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WO1996000259A2 - Membrane de revetement thermodurcie thermosoudable et ses procedes de fabrication et d'utilisation - Google Patents

Membrane de revetement thermodurcie thermosoudable et ses procedes de fabrication et d'utilisation Download PDF

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Publication number
WO1996000259A2
WO1996000259A2 PCT/US1995/007472 US9507472W WO9600259A2 WO 1996000259 A2 WO1996000259 A2 WO 1996000259A2 US 9507472 W US9507472 W US 9507472W WO 9600259 A2 WO9600259 A2 WO 9600259A2
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WO
WIPO (PCT)
Prior art keywords
thermoplastic
polymeric material
vulcanizable elastomeric
elastomeric
thermoplastic polymeric
Prior art date
Application number
PCT/US1995/007472
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English (en)
Other versions
WO1996000259A3 (fr
Inventor
Richard Wayne Tomlinson
Robert Charles Tyler
Original Assignee
Uniroyal Chemical Company Inc.
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 Uniroyal Chemical Company Inc. filed Critical Uniroyal Chemical Company Inc.
Priority to AU29022/95A priority Critical patent/AU2902295A/en
Publication of WO1996000259A2 publication Critical patent/WO1996000259A2/fr
Publication of WO1996000259A3 publication Critical patent/WO1996000259A3/fr

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
    • E04D5/06—Roof covering by making use of flexible material, e.g. supplied in roll form by making use of plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/011—Crosslinking or vulcanising agents, e.g. accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • 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
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

Definitions

  • Our present invention is directed to a weatherable, heat-seamable novel thermoset sheeting membrane as well as to waterproof liners and coverings made from our novel sheeting membrane. Another aspect of our invention is directed to our preferred method for providing a roof with a waterproof covering, utilizing our novel thermoset sheeting membrane.
  • Our novel thermoset sheeting membrane can preferably be prepared advantageously from EPDM terpolymer elastomer and an olefinic polymer additive.
  • EPDM is the abbreviation for a terpolymer elastomer made from ethylene-propylene diene monomer.
  • a particularly preferred polymer additive such as high density polyethylene, enables the heat-seaming of overlapping edge margins of cured adjacent thermoset membrane sheets, resulting in superior adhesion therebetween.
  • membrane roofing offers several distinct advantages over traditional built-up asphalt roofing. Advantages include increased safety for the applicator of the roofing components, easier installation, increased resistance of roofing materials to "cold cracking,” and protection against leaks over an extended period of time.
  • thermoset sheeting membrane as a waterproof membrane
  • Municipal water-storage tanks and other vessels
  • reservoirs irrigation channels, canals, recreational ponds including golf course water hazards, and industrial waste-water treatment facilities including settling ponds.
  • sheeting membrane for uses of this sort possess enough structural integrity as to ensure against undesired water seepage.
  • Various elastomeric membranes, especially vulcanized EPDM, have been widely used for these sorts of applications.
  • Vulcanized EPDM membrane is known to possess such desirable physical properties as high strength, excellent elongation, satisfactory cold-flexibility properties, and general resistance to outdoor weathering.
  • Sheets are typically seamed with commercially available adhesives.
  • thermoset ethylene-propylene rubber sheets having integral thermoplastic adhesive strips.
  • the thermoplastic adhesive strips which are molded along the lateral edge margins of the cured thermoset rubber sheets, are manufactured utilizing a procedure whereby the thermoplastic strips are applied to the edge margins of the uncured thermoset ethylene-propylene rubber sheets prior to vulcanization of the rubber sheeting. The strips are used to bond ethylene-propylene sheets together in an overlapping splice.
  • U.S. Patent No. 4,778,852 to Futamura is a roofing composition "blend,” said to include two principal ingredients, namely a so-called “blocked” thermoplastic elastomer and a vulcanized elastomer.
