EP0141835A1 - Abschirmvorrichtung für lange substrate - Google Patents

Abschirmvorrichtung für lange substrate

Info

Publication number
EP0141835A1
EP0141835A1 EP84901787A EP84901787A EP0141835A1 EP 0141835 A1 EP0141835 A1 EP 0141835A1 EP 84901787 A EP84901787 A EP 84901787A EP 84901787 A EP84901787 A EP 84901787A EP 0141835 A1 EP0141835 A1 EP 0141835A1
Authority
EP
European Patent Office
Prior art keywords
mixture
sheet
free
substrate
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP84901787A
Other languages
English (en)
French (fr)
Inventor
John Malcolm Senior
Martyn Priddle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Raychem Ltd
Original Assignee
Raychem Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB838311232A external-priority patent/GB8311232D0/en
Priority claimed from GB838311231A external-priority patent/GB8311231D0/en
Application filed by Raychem Ltd filed Critical Raychem Ltd
Publication of EP0141835A1 publication Critical patent/EP0141835A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/04Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving separate application of adhesive ingredients to the different surfaces to be joined
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C61/00Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
    • B29C61/06Making preforms having internal stresses, e.g. plastic memory
    • B29C61/0608Making preforms having internal stresses, e.g. plastic memory characterised by the configuration or structure of the preforms
    • B29C61/0616Making preforms having internal stresses, e.g. plastic memory characterised by the configuration or structure of the preforms layered or partially layered preforms, e.g. preforms with layers of adhesive or sealing compositions
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00

