METHOD OF MAKING HEAT RECOVERABLE ARTICLES

Abstract: In the making of heat recoverable hollow articles, a former is coated by dipping into the PVC plastisol. Once dried, the coating is removed from the former and the re­ sultant hollow article is made heat recoverable. The PVC of the hollow article may be crosslinked, preferably by irra­ diation.

Description: MAKING OF HEAT RECOVERABLE ARTICLES This invention relates to methods of making heat recoverable articles. Heat recoverable articles, other than plain tubing, are normally made by injection-moulding, which entails heavy tooling cost and is therefore uneconomic unless large numbers of identical articles are required. In accordance with the present invention, a method of making a heat recoverable hollow article is characterised by the steps of dipping a former into a PVC plastisol to form a coating thereon and, after the plastisol constituting the coating has gelled, removing the coating from the former to form a hollow article and deforming the hollow article under suitable temperature conditions to make it heat recoverable. Preferably, the PVC is crosslinked in the hollow article before the hollow article is deformed as this both increases the extent of heat recovery that can be obtained and improves other properties of the product, for example resistance to oil and solvents and the resistance of the material to mechanical deformation at high temperatures (including the heat recovery temperatures). Thus, the crosslinked article will have greater resistance to thermal abuse during the heat recovery operation than, an article produced from uncrosslinked PVC. Advantageously, the plastisol contains a radiation-crosslinking promoter, and at least a part of the hollow article is irradiated to crosslink the PVC therein. Hollow articles of uncross linked PVC material can be made heat recoverable by deforming them at a temperature below the softening temperature of PVC. In the preferred method of making hollow articles of crosslinked PVC heat recoverable, the articles are heated and deformed, and then locked in the deformed state by quenching or other suitable form of cooling; other suitable known methods may be used. If required, the former is dipped more than once into the plastisol to form a hollow article of increased wall-thickness and to reduce the risk of perforations or thin areas. The method of the present invention is economical, particularly when a wide range of designs is desired as the method does not require the expensive tooling of injection-moulding. The method of the invention is suited to making hollow articles of simple shape and uniform wallthickness, and in particular articles with a cross-section which varies, uniformly or not, along the length of the article and/or with one closed end. Among specific articles that can usefully be made by the method of the invention are splice caps and breeches pieces for electric conductor joints; hand grips for tools, hand levers etc; protective caps and the like for covering the ends of shafts, oil tubes and the like on machinery in transit; ferrules for the ends of furniture legs, walking-sticks, ladders etc; and protective gaiters for telescopic or articulated mechenical Joints. Advantageously, the composition and viscosity of the plastisol are monitored carefully to ensure that they remain within closely defined limits; the viscosity of the plastisol and the rate of dipping may be varied dependent upon the wallthickness required. Preferably the plastisol coating is heated to effect gelling; the coating may then be cooled and stripped from the formers, for example by rolling off. an analternative to irradiation, thermal crosslinking can be utilised in which' case a: suitable initiator such as an azo compound or a peroxide will normally be included in the plastisol in addition to the crosslinking promoter. Gelling and crosslinking of the plastisol may be done in a single continuous heating operation. Preferably the articles, when crosslinked, are heated to at least 150 C before being deformed under control into a cold mould, by pneumatically inflating with air (suitably in most cases at about 3 x 144cm 2) by hydraulically inflating or by using a mechanical expansion device, e.g. a three-fingered expanding mandrel or for simple tubular shapes a tapered mandrel. Expansion ratios at least approaching 100% may be achieved using appropriately formulated crosslinked compositions. Preferably, as many conventional PVC plastisols incorporate plasticisers that have vapours that are flammable at recovery temperatures, a flameretardant is included to inhibit ignition of the article when it is exposed to an open flame, for instance in the recovery operation. Subject to other requirements, the use of plasticisers with high molecular weights, and consequently low volatilities, reduces this risk. Some of the plasticiser used in the plastisol may be replaced with non-flammable chlorinated hydrocarbon extender compatible with the plastisol. EXAMPLES 1. Three plastisol formulations were made up as follows: The first formulation was prepared by mixing 100 parts of an emulsion glade PVC polymer, type P72/850 in the itcorvic" (trademark) range of PVC polymers manufactured by ICI, with 61 parts di-2-ethyl hexyl phthalate and 48 parts diethyl hexyl sebacate plasticisers. 