  • thermoplastic elastomer is said to be made up of both crystalline and amorphous "blocks" or regions.
  • Heat-seamable sheeting which enables the formation of water-tight seams possessing superior strength is highly desirable. Any seam thus formed, moreover, must be of sufficient strength as to resist both short- term and long-term stresses as well as oxidation, hydrolysis, and other chemical attack. Long-term stresses can be caused by roof movement, strong winds, freeze-thaw cycles, etc., as well as oxidation.
  • one aspect of our present invention is directed to a method of making a thermoplastic-containing, cured elastomeric matrix, as well as to the thermoplastic-containing, cured matrix which results.
  • Yet another aspect or feature of our present invention is directed to a method of heat-seaming together adjacent sheets of the thermoplastic- containing, cured elastomeric matrix, and to the thermoplastic-containing, cured and heat-seamed elastomeric matrix thus produced.
  • our present invention is directed to a method for producing a heat-seamable, cured elastomeric matrix.
  • Our preferred method for producing a heat-seamable, cured elastomeric matrix comprises (1 ) combining a vulcanizable elastomeric material and a thermoplastic polymeric material having a predetermined softening/melting temperature, in a manner so as to produce a heterogeneous dispersion of the thermoplastic polymeric material throughout the vulcanizable elastomeric material, while (2) heating the heterogeneous dispersion at a temperature above the softening/melting temperature of the thermoplastic polymeric material, in a manner and for a period of time sufficient to enable the thermoplastic polymeric material to soften or melt and become dispersed throughout the elastomeric material, thereby producing a vulcanizable elastomeric matrix.
  • Another aspect of our invention is directed to the thermoplastic- containing, vulcanizable elastomeric matrix that is produced as a result of employing this method.
  • the vulcanizable, thermoplastic-containing matrix is subjected to heat and pressure sufficient to cure the elastomeric matrix.
  • Our preferred method of joining together edge margins of separate sheets of the cured, thermoplastic-containing elastomeric matrix material described above comprises overlappingly contacting edge margins of adjacent sheets of the thermoplastic-containing, cured elastomeric matrix material and next subjecting the overlappingly contacting edge margins of the elastomeric matrix sheets to heat and pressure sufficient to bond the contacting edge margins of the adjacent sheets together, for purposes of providing a water-tight joint therebetween.
  • One use of our invention is as a heat-sealable thermoset sheeting membrane, while another use is as a waterproof covering made from such a sheeting membrane.
  • sheetsing membrane as a waterproof membrane are contemplated as being utilized in connection with municipal water-storage vessels and reservoirs, canals and irrigation channels, recreational ponds including golf course water hazards, and industrial waste-water treatment facilities including settling ponds and lagoons.
  • Such a membrane may be made from a thermoset elastomer, especially EPDM, advantageously formulated with from about 3 to 75 phr, preferably 5 to 50 phr, of thermoplastic polymeric material, the presence of the thermoplastic polymeric material thereby enabling the membrane to be heat-sealable.
  • a thermoset elastomer especially EPDM
  • thermoplastic polymeric material the presence of the thermoplastic polymeric material thereby enabling the membrane to be heat-sealable.
  • Such a membrane utilizes certain advantages of a thermoset elastomer, such as vulcanized EPDM, while at the same time enabling the obtaining of water-tight heat-sealed bonds between the membrane plies without the use of separately applied adhesive.
  • a thermoset elastomer such as vulcanized EPDM
  • the presence of the EPDM would provide such a membrane with desirable cold flexibility properties, superior strength, as well as significant resistance to outdoor weathering when exposed to natural elements.
  • thermoset membrane of our present invention is unique for thermoset membranes, in that the membrane has the potential of including an integral seam of superior bond strength.
  • the protective membrane of our present invention will prove itself useful as "roof flashing," in that our membrane can readily be made to follow irregular contours of structures, such as chimney tops, typically randomly located atop roofs.