Definitions

  • This invention relates to a method of protectively enclosing elongate substrates, especially, for example, pipelines, and to a protective sheet for use in such a method, the term "sheet” including elongate sheets of generally "tape-like" form.
  • Metal pipelines can be protected against corrosion by means of coatings applied to sections of the pipe before delivery to the construction site, but such coatings are often imperfect or may be damaged during transport and installation of the pipe sections.
  • Protective wrappings of polymeric sheeting can be adhered to the pipeline in situ, using mastics, hot melt adhesives, or heat curable epoxies, after assembly of the pipeline sections, thus avoiding some of the problems of the factory-applied coatings.
  • these methods fail to provide a bond between the sheeting and the pipeline which will withstand conditions encountered in service on the pipeline, such as temperature cycling, elevated tem- peratures, and especially soil stress caused by expan ⁇ sion and contraction of buried pipelines.
  • the present invention introduces an improved method and sheet which have significant advantages for protectively enclosing elongate substrates such as pipelines.
  • the invention provides a method of protectively enclosing an elongate substrate wherein a sheet of polymeric material is adhered around the substrate by arranging between the sheet material and t'he substrate a multi-component adhesive comprising a first component (a) comprising a substantially solid curable mixture of a free-radical-curable monomer, a polymer and a free- radical generator, and a second component (b) compris ⁇ ing a catalyst for the free-radical curing of at least the monomer in mixture (a), and bringing the mixture (a) and the catalyst (b) into contact so as to bring about curing of the mixture (a).
  • a multi-component adhesive comprising a first component (a) comprising a substantially solid curable mixture of a free-radical-curable monomer, a polymer and a free- radical generator, and a second component (b) compris ⁇ ing a catalyst for the free-radical curing of at least the monomer in mixture (a), and bringing the mixture (a
  • the invention provides a dimensionally recoverable sheet of polymeric material carrying on one of its main surfaces (a) a substan ⁇ tially solid curable mixture of a free-radical curable monomer, a polymer and a free-radical generator, for use with (b) a catalyst for the free-radical curing of at least the monomer in mixture (a) in a method of enclosing an elongate substrate in the sheet; or carrying the catalyst (b) for use with mixture (a) in such a method.
  • the method comprises (1) applying either the component (a) or the component (b) to the substrate, (2) enclosing the substrate in the polymeric sheet material carrying the other of the components(s) (a) and (b) such that the other of the components (a) and (b) is between the sheet material and the substrate, and (3) bringing the components (a) and (b) into contact with each other between the sheet material and the substrate so as to bring about curing of the mixture (a), thereby adhering the sheet material to the substrate.
  • substantially solid means that the mixture has sufficiently high viscosity to permit it to be pre-coated on the sheet or substrate without running off to any signifi ⁇ cant extent in contrast to the behaviour of a liquid
  • OMPI (at ambient temperatures) monomer alone Pre-coating on the sheet is preferred, in which case the mixture will preferably be “storage-stable” in the sense that it does not undergo any significant degree of curing at ambient or normal storage temperatures, thus enabling a precoated sheet product to be provided for convenient use in remote locations such as construction sites.
  • curable is understood to have its usual significance in that a “curable” mixture is capable of undergoing a chemical transformation (such as cross- linking or polymerising) resulting in a product which no longer flows appreciably under the combined effects of pressure and temperature greater than ambient.
  • the method and sheet according to this invention can be used for protecting any elongate substrate, for example splices in power or telecommunication cables, and is advantageously used on pipelines.
  • the method is especially useful on metal pipelines, e.g. oil pipe ⁇ lines, since a cured adhesive bond can be achieved without deliberate mixing of the curing components between the substrate and the polymer sheet.
  • Such a bond tends to have superior resistance to soil stress and other environmental effects and can be achieved despite the considerable heat sink effect of the pipeline, which inhibits curing of other curable adhesive formulations, especially when the pipeline is in operation conveying fluids, often at temperatures of not more than 80 ⁇ C, for example 40 ⁇ C.
  • the method may include the further step of burying the enclosed pipeline in the ground.
  • the curable monomer/polymer mixture preferably comprises a flowable liquid or semi-l iquid acryl ic monomer, which may mean so-called oligomers for example polyethylene glycol dimethacrylate or diacrylate, tripropylene glycol diacrylate, 1 ,6-hexane diol dimeth ⁇ acrylate or diacrylate, polytetramethylene ether glycol diacrylate, polybutadiene diacrylate, polyester-meth- acryl ate d imethacrylate, vinyl terminated acryl- onitrile-butadiene, acrylated epoxidised soyabean oil, trimethylol propane trimethacrylate; and a non-reactive polymer, preferably an acrylic polymer, in sufficient amount and having sufficient viscosity to render the mixture with the flowable monomer substant ially solid under ambient storage conditions .
  • oligomers for example polyethylene glycol dimethacrylate or diacrylate, tripropylene glycol diacrylate
  • the free- radical generator is preferably one whose rate of free-radical generation in the mixture is catalysed by an amine preferably an aryl alkyl alkyl amine, for example an organic peroxide such as benzoyl peroxide, and the catalyst is preferably an amine .
  • an amine preferably an aryl alkyl alkyl amine
  • an organic peroxide such as benzoyl peroxide
  • the catalyst is preferably an amine .
  • other catalysts could be used, for example transition metal salts such as cobalt naphthenate.
