EP0672090A1 - Composition et article thermoretractables - Google Patents

Composition et article thermoretractables

Info

Publication number
EP0672090A1
EP0672090A1 EP94903398A EP94903398A EP0672090A1 EP 0672090 A1 EP0672090 A1 EP 0672090A1 EP 94903398 A EP94903398 A EP 94903398A EP 94903398 A EP94903398 A EP 94903398A EP 0672090 A1 EP0672090 A1 EP 0672090A1
Authority
EP
European Patent Office
Prior art keywords
polypropylene
adhesive
weight
pipe
substrate
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Withdrawn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
EP94903398A
Other languages
German (de)
English (en)
Inventor
George Pieslak
Walter J. Greuel, Jr.
Tony G. Alvernaz
Jozef Van Beersel
Noel Marcel Michel Overbergh
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 Corp
Original Assignee
Raychem Corp
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
Application filed by Raychem Corp filed Critical Raychem Corp
Publication of EP0672090A1 publication Critical patent/EP0672090A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/06—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof

Definitions

  • This invention relates to dimensionally recoverable articles, particularly heat- recoverable articles, and to an adhesive suitable for use with such articles.
  • Pipelines composed of steel pipe are commonly used to transport a variety of liquids and gases. Depending on the application and the environment, the pipe may be used above the ground or it may be buried. In order to protect the pipe from abrasion,
  • the protective layer may comprise a polymer tape which is coated with a mastic layer and is then applied to the 0 pipe, or it may comprise an epoxy which is sprayed or painted onto the pipe.
  • the protective layer may comprise a fusion bonded epoxy coating in which the epoxy powder is sprayed onto the pipe and is then cured to form a pinhole-free layer which is suitable for use up to about 60°C.
  • the protective coating comprises a number of layers, for example an epoxy layer which is immediately adjacent the pipe and an outer 5 polymer layer such as polyethylene. Such coatings provide the advantages of the epoxy and the polymer and are useful up to a temperature of about 110°C.
  • coated steel pipe which is designed to withstand exposure temperatures of up to 110°C.
  • Such pipe generally has a coating which comprises an inner layer of fusion bonded epoxy, an optional adhesive layer, and an outer layer of polypropylene.
  • These layers provide excellent protection to the steel pipe because they combine the excellent adhesion and cathodic disbonding resistance of the epoxy with the low moisture absorption, low moisture transmission, and abrasion resistance of polypropylene.
  • the difficulty with such pipe is that there are 5 currently no easily installable coatings for the pipe joints or welds that are created when pipe is repaired or retrofitted, e.g. when two pieces of pipe are attached to one another.
  • One technique for supplying a protective coating layer to a pipe joint or weld in the field is by the use of a heat-recoverable polyme ⁇ c article, i.e. a heat-sh ⁇ nkable l o polyme ⁇ c a ⁇ icle such as a sleeve, sheet, or tape, in combination with a heat-activatable sealant.
  • a heat-recoverable polyme ⁇ c article i.e. a heat-sh ⁇ nkable l o polyme ⁇ c a ⁇ icle such as a sleeve, sheet, or tape
  • the polyme ⁇ c mate ⁇ al of the article has been crosslinked du ⁇ ng the producnon process so as to enhance the desired dimensional recovery.
  • One method of producing a heat-recoverable article comp ⁇ ses shaping the polyme ⁇ c mate ⁇ al into the desired heat-stable form, subsequently crosshnking the poiyme ⁇ c mate ⁇ al, heanng the
  • the article 15 aracle to a temperature above the crystalline melnng point of the polymer (or, for amorphous mate ⁇ als, the softening point of the polymer), deforming the article, and cooling the article while in the deformed state so that the deformed state of the article is retained.
  • the deformed state of the article is heat-unstable, applicauon of heat, by means of a torch or other heat source, will cause the aracle to assume its 0 o ⁇ ginal heat-stable shape.
  • the article is designed to sh ⁇ nk down onto the substrate.
  • such heat-recoverable articles generally comp ⁇ se a layer of a heat-ac ⁇ vatable sealant which is posinoned adjacent the substrate 5
  • a heat-ac ⁇ vatable sealant which is posinoned adjacent the substrate 5
  • Suitable sealants include hotmelt adhesives and masncs.