  • the composition of this invention when used as a roof covering, may cover any roofing base material, such as wood, composition board, concrete, brick or metal.
  • insulating or vapor barrier layers may be first placed over the roof prior to the positioning of the composition of this invention upon the roof. (It is to be understood, however, that any such presence of insulation layers is not essential to this invention.) Detailed Description Of Invention
  • ambient temperature is understood to mean the temperature of the environment in which an experiment is conducted or in which any physical or chemical event occurs.
  • cure is understood to mean the crosslinking of a crosslinkable polymer by any means.
  • styrene- butadiene copolymer includes polychloroprene (also known as "neoprene”); nitrile rubber; butyl rubber; polysulfide rubber; c/ ' s- 1 ,4-polyisoprene; ethylene- propylene copolymers as well as terpolymers (such as EPDM rubber); silicone rubber; and polyurethane rubber.
  • styrene- butadiene copolymer polychloroprene (also known as "neoprene”); nitrile rubber; butyl rubber; polysulfide rubber; c/ ' s- 1 ,4-polyisoprene; ethylene- propylene copolymers as well as terpolymers (such as EPDM rubber); silicone rubber; and polyurethane rubber.
  • terpolymers such as EPDM rubber
  • silicone rubber such as EPDM rubber
  • polyurethane rubber can be crosslinked with
  • melt polymer was subsequently extended — beyond the definition provided immediately above — by those practicing the art, to include uncrosslinked polyolefins that are thermoplastic; and these are generally known as "TPO rubbers.” Their extension and retraction properties are notably different from those of thermosetting polymers, but they are well adapted to such specific uses as wire and cable coating, automobile bumpers, vibration dampers, as well as a wide assortment of specialized mechanical products.
  • matrix as used herein shall mean a composition-of- matter which includes at least one component or ingredient of interest.
  • melting temperature as used herein is understood to mean that temperature range at which a crystalline polymeric material undergoes a phase change.
  • membrane as used herein shall mean a special sort of "matrix,” in that a “membrane” is a polymeric sheet or film of generally planar shape and substantially uniform thickness, wherein the membrane includes at least one component or ingredient of interest.
  • pressure as used in this specification to refer to pressure or shear stresses, is understood to mean “pounds per square inch.”
  • room temperature means 25 °C (77 °F).
  • softening temperature is understood to mean that temperature range at which a polymeric material ceases to possess such physical properties as hardness, stiffness and brittleness.
  • thermoplastic polymer is one that is able to be repeatedly (1 ) softened by heating and (2) hardened by cooling, through a characteristic temperature range.
  • a thermoplastic polymer when in the softened state, can be made into various articles by such "forming” or “shaping” steps as —for example— calendering, molding, stretching or extruding.
  • thermosetting polymer is one that is capable of being changed into a substantially intractable or infusible (i.e. insoluble) product, upon being cured by heat or other means.
  • vulcanization is understood to mean a physicochemical change which results from the cross-linking of the unsaturated hydrocarbon chain of natural rubber, polyisoprene, EPDM, etc. with sulfur, usually with application of heat.
  • the overall effect of vulcanization is to convert a rubber-like hydrocarbon from a soft, tacky, thermoplastic to a strong, temperature-stable thermoset having unique elastic modulus and yield properties.
  • thermoplastic-containing, heat-seamable, cured elastomeric matrix is directed to a process or method for producing a thermoplastic-containing, heat-seamable, cured elastomeric matrix.
  • Our preferred method for producing a heat-seamable, cured elastomeric matrix comprises
  • thermoplastic polymeric material having a predetermined softening/melting temperature
  • thermoplastic polymeric materials disclosed in this specification generally consist of crystalline polymeric material as well as amorphous polymeric material, wherein the crystalline polymeric material has a characteristic melting temperature range and the amorphous polymeric material has a characteristic softening temperature range.
  • thermoplastic-containing, vulcanizable elastomeric matrix which is produced as a result of employing our method, briefly noted above.