  • the acrylic polymer referred to above is thermo- plastic and may also be elastomeric.
  • polybutyl methacrylate e.g. Elvacite 2044 , Du Pont , or
  • Plexigum P24 Plexigum P24 , Rohm
  • Plexigum P24 thermoplastics with a
  • Non-acrylic polymers may be used , e. g. a vinyl acetate - ethylene copolymer, (e.g. VAE711 , Wacker, 70% vinyl acetate) . This is an elastomer.
  • a vinyl acetate - ethylene copolymer e.g. VAE711 , Wacker, 70% vinyl acetate
  • thermoplastic materials may be useful, e.g. ethylene-vinyl acetate copolymers (EVA) including less than 50% VA, ethylene-ethylacrylate copolymers (EEA), polyethylene-butyl acrylate.
  • EVA ethylene-vinyl acetate copolymers
  • EAA ethylene-ethylacrylate copolymers
  • polyethylene-butyl acrylate polyethylene-butyl acrylate
  • a plasticiser may also be used if required, e.g. N-ethyl-o-,p-toluenesulphonamide (Santicizer 8, Mon ⁇ santo) or 2-ethyl hexyl diphenyl phosphate (Santicizer 141 , Monsanto) .
  • the polymer/monomer mixture may be coated on the substrate at the time when the sheeting is to be applied thereto, in which case the catalyst could be applied to the mixture on the substrate immediately before application of the polymer sheet thereto, but it may be preferable for the sheet to be pre-coated with the catalyst to promote adhesion to the sheet.
  • the catalyst could be applied to the sheet before application to the substrate, but the catalyst is preferably applied to the substrate, in which case it may be applied in a composition incorporating corrosion inhibitors or other agents to enhance the life of the substrate.
  • the monomer/polymer mixture may be applied to the catalyst- coated substrate immediately before the sheet is applied but is preferably pre-coated on the sheet, in which case suitable surface treatments or primers may be applied to the sheet to promote adhesion thereto.
  • the polymer/monomer mixture itself may incorporate materials for promoting adhesion, especially when polyolefin-based sheet is used.
  • the curing of the free-radical curable monomer proceeds upon surface-to-surface contact of the mon ⁇ omer/polymer mixture with the catalyst but may if desired be enhanced by application of heat, preferably sufficient to cause the curable mixture to soften or melt and enhance its surface wetting ability.
  • the polymeric sheet is preferably dimensionally recov- erable, especially heat-recoverable, about the sub ⁇ strate to compress the curing components.
  • a heat recoverable article is an article the dimensional configuration of which may be made substan ⁇ tially to change when subjected to heat treatment.
  • such articles comprise a heat-shrinkable sleeve made from a polymeric material exhibiting the property of elastic or plastic memory as described, for example, in U.S. Patents 2,027,962; 3,086,242 and 3,597,372.
  • the original dimen- sionally heat-stable form may be a transient form in a continuous process in which, for example, an extruded tube is expanded, whilst hot, to a dimensionally heat-unstable form but, in other applications, a preformed dimensionally heat stable article is deformed to a dimensionally heat unstable form in a separate stage.
  • the polymeric material may be cross-linked at any stage in the production of the article that will enhance the desired dimensional recoverability.
  • One manner of producing a heat-recoverable article comprises moulding the polymeric material into the desired heat-stable form, subsequently cross-linking the polymeric mat ⁇ erial, heating the article to a temperature above the crystalline melting point or, for amorphous materials, the softening point, as the case may be, of the poly ⁇ mer, deforming the article and cooling the article whilst in the deformed state so that the deformed state of the article is retained.
  • application of heat will cause the article to assume its original heat-stable shape.
  • an elastomeric member such as an outer tubular member is held in a stretched state by a second member, such as an inner tubular member, which, upon heating, weakens and thus allows the elastomeric member to recover.
  • Th e expre ss ion " d imens ional ly recoverabl e" includes articles which are recoverable upo n sub j ect ion to st imul i other than heat , for example solvents , or impact weakening of a second "hold out" member, which may be useful as alternatives to heat-recoverable articles, for example in circum ⁇ stances where heating, especially flame heating, may be undesirable.
  • a polymeric composition may be cross-linked either by the incorporation of a chemical crosslinking agent or by exposure to high energy radiation.
  • a chemical crosslinking agent or by exposure to high energy radiation.
  • suitable cross-linking procedures are well known nowadays from numerous patents in the name of Raychem Corporation, and need not be further described here.
  • the degree of cross-linking of the compositions may be expressed in terms of the gel content (ANSI/ASTM D2765-68 ) of the cross-linked polymeric composition, i. e . exclud ing non-polymeri c additives that may be present.
  • the gel content of the cross- linked composition is at least 10% , more preferably at least 20% , e.g. at least 30% , more preferably at least 40% .
  • the sheet may be in the form of a tube, it is preferably in the form of a "wrap-around" sheet to be wrapped around the substrate and suitably fastened.
  • the sheet material preferably is recover ⁇ able to an extent of at least 10% , more preferably 20 - 40% , and preferably not more than 50% of its unre- covered dimensions. A recovery of about 30% provides adequate compression to promote good sealing contact
  • a preferred form of sheet carries the monomer/ polymer mixture on one of its main surfaces and the catalyst on its other main surface, at least in those areas which are to be overlapped by the mixture-coated surface in use, so promoting curing of the mixture in the overlap areas to minimise leakage and promote sealing and bonding.
  • the catalyst can be applied to the required areas either during manufacture of the sheet or subsequently, for example, immediately before or during installation on the substrate.