  • Good adhesion of the coaung to the substrate is particularly important to avoid cathodic disbonding Cathodic disbonding occurs as a result of the impressed elect ⁇ c current that is applied 0 to the pipe to prevent corrosion of the iron in the steel pipe.
  • conventional heat-recoverable articles are sleeves which comp ⁇ se a backing layer, generally polyethylene or a copolymer comp ⁇ smg ethylene. in contact with a hotmelt adhesive, which is often a polyethylene- based adhesive
  • the hotmelt adhesive is selected to have adequate adhesion both to the backing layer and to the substrate.
  • Most conventional polyethylene-based heat-recoverable sleeves do not adhere well to a polypropylene-coated pipe, and those sleeves which do have good adhesion cannot be used for pipelines which are exposed to high temperatures, e.g. 5 more than 110°C, because they contain adhesives or mastics which soften and disbond from the pipe at high temperatures.
  • this invention provides an adhesive composition suitable for sealing to a 0 substrate which comprises polypropylene, said composition comprising
  • ethylene polymer which is an ethylene homopolymer, an ethylene copolymer, or a modified ethylene polymer in which a chemical moiety has been grafted onto a polyethylene
  • (i) comprises a chemical moiety which is an unsaturated carboxylic acid or acid derivative and which has been grafted onto a polypropylene backbone, and
  • this invention provides a heat-recoverable article comprising a heat-recoverable polymeric element, said element having coated on at least a part of a surface thereof an adhesive composition according to the first aspect of the invention.
  • this invention provides an assembly which comp ⁇ ses
  • Figure 1 shows a perspective view of a heat-recoverable article of the invention positioned on a substrate
  • Figure 2 shows a cross-sectional view of the article of the invention along line 2-2 of Figure 1 ;
  • Figure 3 shows a cross-sectional view of an article of the invention covering a weld between two pipes.
  • the adhesive composition of the invention is particularly useful in adhe ⁇ ng to polypropylene.
  • Particularly preferred compositions of the invention adhere to steel and/or to polyethylene, in addition to polypropylene.
  • a composition is said to have adhesive character if the peel strength of the composition to the substrate, as measured by ASTM D- 1000, is greater than 0 N/mm at 23°C.
  • Adhesives of the invention preferably have a peel strength to polypropylene of at least 0.9 N/mm (5 pli), particularly at least 1.2 N/mm (7 pli), especially at least 1.8 N/mm (10 pli) at 23°C.
  • the adhesives of the invention exhibit adhesive character at elevated temperature, e.g. 110°C or 120°C.
  • the adhesives preferably have a peel strength of at least 0.02 N/mm (0.1 pli), particularly at least 0.05 N/mm (0.3 pli), especially at least 0.09 N/mm (0.5 pli).
  • ASTM D- 1000 is incorporated herein by reference.
  • adhesives of the invention have similar peel strengths at 23°C and 110°C as those described for polypropylene for substrates comprising steel and substrates comprising polyethylene.
  • the polypropylene to which the adhesive composition adheres may be a film, sheet, or article of polypropylene which has sufficient thickness and integrity to stand alone, or it may be in the form of a coating 5 over a part or all of a substrate such as a pipe.
  • the compositions of the invention are particularly useful in adhering to polypropylene-coated steel pipe.
  • the polypropylene present in the substrate i.e. the material to which the adhesive composition adheres, may be either a crystalline isotactic polypropylene or an l o amorphous polypropylene, depending on the specific application.
  • the polypropylene may be conventional, unmodified polypropylene which comprises at least 75% by weight of the polypropylene homopolymer, i.e. at least 75% of the polymer has a polymer backbone -(CH-CH(CH3))-.
  • the polymer may be modified polypropylene.
  • the term "modified polypropylene" is used to
  • modification can be achieved during the polymerization process or in a post-polymerization step, for example by grafting a chemical moiety such as an unsaturated carboxylic acid or acid derivative onto the polymer backbone, by inserting a
  • modified polypropylene includes those polymer alloys and blends, either reacted or unreacted, which comprise polypropylene and which have different chemical and/or physical properties from conventional unmodified polypropylene. Alloys and blends include those materials in 5 which polypropylene is mixed with rubber such as ethylene propylene diene rubber (EPDM).