  • the vulcanizable, thermoplastic-containing matrix which results is subjected to heat and pressure sufficient to cure the elastomeric matrix.
  • Our preferred method of joining together edge margins of separate sheets of the cured, thermoplastic-containing elastomeric matrix material described above comprises overlappingly contacting edge margins of adjacent sheets of the thermoplastic-containing, cured elastomeric matrix material and next subjecting the overlappingly contacting edge margins of the elastomeric matrix sheets to heat and pressure sufficient to bond the contacting edge margins of the adjacent sheets together, for purposes of providing a water-tight joint therebetween.
  • yet another aspect of our present invention is directed to a compoundable (i.e. mixable) polymeric composition-of- matter comprising vulcanizable elastomeric material and thermoplastic polymeric material, and optionally including such traditional rubber additives such as "carbon black” fillers, various mineral fillers, plasticizers (such as mineral oils), curatives (such as sulfur), as well as certain "processing" ingredients which are used to aid in mixing, molding, extruding, calendering, or stabilizing an intermediary or ultimate elastomeric matrix product.
  • traditional rubber additives such as "carbon black” fillers, various mineral fillers, plasticizers (such as mineral oils), curatives (such as sulfur), as well as certain "processing" ingredients which are used to aid in mixing, molding, extruding, calendering, or stabilizing an intermediary or ultimate elastomeric matrix product.
  • thermoplastic polymeric material is added to the rubber-containing compoundable mixture of ingredients before cure, the ingredients being mixed to make the desired compound, whereupon the compound can be shaped into sheet-like membranes, and — if so shaped — subsequently cured, to enable secure heat-seaming of the membrane to itself after application of the membrane to a roof or other surface.
  • Crystalline/amorphous thermoplastic polymeric material of suitable melting/softening temperature range is preferred.
  • the melting/softening temperature value is too high — greater than about 232 °C (ca. 450 °F) for example — those skilled in the art will generally agree that it is difficult to satisfactorily heat-seam at field conditions; and if the melting/softening temperature value is too low — e.g. 93 °C (ca. 200 °F) — the roof surface ambient temperatures during summer months could cause seam failure.
  • the melting/softening temperature value is too high — greater than about 232 °C (ca. 450 °F) for example — those skilled in the art will generally agree that it is difficult to satisfactorily heat-seam at field conditions; and if the melting/softening temperature value is too low — e.g. 93 °C (ca. 200 °F) — the roof surface ambient temperatures during summer months could cause seam failure.
  • the melting/softening temperature value is too low — e.g. 93 °C (ca. 200 °F) — the
  • thermoplastic polymer material preferably has a melting/softening temperature range of about 35 °C to about 140 °C and is about 35 % to 1 00 % crystalline, based on weight. The remainder of the thermoplastic polymer material is amorphous.
  • suitable vulcanizable elastomeric material for purposes of our present invention — includes but is not limited to chlorinated polyethylene; ethylene/acrylic; isoprene-acrylonitrile; polybutadiene; polyisobutylene; styrene-butadiene copolymer; polychloroprene (also known as "neoprene”); nitrile rubber; butyl rubber; polysulfide rubber; c/s- 1 ,4-polyisoprene; ethylene-propylene terpolymers (such as EPDM rubber); silicone rubber; and polyurethane rubber; as well as combinations (or “blends") of these.
  • chlorinated polyethylene ethylene/acrylic; isoprene-acrylonitrile; polybutadiene; polyisobutylene; styrene-butadiene copolymer; polychloroprene (also known as "neoprene”); nitrile rubber
  • the diene monomer which is utilized in forming the EPDM terpolymer be a non-conjugated diene.