  • polymeric sheet material carrying the appropriate curing components can readily be devised by persons familiar with polymer extrusion and coating technology. It has, however, been found advantageous that the preferred acrylic polymer/monomer mixture can be prepared by standard mixing techniques using liquid monomer without added solvent to give an appropriate viscosity for coating and the mixture, without heating or other treatment, then gels and becomes substantially solid after coating onto a suitable polymer sheet. These gelled polymer- in-monomer curable mixtures produce unexpectedly superior curing performance when used to adhere dimensionally recoverable article to a substrate about which the article is recovered in use.
  • doctor blade for example, may be used, preferably to give a finished solid coating of thickness within the range from 0.5 mm to 1.5mm.
  • the catalyst can also be applied to the other surface of the sheet by standard techniques, for example spray or roller coating.
  • Modified mixing and coating methods may be re ⁇ quired for polymers such as the aforementioned VAE711, which require relatively high shear forces to dissolve them directly in the monomer, since such high shear rates may induce premature curing.
  • mixing with the aid of auxiliary solvents, and coating by applying pre-cast films of the mixture to the sheet may be adapted to suit the requirements of the mat ⁇ erials in question according to criteria which will be readily determinable by persons skilled in the relevant technology.
  • Suitable polymer sheet materials are known, for example polyolefins such as polyethylene, ethylene- vinyl acetate copolymers (EVA), polyvinyl chloride, polyethylene blended with EVA, or with ethylene-acrylic acid copolymers (EAA), ethylene-ethyl acrylate copoly ⁇ mers (EEA), or ethylene-propylene copolymers.
  • EVA ethylene- vinyl acetate copolymers
  • EAA ethylene-acrylic acid copolymers
  • EAA ethylene-ethyl acrylate copoly ⁇ mers
  • EOA ethylene-propylene copolymers
  • the curing components can be selected from known monomers, polymers, free-radical generators and cata ⁇ lysts and formulated to give a curing system having adequate shelf life, curing speed, and cured adhesion characteristics.
  • Any polymer may be used which is compatible with the curable monomer in the sense that a pre-coatable (that is, substantially non-flowable at ambient or storage temperatures) mixture can be pre- pared in which the polymer does not unacceptably affect the curing.
  • Any unsaturated monomer, free-radical generator and catalyst may be used which produce the desired curing reaction on contact between the solid coating containing the monomer (and free-radical generator) and the catalyst.
  • Acrylic monomers are preferred, by which is meant acrylic and methacrylic acids and mono-, di-, and multi- (meth) acrylates, e.g. 2-ethylhexylacrylate, tetraethylene glycol dimeth ⁇ acrylate, trimethylol propane trimethacrylate.
  • the free-radical generator/catalyst system may be selected according to known criteria to suit the other materials and conditions of use.
  • Peroxide free-radical generators e.g. benzoyl peroxide
  • amine catalysts such as amines, for example N,N-di- methyl-p-toluidine or its saccharin salt, N-phenyldi- ethanolamine
  • catalysts such as organic compounds of metals of vari able oxidation state, e.g. iron, cobalt , or manganese salts (such as cobalt naphthenate ) or copper acetylacetonate or vanadium salts may be used.
  • the catalyst may be mixed with suitable carriers, binders, corrosion inhibitors, fillers , etc. according to need.
  • suitable binders include polyvinyl butyral, VAE, EVA, EAA, EEA, and polybutylmethacrylate.
  • the relative proportions of the materials in the curable mixture may be varied widely according to the desired balance of properties before and after curing. For example, in parts by weight % of mixture.
  • the mixture will be formulated to remain somewhat flexible after curing.
  • additives which may be used in known manner and proportions include fillers such as carbon black, (5% preferred), plasticisers such as 2-ethylhexyldi- pheylphosphate (15% preferred), and corrosion inhib ⁇ itors such as disodium hydrogen orthophosphate (2% preferred) .
  • the cat- alyst may be included in the curable monomer/polymer mixture and the free radical generator provided separ ⁇ ately, but the aforementioned forms with the free- radical generator in the mixture are preferred for optimum curing in practice.
  • Santomer 210 polyethylene glycol dimethacrylate , M .W.
  • Example 1 Parts by wt 3.
  • Plexigum P24 45 900 VAE 711 5 100 Santomer 210 30 600 Santicizer 141 15 300 tertiary butyl peroxy benzoate 2.5 50 ⁇ T f O
  • the premixed Plexigum P24 and VAE 711 (coarse powders) were added with hand stirring to the premixed Santomer 210, Santicizer 141 and tertiary butyl peroxy benzoate liquids, and stirred to break down any aglom- erates.
  • the paste was poured into a 100mm X 150mm X 1.5mm mould on heat-shrinkable polyolefin/EVA sheet (30% free recovery) and a doctor blade passed across the mould to give a 1.5mm thick coating on the sheet.
  • a sheet of siliconised paper was laid over the ad- hesive. After 1 hour the adhesive had 'gelled* and the siliconised paper could be peeled off.
  • the adhesive was bonded to steel as follows using a primer solution of cobalt (II) acetylacetonate (2 pts) and N,N-dimethyl -p-toluidine (25 pts) in trichloroethane (50 pts) plus methyl ethyl ketone (50 pts).
  • a 2" diameter mild steel tube of 1/4" wall thick ⁇ ness was grit blasted then degreased with methyl ethyl ketone. The steel was then primed with the solution and the excess primer was wiped off and the solvents allowed to evaporate.
  • the adhesive-coated sheet was wrapped around the steel tube and held as a complete tube by means of an adhesive patch.
  • the sheet was then recovered by heating with a gas torch, and the bond left 24 hrs at 40 ⁇ C. After the 24 hrs the sheet was cut open.
  • the adhesive was found to have cured and formed a strong bond between the steel and the backing sheet.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
EP84901787A 1983-04-25 1984-04-24 Abschirmvorrichtung für lange substrate Withdrawn EP0141835A1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB838311232A GB8311232D0 (en) 1983-04-25 1983-04-25 Protective sheet
GB8311232 1983-04-25
GB838311231A GB8311231D0 (en) 1983-04-25 1983-04-25 Protective enclosing of elongate substrates
GB8311231 1983-04-25