  • EPDM ethylene propylene diene rubber
  • the polypropylene of the adhesive is a modified polypropylene as described above.
  • Particularly preferred are polypropylenes in which a chemical moiety such as an 0 unsaturated carboxylic acid or acid derivative has been grafted onto the polymer backbone.
  • suitable chemical moieties are acrylic acid, methacrylic acid, and maleic acid.
  • Polymers in which the chemical moiety is an anhydride, especially maleic anhydride, are particularly preferred. When an anhydride is present, it is prefe ⁇ ed that there be at least 0.1% by weight of the polymer of anhydride grafted onto the 5 polypropylene backbone.
  • modified polymer contain less than 10%, preferably less than 8%, particularly less than 6% by weight of acid (present as an acid moiety), as determined by titration.
  • modified polypropylenes which can be used in this invention include anhydride-modified polypropyienes such as OrevacTM PP-M, OrevacTM PP-CA100. and Orevac' PP-C (also known as Orevac M, Orevac CA100. and Orevac C. respectively), available trom Atochem; AdmerTM QF500E and AdmerTM QB540E, available from Mitsui. FusabondTM 108, FusabondTM 109, and FusabondTM 203, available from DuPont.
  • the modified polypropylene ot the adhesive have a 2% secant modulus, as measured in accordance with ASTM D-882- 15 91, Test Method A, desc ⁇ bed hereinafter, of less than 690 MPa (100,000 psi), preferably less than 620 MPa (90,000 psi), particularly less than 552 MPa (80,000 psi), especially less than 483 MPa (70,000 psi).
  • convennonal, unmodified polypropylene may be present
  • the adhesive composition also comp ⁇ ses 10 to 90% by weight ot an ethvlene polymer, preferably 15 to 85% by weight of an ethylene polymer, particularly 20 to 80% by weight of an ethylene polymer, especially 20 to 75% by weight ot an ethylene polymer, the weight percent being measured in terms of the total composition
  • the ethylene polymer may be an ethylene homopolymer, e.g. very low density 0 polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, or high density polyethylene; an ethylene copolymer, e.g copolymers of ethylene and vinyl acetate, ethyl acrylate. methyl acrylate, or acrylic acid. an ethylene terpolymer; or blends thereof.
  • the ethylene polymer may be any conventional ethylene polymer in which the chemical properties are not changed
  • the 5 exact type and formulation of the convennonal ethylene polymer is selected based on the identity of the mate ⁇ al to which the adhesive is to be adhered and the required exposure temperature of the final product du ⁇ ng normal operation.
  • the ethylene polymer may be a modified ethylene polymer, i.e. any ethylene polymer which has been chemically changed or otherwise altered to enhance its physical or chemical properties.
  • polypropylene such modification can be achieved by grafting a chemical moiety such as an unsaturated carboxylic acid or acid derivative, e.g. acrylic- acid, maleic acid, or maleic anhydride, onto the polymer backbone, by inserting a chemical moiety such as an unsaturated carboxylic acid or acid derivative, e.g. acrylic- acid, maleic acid, or maleic anhydride, onto the polymer backbone, by inserting a chemical moiety such as an unsaturated carboxylic acid or acid derivative, e.
  • modified polyethylenes which can be used in this invention include polyethylenes sold by Quantum under the tradename Plexar, e.g. PlexarTM 013 or PlexarTM 206; those sold by DuPont under the tradename Fusabond, e.g. Fusabond I DUO, FusabondTM D158, and FusabondTM D185; those sold by BP Performance l o Polymers under the tradename Polybond, e.g. PolybondTM 1009 and Polybond TM
  • rubber be 15 present to increase the flexibility of the composition and to enhance the adhesive nature of the composition.
  • rubbers which may be used are natural and synthetic rubbers, particularly ethylene propylene rubbers, ethylene- propylene-diene rubbers (EPDM), butyl rubbers, polyisobutylene rubbers, and thermoplastic elastomers such as those based on styrene-butadiene-styrene or styrene-isoprene-styrene linear or radical 20 block copolymers.
  • the rubber is optional in the adhesive composition.
  • Rubber may comprise 0 to 30% by weight of the total composition, preferably 5 to 30% by weight, particularly 10 to 30% by weight, especially 15 to 25% by weight.