  • suitable non-conjugated dienes include but are not limited to dicyclopentadiene; alkyldicyclopentadiene; 1 ,4-pentadiene; 1 ,4-hexadiene; 1 ,5-hexadiene; 1 ,4-heptadiene; 2-methyl-1 ,5-hexadiene; 1 ,4-octadiene; 1 ,7-octadiene; 5-ethylidene-2-norbornene; 5-(2-methyl-2-butenyl)-2-norbornene; and cyclooctadiene.
  • Fillers suitable for inclusion in the compoundable polymeric matrix of our invention include but are not limited to carbon black, ground coal, calcium carbonate, clay, silica, cryogenically ground rubber, and the like.
  • Carbon black may advantageously be used in an amount ranging from about 20 phr to about 300 phr.
  • Any such carbon black that is used may, for example, be selected from general purpose furnace (“GPF”), fast extrusion furnace (“FEF”), or semi-reinforcing furnace (“SRF”) commercially available carbon black.
  • GPF general purpose furnace
  • FEF fast extrusion furnace
  • SRF semi-reinforcing furnace
  • Suitable processing materials include oils, waxes, and the like.
  • Mineral oils are the preferred processing materials that are used in compoundable polymeric matrices which contain EPDM, with naphthenic and paraffinic oils being most preferred.
  • Such processing materials may advantageously be included in the compoundable polymeric matrix in an amount ranging from about 10 phr to about 300 phr, and preferably in an amount ranging from about 20 phr to about 1 50 phr, based upon EPDM.
  • inorganic or mineral fillers such as talc, mica, clay, silicates, and whiting. Fillers of these sorts may advantageously be included in the compoundable polymeric matrix or composition-of-matter in an amount ranging from about 10 phr to about 1 50 phr.
  • Sulfur curatives are generally preferred.
  • Sulfur preferably in elemental form, such as the commonly used “rhombic" crystalline form (called rubber makers' sulfur or spider sulfur), provides optimal tensile, tear, and cure characteristics to the cured rubber composition.
  • Sulfur curative may thus advantageously be used in amounts ranging from about 0.3 phr to 2 phr.
  • thermoplastic-containing, vulcanizable elastomeric matrix of our invention may optionally further include a cure accelerator such as a thiazole or a thiuram monosulfide.
  • a cure accelerator such as a thiazole or a thiuram monosulfide.
  • Suitable thiazoles include but are not limited to thiuram monosulfides and disulfides, benzothiazyl disulfide, and 2-mercaptobenzothiazole.
  • thermoplastic-containing, vulcanizable elastomeric matrix of our present invention may further optionally include a dithiocarbamate- type accelerator, such as a salt of a dialkyldithiocarbamate, wherein any alkyl groups may advantageously have from 1 to 6 carbon atoms and any such salt may advantageously be formed with bismuth, cadmium, copper, iron, lead, potassium, selenium, sodium, tellerium or zinc.
  • a dithiocarbamate- type accelerator such as a salt of a dialkyldithiocarbamate, wherein any alkyl groups may advantageously have from 1 to 6 carbon atoms and any such salt may advantageously be formed with bismuth, cadmium, copper, iron, lead, potassium, selenium, sodium, tellerium or zinc.
  • composition of this invention may be accomplished by any suitable means including an internal mixer, a two-roll mill, a transfer mixer, as well as an extruder.
  • a high density polyolefin is first compounded with a vulcanizable elastomeric material, and the compounded mixture is next processed or formed into the shape of a sheet-like membrane.
  • the vulcanizable, thermoplastic- containing membrane is then cured. Thereafter, edge margins of separate thermoplastic-containing sheet-like membranes, each cured thusly, can advantageously be overlappingly contacted and heat-seamed together, for purposes of providing a water-tight seal therebetween.
  • a particularly preferred polyolefin material used to promote adhesion in our invention is high density polyethylene (“HDPE").
  • HDPE high density polyethylene
  • ingredients can advantageously be combined and subsequently compounded utilizing equipment such as an internal mixer, a two-roll mill, an extruder, a "Banbury” mixer, or any other mixer suitable for forming a viscous, relatively uniform admixture.