Publications (1)

Publication Number Publication Date
EP0141835A1 true EP0141835A1 (de) 1985-05-22

Family

ID=26285942

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84901787A Withdrawn EP0141835A1 (de) 1983-04-25 1984-04-24 Abschirmvorrichtung für lange substrate

Country Status (3)

Country Link
EP (1) EP0141835A1 (de)
IT (1) IT1176122B (de)
WO (1) WO1984004320A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0313071B1 (de) * 1987-10-22 1993-04-21 Nichiban Co. Ltd. Reaktiver Haftklebstoff; Haftklebstoffband, Film oder Formmasse, daraus hergestellt
US5470622A (en) * 1990-11-06 1995-11-28 Raychem Corporation Enclosing a substrate with a heat-recoverable article

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4182644A (en) * 1975-03-27 1980-01-08 E. I. Du Pont De Nemours And Company Polymer in monomer adhesive composition and method employing same
EP0074218B1 (de) * 1981-08-26 1985-11-13 Raychem Limited Wärmerückstellfähiges Produkt

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8404320A1 *

Also Published As

Publication number Publication date
IT1176122B (it) 1987-08-12
IT8420672A1 (it) 1985-10-20
IT8420672A0 (it) 1984-04-20
WO1984004320A1 (en) 1984-11-08

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Inventor name: PRIDDLE, MARTYN

Inventor name: SENIOR, JOHN, MALCOLM