  • a single rubber or two or more different types of rubber may be present in order to achieve different physical and adhesive properties.
  • the rubber 25 component reflects the total weight percent of all the rubbers.
  • tackifier is used in adhesive art to denote a material which, when added to an adhesive composition, promotes its adhesion to a substrate by increasing its ability to 0 wet the substrate. It is often preferred that the tackifier be a low molecular weight polymer of monomers which contain ethylenic unsaturation and are free of polar groups. Suitable tackifiers include NevpeneTM 9500, available from Neville Chemical.
  • the tackifier is optional in the adhesive composition. Therefore, the tackifier comprises 0 to 25% by weight of the total composition, preferably 5 to 20% by weight. particularly 10 to 18% by weight.
  • the adhesive composition can also contain additional additives such as stabilizers, pigments, flame retardants, fillers, waxes, and crosslinking agents It present, these components generally comp ⁇ se at most about 20% by weight ot the total 5 composition, preferably at most about 15% by weight, particularly at most about 10% by weight.
  • the components of the composition can be mixed in any convenient manner, for example by using convennonal mixing equipment such as BrabenderTM or l o BanburyTM mixers, extruders, or mills. Following mixing, the composition can be shaped approp ⁇ ately for the desired use.
  • the composinon can be formed into a sheet, e.g. by extrusion, which can be wrapped or arranged around a substrate, or the composition can be coated onto a backing layer, e.g by extrusion, spraying, painnng, or other type of coanng app canon.
  • the adhesive compositions of the invention can be used for any apphcauon
  • the adhesive is used as part of a heat-recoverable article which is used to provide a cove ⁇ ng on a pipe.
  • a heat-recoverable article is an article, the dimensional configuration of which may be changed by subjecnng the article to heat 0 treatment.
  • such articles comp ⁇ se a heat-sh ⁇ nkable sleeve made from a polyme ⁇ c mate ⁇ al exhibiting the property of elastic or plastic memory
  • heat-recoverable articles can be molded into shapes intended for specific applications.
  • Articles comp ⁇ sing such elasnc or plastic memory are desc ⁇ bed, for example, in U.S. Patents Nos. 2,027,962 (Cur ⁇ e); 3,086.242 (Cook et al); and 5 3,597,372 (Cook), the disclosures of which are incorporated herein by reference
  • Conventional heat-recoverable sleeves used to provide a protective coanng to pipes have either a tubular elongate configuranon or a flat configurauon. Where the diameter of the pipe or other substrate is very large, thus making extrusion of a 0 sufficiently large tubular sleeve difficult, or where no free end of the substrate is available, thus preventing positioning of a tubular sleeve, it is common to use a wrap ⁇ around article.
  • a wrap-around article is an article, typically in the form of a sheet, that is installed by wrapping it around the object to be covered so that opposed longitudinal edges overlap. A closure means is applied to secure together the opposed longitudinal 5 edges. Such articles are desc ⁇ bed in U.S. Patent Nos.
  • the adhesive of the invention is particularly suitable for use in making a bond between a polypropylene-coated steel pipe and a polyethylene-based heat-recoverable sleeve.
  • the adhesive can be applied to the sleeve prior to installation on the pipe or other substrate, it can be applied directly to the pipe or other substrate prior to 5 installation of the sleeve, e.g. as a coating applied in the factory, or it can be used in the form of a sheet which is inserted between the pipe or other substrate and the heat- recoverable sleeve.
  • the heat-recoverable sleeve may have one or more coating layers which are applied before the adhesive of the invention.
  • many conventional heat-recoverable sleeves are coated with a layer of polyamide which l o lies between the backing layer of the sleeve and the adhesive of the composition.
  • the adhesive composition When the adhesive composition is applied to the heat-recoverable sleeve, it generally has a thickness of 0.025 to 1.0 mm (0.001 to 0.040 inch). It is not necessary that the adhesive composition cover an entire surface of the heat-recoverable sleeve; often strips of adhesive at the edges of the sleeve or wraparound article are sufficient to make
  • the preferred failure mechanism is between the adhesive and the backing, i.e. the heat-recoverable article, rather than between the adhesive and the substrate, e.g. the polypropylene-coated pipe. It is particularly important that the adhesive failure be uniform, i.e. that all of the adhesive
  • a “mixed” failure in which there is partial adhesion to both the backing and the pipe, indicates that the strength of the bond to the substrate is less than desirable.