  • equipment such as an internal mixer, a two-roll mill, an extruder, a "Banbury” mixer, or any other mixer suitable for forming a viscous, relatively uniform admixture.
  • the resulting admixture may advantageously subsequently be sheeted to thicknesses ranging from 5 to 200 mils, sheet thicknesses generally ranging from about 35 to about 60 mils, utilizing conventional sheeting methods such as milling, calendering, or extrusion.
  • the commercial approach is to roll the sheeted membrane onto curing mandrels, with a liner placed between the membrane plies, and curing in a steam autoclave.
  • the sheet may be dusted with talc or mica, rolled upon itself on the curing mandrel, and cured in a steam autoclave.
  • the sheet could also be cured, without utilizing such a liner, by transporting the sheet through a heated oven, and the sheet subsequently cooled. After cooling, the sheet can be rolled up with a release liner for transport.
  • thermoplastic-containing sheet-like membranes of the present invention One preferred method of heat-seaming edge margins of cured, thermoplastic-containing sheet-like membranes of the present invention is described as follows. As a sheet is unrolled over a preselected surface such as a roof or other substructure in a conventional manner, the seams of adjacent sheet layers are overlapped.
  • the next step is to apply sufficient heat and pressure to the edge margins, to form the seams.
  • the resultant seam area consisting of overlapping edge margins of adjacent sheets, is preferably heated to the softening point of the sheet material.
  • Temperature is advantageously maintained at a value greater than the melting/softening temperature of the thermoplastic polymeric material while sufficient pressure is applied for a suitable period of time.
  • the seaming temperature had to be equal to or greater than the melting point of the HDPE utilized.
  • compositions-of-matter were subjected to peel adhesion testing at room temperature and at 70 °C, as well as tests which determined tensile properties, and trouser-tear properties.
  • compositions-of-matter of our present invention were prepared according to procedures set forth in detail below.
  • the sheets may be wrapped-cured in liners of nylon, polyester, or other such material.
  • Talc or mica usually used to separate such sheets, were not able to be used, as use of such would undesirably affect the ability of the thermoplastic-containing, cured sheets to achieve desired adhesion.
  • thermoset roofing compositions of our present invention comprise blends of EPDM and high density polyethylene ("HDPE").
  • HDPE high density polyethylene
  • EPDM EPDM, phr 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
  • EPDM is "Royalene 3180,” a Trademark of Uniroyal Chemical Co. Inc.
  • HDPE is "Fortiflex T50-200", available from Solvay Polymers.
  • N-650 Black is carbon black, Iodine No. 36, absorption no. 122.
  • Paraffinic Oil is "Sunpar 2280", ASTM-D 2226, Type 104B.
  • Zinc Oxide is "Kadox 720", French process.
  • Delac NS is N-te/ -butyl-2-benzothiazole sulfenamide, delayed action accelerator, a trademark of Uniroyal Chemical Company, Inc.
  • the formulations of Table I were prepared by first mixing the EPDM, the HDPE, the N-650 carbon black, and the paraffinic oil ingredients in a "Brabender" Prepcenter (mixer) having a jacket temperature of 1 35 °C to form a masterbatch. The final mix temperature of this batch was 145-1 55 °C. The speed of the mixer was set at 50 revolutions per minute (“rpm").
  • the masterbatches were then mixed with the other ingredients including zinc oxide, stearic acid, Delac NS, Tuex, Ethyl Tuex, and sulfur in the Brabender Prepcenter mixer at a jacket temperature of 50 °C.
  • the temperature of the mixed stock did not exceed 100 °C.
  • the stocks were then refined and sheeted out on a mill, the temperature of this also did not exceed 100 °C.
  • the stocks were cured for 20 minutes at 1 60 °C in an ASTM mold having dimensions of 1 5 cm by 1 5 cm by 1 .9 mm (6 in by 6 in by 0.075 in).