12 parts lead phthlate powder was added as stabiliser, (this being a greater amount than in the standard formulation), together with 14 parts trimethylol propane trimethacrylate, a crosslinking promoter, the mixing being done with mechanical stirring under vacuum until the dispersion was uniform (about 3 hours). The resultant plastisol was left to stand under vacuum without stirring for 30 minutes. 2. In the second formulation the amount of trimethylol propane trimethacrylate was decreased to 7 parts and the amount of di-2-thyl hexyl phthalate was correspondingly increased to 68 parts, the amounts of the remaining constituents being kept the same as before. The mixing operation was the same as before. 3. in the third formulation, which is at present considered the most satisfactory, the ingredients were as follows: Parts by eight FZ paste lyrre (Corvic P72/850) 100 C7-Cg trimellitate plasticiser (Elonoplas 530) 68 Dioctyl adipate plasticiser 14 Trimethylolpropane trimethacrylate (Sartomer Sr-350) 10 Dibasic lead phthalate stabiliser 12 Antimony trioxide 6 and the mixing procedure as before. Tubular formers with diameters ranging from 13 to 38mm and with rounded bottoms were suspended in an oven at 168 C for ten minutes and then were dipped into and removed from a supply of one of the plastisols, each such dipping operation taking two minutes. The coated formers were then 'suspended in the oven at 1680C for 30 minutes to gel the plastisol coating. The coatings were stripped from the former by unrolling and the resultant end caps were up to 80mm in length and had walls of up to 2mm thick. The caps were then crosslinked by electron irradiation at doses of 2.5, 5.0 and 7.5 Trad. The caps were heated to 1500C and then air pressure of about 3.3 x lO4Nm 2was applied so that they were inflated into a tubular mould which was kept cold to make the caps shrink from the mould enough to ensure they did not adhere to the mould; air pressures of 1.3 x 104 to 2.0 x 104 Nm-ê were found adequate for the larger caps. Expansion of up to 50% could readily be obtained from the first and second formulations: the third formulation could be expanded up to nearly 100%. The expanded caps could be shrunk onto test mandrels by heating the caps to about 2000C, full recovery being effected after about 70 seconds. On expansion, the @terial was robus@ and a cap could be re-expand@@ and used a second time and recovery occurred. The general properties of the product derived from the third formulation after irradiation at 5 Mrad were: Modulus at 100% extension at 230 C 13 MN/m2 2 Tensile strength at break at 23 0C 17 EN/m Elongation at break at 23 0C 150 % 2 Tensile stress at 505 extension at 1500C 0.3,¯0MN/m Elongation at break at 1500C 100% Congo Red heat stability at 1800C 12 hours A hot air gun or a lambent flame was used satisfactorily to heat the cap to bring about recovery. The expanded caps made from the first and second formulations showed no measurable shrinkage after 5 days storage at room temperature (21 2 C): after 28 days the -expanded diameters had decreased by about 3.5 from their original expanded values. The expanded caps made from the third formulation at 5.0 Mrad showed less than 5% shrinkage after 7 days storage at 50 C and remained capable of substantially complete recovery A heat--destruction test was made on one of the caps which started to shrink above 1600C and at 200 C was fully recovered. It remained tough and elastic up to 3000C when it was then showing signs of degradation and after about 5 minutes at this temperature had started to embrittle and was badly discoloured Thus the composition was found to react in a similar manner to crosslinked polyethylene.

Claims: CLAIMS 1. A method of making a heat recoverable hollow article characterised by the steps of dipping a former into a PVC plastisol to form a coating thereon and, after the plastisol constituting the coating has gelled, removing the coating from the former to form a hollow article and deforming the hollow article under suitable temperature conditions to make it heat recoverable. 2. A method as claimed in Claim 1 characterised by crosslinking the PVC in the hollow article before deforming thy hollow article to make it heat recoverable. 3. A method as claimed in Claim 2 characterised in that the PVC plastisol contains a radiationcrosslinking promoter. 4. A method as claimed in Claim 2 or Claim 3 characterised by heating the hollow article to at least 150 C and deforming it by expanding it pneumatically into a cold mould. 5. A method as claimed in any one of the preceding claims, characterised by dipping the former more than once into the plastisol to form each hollow article. 6. A heat recoverable article made by the method of any one of Claims 1 to 5.

Inventors: MARGOLIS, DAVID SAUL
Applicants: BICC PUBLIC LIMITED COMPANY
Application year: 1980
Main classification: B29C25
IPC codes: B29C61, B29C41, B29C35