  • Adhesives of the invention have good performance for cathodic disbondment at 5 elevated temperature, e.g. 80 to 95°C or hotter, when tested according to ASTM G-42. described below.
  • the cathodic disbonding radius at 95°C after 30 days is less than 35 mm, preferably less than 30 mm, particularly less than 25 mm, especially less than 20 mm.
  • the adhesive retains its adhesive character at the elevated temperature.
  • the adhesive of the composition is also useful for making a seal over a component, around one or more components, or between two components which are designed to survive exposure to relatively high temperatures.
  • the adhesive composition can be used to seal a fiber optic splice case outlet or to make a 35 seal between the base plate and the dome-shaped cover of a fiber optic splice case such as that disclosed in U.S. Patent No. 4,913,522 (Nolf et al), the disclosure of which is incorporated herein by reference.
  • Fiber optic splice closure systems in which the adhesive of the invennon can be used are sold by Raychem Corporation of Menlo Park. California under the tradename FOSCTM.
  • the adhesive of the invention is also useful as part of an assembly in which a substrate which comprises polypropylene is in contact with the adhesive.
  • the polypropylene of the substrate may comprise all or part of a surface coating of the substrate, e.g. a pipe, or the entire substrate may be made of polypropylene, e.g. a molded part or component.
  • the polypropylene of the substrate be in the form of a layer which surrounds the substrate.
  • the adhesive of the invention may also be used as part of a method for making a connection between a layer or an article which comprises polypropylene, e.g. a polypropylene-coated pipe, and a layer or an article which comprises polyethylene, e.g. a polyethylene-containing backing layer of a heat-recoverable article.
  • the adhesive layer is positioned in contact with the substrate which comprises polypropylene, heat is applied to allow the adhesive to melt and flow while in contact with the substrate, and the adhesive is then allowed to cool, producing a bond between the adhesive (and any backing or carrier to which it is attached) and the substrate.
  • Figure 1 shows a heat- recoverable article 2 in the form of a polymeric tube recovered onto substrate 4 which is a pipe.
  • substrate 4 which is a pipe.
  • Figure 1 the polypropylene layer 6 which coats pipe 4.
  • Adhesive layer 8 which is part of the heat-recoverable article 2 lies between the pipe 4 and the backing layer 10 of heat-recoverable article 2.
  • Figure 2 Shown in Figure 2 is a cross-sectional view along line 2-2 of Figure 1. Visible in this view is the polypropylene coating layer 6 and the adhesive layer 8.
  • Figure 3 shows a cross-sectional view of a weld 12 between two pipes, 4, 14.
  • Adhesive layer 8 bonds to the backing layer 10 of the polymeric heat-recoverable sleeve 2, the polypropylene coating 6,16 of the two pipes, and to the weld 12 itself.
  • Adhesive A listed in Table I, were mixed and applied by extrusion to a 0.75 mm (0.030 inch) thick high density polyethylene backing layer which had been crosslinked and expanded about 28% prior to the application of the adhesive.
  • the adhesion of the adhesive to various substrates was then measured at room temperature (approximately 23°C) and at 120°C following the peel strength test procedure of ASTM D-1000, the disclosure of which is incorporated herein by 5 reference.
  • ASTM D-1000 the disclosure of which is incorporated herein by 5 reference.
  • the adhesive-coated backing was recovered onto a pipe and was cut on the pipe into test specimens with a width of 25 mm ( 1 inch). Each specimen was cut parallel to the direction of the pipe to create a free end which was clamped in the jaw of an InstronTM tester.
  • the jaw l o separation speed of the Instron tester was set at 51 mm/minute (2 inches/minute ). The amount of force required to peel the layer from the pipe was recorded as pounds/linear inch.
  • the adhesive-coated backing was recovered onto a steel pipe with an outer diameter (OP) of 60 mm (2.36 inch) which had been preheated to 170-180°C.
  • OP outer diameter
  • Adhesive A showed no adhesion to the polypropylene-coated pipe, but had good adhesion to the polyethylene 5 backing and to uncoated steel.
  • Adhesive A under cathodic disbonding.