  • the cured slabs were then used to prepare tensile-test samples, trouser-tear samples, and peel- adhesion samples.
  • the resultant compounds were tested for stress-strain and peel adhesion properties after aging at 23 °C for 24 hours. Stress-strain samples were prepared and tested according to ASTM D 41 2-87, Method A. Peel adhesion samples were prepared at a cross-head speed of two (2) inches/minute according to the following method.
  • the adhesion pads were wiped with mineral spirits solvent (e.g. white gasoline, and the like). In field installations, the seam area is always washed with solvent to clean the surface of foreign material prior to applying an adhesive.
  • mineral spirits solvent e.g. white gasoline, and the like.
  • the 6 in by 6 in slabs were cut in half, and the halves were next sandwiched together along with a 2.5 cm by 17.5 cm ( 1 in by 7 in) long Teflon spacer placed along the top edge.
  • the composite was subsequently placed between two additional Teflon sheets of similar dimension and next placed in a hot press which was set at 1 60 °C.
  • the heated platens of the press were closed until both just touched the surface of the composite.
  • the sample was heated at 1 60 °C for 5 minutes.
  • the heat-joined section of the composite was rolled with a metal hand roller weighing 850 grams.
  • the rolled composite was then cooled for one (1 ) hour, and the Teflon spacer subsequently removed. Thereafter, five (5) adhesion pad samples measuring 2.5 cm by 7.5 cm (1 in by 3 in) were cut from the composite.
  • Example A is a comparative sample.
  • Examples 7 through 8 illustrate the importance that mixing temperature plays, when maximizing heat-seamable peel adhesion values.
  • the same formulation was used as in Example 2, with the exception of the type of HDPE used, mixed at the temperatures presented in Table III. Table III
  • the high density polyethylene used in Examples 7 and 8 was "Microthene MA 795-00," a high density polyethylene powder, rotational molding grade, having a melt index of 5.0, a density of 0.946 and a flexural modulus (1 % secant) of 1 17,250 psi, available from USI Chemicals Co. of Cincinnati, Ohio.
  • Example 8 The higher value of peel adhesion at a masterbatch mixing temperature is evidence of the need to mix the HDPE into the formulation at or above the crystalline melting temperature. Even though the HDPE used in Example 8 was a fine powder, it formed a grainy appearance on the surface of both the uncured and cured samples, presenting an unsightly appearance which might preclude use in many fabricated rubber articles. Examples 9 Through 1 2
  • the standard method for calculating crystallinity is to compare a particular J/gm value with that of a very crystalline PE.
  • Polyethylene at near 100 % crystallinity has a Heat of Fusion value of 277-280 J/gm, as reported in the POLYMER HANDBOOK.
  • the J/gm value of each polymer is divided by the value 279 J/gm, the quotient when multiplied by 100 becomes the percent crystallinity value, as based upon the 100 % crystalline PE standard.
  • Our preferred DSC crystallinity determining procedure is set forth hereinbelow.
  • Peel Adhesion 55 30 32 49 (g> RT, pli Motes for Table IV: (1) EXXON (brand) polyolefins are available from Exxon Corporation, which has a business office in Irving, Texas, United States of America (U.S.A.); (2) AC617A (brand) polyethylene is available from R.T. Vanderbilt of Norwalk, Connecticut, U.S.A. and (3) FLEXOMER (brand) polyolefins are available from Union Carbide, of New York, New York, U.S.A. Procedure For Differential Scanning Calorimeter Analysis of EPDM Rubber
  • thermoplastic-containing, cured elastomeric matrix What has been described herein is a novel method for making a thermoplastic-containing, cured elastomeric matrix.

