - Composition according to claim 1, wherein the amount of polyoctenamer in the composition is from 1 to 20% by weight of the composition.

3. - Composition according to claim 2, wherein the amount of polyoctenamer in the composition is from 5 to 10% by weight of the composition.

4. - Composition according to claim 1, further comprising at least one other component chosen from among fire retardant synergists, UV stabilizers, lubricants, anti-oxidants, heat stabilizers, cross-linking agents and pigments.

5. - Composition according to claim 4, wherein said other component is chosen from among AO, Mg stearate, stearic acid, DCUP, CC-DBF, peroxides and triallyl cyanurate.

6. - Composition according to claim 1, wherein the halogen content, when halogenated fire retardants are present, is comprised between 1 and 30 % by weight, and the fillers and intumescent and/or metal hydrate fire retardants, when present, are comprised between 20 and 80 % by weight of the composition. 102190/3 -18-

7. - Composition according to claim 6, wherein the halogen content when halogenated fire retardants are present, is comprised between 10 and 20 % by weight, and the fillers and intumescent and/or metal hydrate fire retardants, when present, are comprised between 50 and 70 % and 30 and 70%, respectively, by weight of the composition.

8. - As new compositions of matter, masterbatches characterized in that they comprise at least one polyoctenamer and at least one additive chosen from among fire retardants and/or fillers.

9. - Masterbatch according to claim 8, further comprising at least one styrene polymer.

10. - Masterbatch according to claim 8, further comprising at least one additive chosen from among those listed in claim 4.

11. - Process for the preparation of compositions according to claim 1, comprising preparing a masterbatch comprising at least one polyoctenamer and at least one additive chosen from among fire retardants and/or fillers and blending it with a base polymer.

12. Process for the preparation of compositions according to claim l,or of masterbatches according to claim 8, comprising thermo-blending and thermo-mixing operations.

13. Process for the preparation of compositions according to claim 12 , comprising an operation chosen from among injection molding, cast molding, extrusion, vacuum forming, press molding and rotational molding. L U Z Z ATT O & L U ZZATT O By : - * l*y 102190/2 -19-

14. Polymer composition according to any one of claims 1 to substantially as described an illustrated by any one of the examples.

15. Masterbatch according to any one of claims 8 to 10, substantially described and illustrated by any one of the examples.

16. Process according to any one of claims 11 to 13, substantially described and illustrated by any one of the examples. •HJ N S V? JIM LUZZATTO & LUZZATTO