  • the resistance of the adhesive to cathodic disbonding was measured following the procedure of ASTM G-42, the disclosure of which is incorporated herein by reference. 0
  • a slab of the adhesive was attached to a polyethylene backing layer and was then recovered onto a shot-blasted steel pipe with an outer diameter of 51 mm (2 inches). The end of the pipe which was to be immersed was sealed with a watertight end cap. A hole (holiday) was drilled through the backing and the adhesive (but not through the pipe) in the center of the pipe to expose the metal 5 surface of the pipe at that point.
  • the pipe was then immersed in an electrolyte solution comprising water and 1 % by weight of each of sodium chloride, sodium sulfate. and sodium carbonate. A potential of 1.5 volts was applied to the pipe, thus making the pipe a cathode in the electrolyte solution which also contained a sacrificial anode. The sa ple and electrolyte solution were maintained at 95°C for 30 days.
  • the pipe was then removed and the area around the holiday was inspected to determine the extent of disbondment. The approximate radius of the disbondment area surrounding the holiday was measured in millimeters (mm) and recorded. Adhesive A had a cathodic 5 disbonding radius of 10 to 15 mm.
  • Adhesive B was prepared and tested, l o This adhesive showed good adhesion to polyethylene and steel but low adhesion to polypropylene-coated steel. Adhesive B had a cathodic disbonding radius of 22 mm.
  • This adhesive showed good adhesion to polyethylene, steel, and polypropylene-coated steel.
  • Tests of peel strength for this adhesive were conducted on Atochem polypropylene-coated pipe (2.59 N/mm (14.8 pli) at 23°C, 0.16 N/mm (0.9 pli) at 110°C), Himont polypropylene-coated pipe (2.24 N/mm (12.8 pli) at 23°C, 0.12 N/mm
  • Adhesive C a film with a thickness of 0.25 mm (0.010 inch) was prepared and installed on both the steel pipe and the polypropylene-coated steel pipe which had been preheated to a temperature of 230°C.
  • a backing layer coated with Adhesive A (as described in Example 1) was installed.
  • the 0 composite device was then tested as in Example 1. It exhibited good adhesion to polyethylene, steel, and polypropylene-coated steel. TABLE I Adhesive Compositions (Weight %)
  • Modified HDPE is PlexarTM 013, a modified high density polyethylene available from Quantum.
  • Modified PP is OrevacTM C, a polypropylene modified by the addition of more than
  • MPa (61,800 psi), available from Atochem.
  • PIB is VistanexTM L-80, solid polyisobutylene rubber available from Exxon.
  • EPDM is DutralTM 044, ethylene propylene diene rubber available from
  • Tackifier is NevpeneTM 9500, a tackifier available from Neville Chemicals.
  • Pigment is a color concentrate containing carbon black and ethylene/ethyl acrylate copolymer.
  • Stabilizers include antioxidant and a metal deactivator such as that described in U.S.
  • PP-coated Steel was a polypropylene-coated steel pipe available from Atochem (conventional polypropylene) or Duval (modified polypropylene). "NT” indicates that no test was conducted for that condition. "Low” indicates that the adhesion was 0.35 to 0.52 N/mm (2 to 3 pli) at 23°C and that there was adhesive failure to the polypropylene coating, i.e. between the adhesive and the polypropylene coating. "Good” indicates that the adhesion was in the range of 3.68 N/mm (20 pli) or greater at 23°C and that any failure occurred between the adhesive and the backing.
  • Example 2 Following the procedure of Example 1, a number of formulations were prepared using the components listed for Adhesive C, but using different grades of modified polypropylene at 27.8% by weight of the composition.
  • the peel strength at 23°C and 120°C was measured as in Example 1 after the adhesives were recovered onto a polypropylene-coated steel pipe. Also measured was the melt index of each adhesive, following the procedure in ASTM D-1238, Condition E, and the 2% secant modulus at 23°C of each polypropylene, following the procedure of ASTM D-882-91, Test Method A. In that test, a 250 mm (10 inch) strip of the polymer was clamped between the jaws of a mechine with a constant rate of jaw separation.
  • NT* indicates that this property was not tested.
  • Melt index numbers are in grams/ 10 minutes.