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Abstract

L'invention concerne un procédé de production d'une matrice élastomérique thermodurcie, thermosoudable, consistant: (1) à combiner un matériau élastomérique vulcanisable à un matériau polymérique thermoplastique présentant une température de ramollissement/fusion prédéterminée, de façon à produire une dispersion de matériau polymérique thermoplastique dans l'ensemble du matériau élastomérique vulcanisable, (2) tout en chauffant suffisamment longtemps la dispersion à une température supérieure à la température de ramollissement/fusion du matériau polymérique thermoplastique, de manière à permettre au matériau polymérique thermoplastique de se ramollir ou de fondre et de se disperser dans l'ensemble du matériau élastomérique, et de former ainsi une matrice élastomérique vulcanisable et (3) à faire durcir la matrice contenant le matériau thermoplastique, ce qui permet d'obtenir la matrice élastomérique thermodurcie, thermosoudable
PCT/US1995/007472 1994-06-23 1995-06-12 Membrane de revetement thermodurcie thermosoudable et ses procedes de fabrication et d'utilisation WO1996000259A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU29022/95A AU2902295A (en) 1994-06-23 1995-06-12 Heat-seamable thermoset sheeting membrane and methods of manufacturing and using same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US26439094A 1994-06-23 1994-06-23
US08/264,390 1994-06-23

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WO1996000259A2 true WO1996000259A2 (fr) 1996-01-04
WO1996000259A3 WO1996000259A3 (fr) 1996-01-25

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1473321A1 (fr) * 2003-04-18 2004-11-03 Sumitomo Rubber Industries Limited Composition de caoutchouc pour pneumatique et pneumatique utilisant celle-ci
EP1378543A4 (fr) * 2001-02-28 2006-08-16 Daicel Degussa Ltd Materiau a base d'une composition de resine thermoplastique et article faconne au moyen de ce materiau
WO2011000935A1 (fr) 2009-07-02 2011-01-06 Sika Technology Ag Dispersions de polyuréthane-polymère acrylique et leurs utilisations
WO2025076110A1 (fr) 2023-10-02 2025-04-10 Henry Company, Llc Formulations hybrides stables d'émulsion acrylique et de dispersions de polyuréthane et leurs applications

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3316302A1 (de) * 1983-05-04 1984-11-08 Metzeler Kautschuk GmbH, 8000 München Dichtungsbahn
JPS60116431A (ja) * 1983-11-30 1985-06-22 Bridgestone Corp 防水シ−トの接合方法
US4722961A (en) * 1986-06-16 1988-02-02 Union Carbide Corporation Roofing membranes
US5242727A (en) * 1991-01-04 1993-09-07 Adco Products, Inc. Adhesive composition and method for providing water-tight joints in single-ply roofing membranes

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1378543A4 (fr) * 2001-02-28 2006-08-16 Daicel Degussa Ltd Materiau a base d'une composition de resine thermoplastique et article faconne au moyen de ce materiau
EP1473321A1 (fr) * 2003-04-18 2004-11-03 Sumitomo Rubber Industries Limited Composition de caoutchouc pour pneumatique et pneumatique utilisant celle-ci
US7165585B2 (en) 2003-04-18 2007-01-23 Sumitomo Rubber Industries, Ltd. Rubber composition for tire and pneumatic tire using the same
WO2011000935A1 (fr) 2009-07-02 2011-01-06 Sika Technology Ag Dispersions de polyuréthane-polymère acrylique et leurs utilisations
EP2277961A1 (fr) 2009-07-02 2011-01-26 Sika, S.A.U. Dispersions de revêtement de polymères pour le toit à base de polyuréthane acrylique
US8536263B2 (en) 2009-07-02 2013-09-17 Sika Technology Ag Polyurethane-acrylic polymer dispersions and uses thereof
WO2025076110A1 (fr) 2023-10-02 2025-04-10 Henry Company, Llc Formulations hybrides stables d'émulsion acrylique et de dispersions de polyuréthane et leurs applications

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Publication number Publication date
AU2902295A (en) 1996-01-19
WO1996000259A3 (fr) 1996-01-25

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