  • Example 2 Following the procedure of Example 1, a number of formulations were prepared and tested. Each formulation contained 13.9% by weight VistanexTM L-80. a solid polyisobutylene rubber available from Exxon. 10.0% by weight DutralTM 044. ethylene propylene diene rubber (EPDM) available from Montedison. 15.0% by weight NevpeneTM 9500, a tackifier available from Neville Chemicals, 3.0% by weight of pigment which comprised a color concentrate containing carbon black and ethylene/ethyl acrylate copolymer, and 2.5% by weight stabilizers which included 5 antioxidant and a metal deactivator such as that described in U.S. Patent No.
  • VistanexTM L-80 a solid polyisobutylene rubber available from Exxon. 10.0% by weight DutralTM 044. ethylene propylene diene rubber (EPDM) available from Montedison. 15.0% by weight NevpeneTM 9500, a tackifier available from Neville Chemicals, 3.0% by weight of pigment which
  • Adhesion to polypropylene-coated steel was measured using pipe with an outer diameter of 0.4 m (16 inches) which had been coated with an unmodified 15 polypropylene from Atochem.
  • the polypropylene coating was roughened and the pipe interior was preheated to achieve a temperature of about 110°C on the pipe surface prior to recovering the adhesive-coated backing onto the pipe. To ensure that the adhesive flowed adequately, additional heat was applied to the backing following recovery. The assembly was cooled and the adhesion was measured at 23°C. 0
  • melt index of the adhesive compositions was measured as in Example 5. Softening points were measured using a thermal mechanical analyzer (TMA) with a 50 gram load. Cathodic disbonding at 95°C for 30 days was also measured. The results of these tests are shown in Table V. 5
  • PE1 is PlexarTM 013, a modified high density polyethylene available from
  • PE2 is LotaderTM 8200, a polyethylene terpolymer available from Atochem.
  • l o PE3 is LotaderTM 6600, a polyethylene terpolymer available from Atochem.
  • PPl is OrevacTM C, a polypropylene modified by the addition of more than 1% by weight anhydride and having a 2% secant modulus of about 426 MPa (61,800 psi), available from Atochem.
  • PP2 is QestronTM EP2070G, a polypropylene modified by the addition of more than 15 1 % by weight anhydride and having a 2% secant modulus of about 555 MPa
  • PE/Steel indicates the peel strength in Newtons/mm (N/mm) and pounds/linear inch (pli) when the adhesive-coated polyethylene backing was attached to a bare steel pipe.
  • M indicates that the failure was "mixed", i.e. that there was l o some adhesive failure to the polyethylene backing and some adhesive failure to the steel. In non-mixed failure, the adhesive failure is to the backing.
  • PE/PP indicates the peel strength in N/mm (pli) when the adhesive-coated polyethylene backing was attached to a polypropylene-coated steel pipe.
  • Type indicates the type of failure observed during the peel test.
  • AFPE indicates that 15 there is adhesive failure to the polyethylene.
  • AFPP indicates that there is adhesive failure to the polypropylene.
  • MI melt index in grams/10 minutes as measured according to ASTM D-1238,
  • Soft.Pt. is the softening point in °C of the adhesive composition as measured using a TMA with a 50 g weight. For adhesive 21, two softening points were measured.
  • CD radius is the cathodic disbonding radius in mm measured after 30 days at 95°C.
  • Total indicates that the polymer completely disbonded from the substrate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Composition adhésive apte à se coller sur du polypropylène. Cette composition renferme de 10 à 90 % en poids d'un polymère éthylène, par exemple un homopolymère éthylène tel que le polyéthylène ou un copolymère éthylène, de 10 à 90 % en poids d'un polypropylène modifié, de 0 à 30 % en poids de caoutchouc et de 0 à 25 % en poids d'un agent adhésif. Cette composition se révèle utile pour faire partie intégrante d'un article thermodurcissable (2) utilisé pour réaliser une enduction de protection sur une conduite d'acier à revêtement de polypropylène (4), notamment sur une jonction ou une soudure (12) de tuyau.
EP94903398A 1992-12-03 1993-12-02 Composition et article thermoretractables Withdrawn EP0672090A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US98480692A 1992-12-03 1992-12-03
US984806 1992-12-03
PCT/US1993/011686 WO1994012581A1 (fr) 1992-12-03 1993-12-02 Composition et article thermoretractables

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EP0672090A1 true EP0672090A1 (fr) 1995-09-20

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EP (1) EP0672090A1 (fr)
JP (1) JPH08504226A (fr)
CA (1) CA2150469A1 (fr)
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WO (1) WO1994012581A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022002785A1 (de) 2022-07-28 2024-02-08 Hochschule für Angewandte Wissenschaften Hamburg Körperschaft des Öffentlichen Rechts Werkzeug für die Schraubenmontage mit Magnetsensor-Array zur Torsions-Messung

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL179652B1 (pl) 1994-03-11 2000-10-31 Raychem Corp Utwardzalna polimerowa kompozycja podkladowa PL PL
CA2284055A1 (fr) 1997-04-29 1998-11-05 Dupont Canada Inc. Substrats metalliques enrobes et resistant a l'humidite
US7064163B2 (en) * 2002-09-04 2006-06-20 Msi Technology Llc Polyolefin-based adhesive resins and method of making adhesive resins
WO2005005528A1 (fr) 2003-07-14 2005-01-20 Frans Nooren Afdichtingssystemen B.V. Composition pour proteger un article usine contre la corrosion
EP1630514A1 (fr) * 2004-08-16 2006-03-01 Isocoll Chemie GmbH Procédé pour la fixation d'un tube sur une plaque
SI2081761T1 (sl) 2006-11-08 2010-06-30 Frans Nooren Afdichtingssystem Postopek za opremljanje podaljšanega cevastega izdelka z antikorozijskim zaščitnim prevlečnim sistemom s samo obnovljivimi lastnostmi
EP2119751A1 (fr) * 2008-05-15 2009-11-18 Sunstar Giken Kabushiki Kaisha Composition de revêtement préliminaire adhésif à un paquet
US20100112248A1 (en) * 2008-10-31 2010-05-06 E.I. Du Pont De Nemours And Company Highly abrasion-resistant grafted polyolefin pipe
US8728600B1 (en) 2008-10-31 2014-05-20 E I Du Pont De Nemours And Company Highly abrasion-resistant grafted polyolefin pipe
CN110591464A (zh) 2012-07-13 2019-12-20 弗兰斯诺雷恩阿福迪柯汀斯系统公司 潮湿环境中物品的抗腐蚀的保护方法及其组合物
PL3156208T3 (pl) * 2015-10-16 2019-09-30 Henkel Ag & Co. Kgaa Sposób zgrzewania dwóch różnych poliolefinowych tworzyw sztucznych przy pomocy zastosowania podkładu, przedmiot wytworzony tym sposobem
JP6644957B2 (ja) * 2017-07-11 2020-02-12 サンスター技研株式会社 熱架橋性組成物
JP7505494B2 (ja) * 2019-11-29 2024-06-25 東洋紡エムシー株式会社 ポリオレフィン系接着剤組成物及び積層体
JPWO2021161735A1 (fr) * 2020-02-14 2021-08-19
CN112760068A (zh) * 2021-01-25 2021-05-07 黄山贝诺科技有限公司 一种铝塑管用热熔胶及其制备方法
KR102891907B1 (ko) * 2023-05-24 2025-11-26 롯데케미칼 주식회사 폴리올레핀 수지 조성물 및 이로부터 제조된 성형품

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3987122A (en) * 1972-04-03 1976-10-19 Exxon Research And Engineering Company Thermoplastic adhesive compositions
BE852120A (fr) * 1976-03-05 1977-09-05 Raychem Corp Procede pour assembler des matieres en feuille susceptibles de reprise thermique
JP2672354B2 (ja) * 1988-11-22 1997-11-05 三井東圧化学株式会社 ポリプロピレン樹脂組成物
GB9021090D0 (en) * 1990-09-27 1990-11-07 Bp Chem Int Ltd Adhesive and its uses

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9412581A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022002785A1 (de) 2022-07-28 2024-02-08 Hochschule für Angewandte Wissenschaften Hamburg Körperschaft des Öffentlichen Rechts Werkzeug für die Schraubenmontage mit Magnetsensor-Array zur Torsions-Messung

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WO1994012581A1 (fr) 1994-06-09
JPH08504226A (ja) 1996-05-07
CA2150469A1 (fr) 1994-06-09
RU95113348A (ru) 1997-06-10

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