WO2020069132A2 - Composition adhésive de polyuréthane durcissable à l'humidité à un constituant pour des applications de toiture - Google Patents

Composition adhésive de polyuréthane durcissable à l'humidité à un constituant pour des applications de toiture Download PDF

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Publication number
WO2020069132A2
WO2020069132A2 PCT/US2019/053157 US2019053157W WO2020069132A2 WO 2020069132 A2 WO2020069132 A2 WO 2020069132A2 US 2019053157 W US2019053157 W US 2019053157W WO 2020069132 A2 WO2020069132 A2 WO 2020069132A2
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Prior art keywords
adhesive
weight
roofing
recited
liquid
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PCT/US2019/053157
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English (en)
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WO2020069132A3 (fr
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Kaspar SCHAERER
Benjamin M. BIBER
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Henkel IP & Holding GmbH
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Publication of WO2020069132A2 publication Critical patent/WO2020069132A2/fr
Publication of WO2020069132A3 publication Critical patent/WO2020069132A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C08G18/698—Mixtures with compounds of group C08G18/40
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2081—Heterocyclic amines; Salts thereof containing at least two non-condensed heterocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers

Definitions

  • the present disclosure relates generally to adhesives for use in roofing applications, and more particularly to a single component moisture-curable
  • polyurethane adhesive for use in roofing applications and to methods for its use.
  • Membrane based roofing systems are used on many commercial building roofs, especially on flat or low slope roofing systems. They are also used in residential applications.
  • the membrane roofing system comprises a roof deck and a membrane bonded thereto.
  • the roof deck is the upper part of the building structure and provides support.
  • the roof deck can be steel, concrete, gypsum, wood board and plywood.
  • the roof deck may also include one or more layers of, for example, vapor barrier, insulation such as polyisocyanurate foam and thermal barrier.
  • the membranes are typically polymeric materials with thicknesses of 20 mils to over 100 mils.
  • the membrane can be provided in a single roll for smaller roofs or as a series of rolls that need to be joined together along an edge for larger roofs.
  • a perimeter is marked around the entire roof of about 100 mm from the edge, this will be the location of a second edge contact adhesive.
  • the roofing membrane is rolled out over the roof and allowed to relax for a period of time such as 30 minutes or so. Then portions of the roofing membrane are rolled back, typically half of the roof, to allow a deck adhesive to be applied to the roof deck in sections and the membrane is rolled back over the applied deck adhesive sections. After a first half of the roof is completed the roofer goes over the half of the membrane with the deck adhesive applied using a broom to brush off the talc, which is pre-applied to make the membrane easy to maneuver, and to remove any air bubbles from under the membrane.
  • the second half of the roof is done in the same manner.
  • the next step is to go back and apply the contact adhesive to both the roof deck and the backside of the membrane in the pre- marked 100 mm edge portion.
  • This adhesive is often different from that applied to the main portion of the membrane and generally must be allowed to tackify on each surface then the membrane is rolled back into position and again it is brushed.
  • the roof is finished by applying an edging, typically formed from hard foam or PVC edging, which is nailed or stapled into the edge of the building where it joins the roof to further secure the membrane to the roof and form a watertight seal. As a final step the membrane excess is trimmed away.
  • thermoplastics such as polyvinyl chloride (PVC) membranes, copolymer alloys (CPA), chlorinated polyethylene (CPE), ethylene interpolymer (EIP), nitrile alloys (NBP), polyisobutylene (PIB), thermoplastic olefin (TPO), synthetic rubber elastomeric materials such as ethylene propylene diene terpolymer (EPDM) and modified bitumen.
  • PVC polyvinyl chloride
  • CPE chlorinated polyethylene
  • EIP ethylene interpolymer
  • NBP nitrile alloys
  • PIB polyisobutylene
  • TPO thermoplastic olefin
  • EPDM ethylene propylene diene terpolymer
  • membrane materials can be sealed to adjacent membrane sheets via sealing tapes or rubber strips.
  • roofing adhesives are two component systems meaning they have an A component which is stored separately from a B component. To use these adhesives right before application step the A component is mixed in a defined ratio with the B component to form the actual adhesive and then the mixture is applied to the roofing materials.
  • Each component may comprise a plurality of ingredients, but it is called a two component system because there is an A component and a B component that need to mixed right at or close to the actual use time.
  • a one component adhesive composition means the entire adhesive comes as a single component to be applied, there are not an A component and a B component that need to be mixed prior to use of the adhesive.
  • the one component adhesive can comprise a plurality of ingredients, however it is supplied as a ready to use single component to a user.
  • VOC solvents are usually a blend of toluene, xylene and hexane.
  • the adhesive is preferably a two-component system comprising a polyol component and a diisocyanate component.
  • the polyol component includes a polyol, a surfactant such as a silicone and at least one catalytic agent.
  • the diisocyanate is conventional.
  • the adhesive is used to adhere a membrane that is fleece lined with a non-woven polyester fleece like layer on one side to a roof.
  • the fleeced material is pressed into the uncured polyurethane foam adhesive to improve the adhesion.
  • the fleece material improves the adhesion between the membrane and the roof structure, but production of these membranes is expensive and suffers from manufacturing inefficiencies in attaching the fleece to the membrane and the application requires the formation of vapor venting spacing the construction of the roof.
  • a two component, solvent free, 100% solids, polyurethane adhesive for adhering polymeric roofing membranes to roof-deck substrates is described in U.S. Patent No. 5,872,203.
  • the two component adhesive may be applied and cured on the job site and it is claimed that it has a low toxicity risk, good bond strength, is solvent free, and resists aging from exposure to heat and moisture.
  • the adhesive preferably uses a 2k polyisocyanate prepolymer as a first component and a polyol as a second component of the two component system.
  • the disadvantages of the system are that it is a two component system and it requires additional equipment to ensure that the mix ratio of the components is correct to thereby ensure proper adhesion. This additional equipment is expensive, heavy, large, and not user friendly.
  • the delicacy and equipment used during the mixing of the adhesive is undesirable in the industry.
  • a moisture-curable bond adhesive comprising a polymer having silicone- containing hydrolyzable terminal groups, a phenolic resin, and a non-polymeric silicone- containing hydrolyzable compound is described in U.S. Patent No. 7,767,308. These adhesives are desirable because they can be formulated to be VOC free, safe for chronic exposure, non-flammable, and have high initial peel strength upon being fully cured. A disadvantage of this system is, however, that the adhesive contains a phenolic resin and it is a disadvantage to have to use this resin.
  • U.S. Patent No. 8,701 ,367 describes a low slope roofing system that uses a roofing EPDM membrane again having a non-woven polyester fleece attached to one side of the membrane. It describes polyether based moisture curing adhesive that comprises a silyl-terminated polymer, pigments, a plasticizer, a thixotropic material, an antioxidant, a catalyst, and an adhesion promoter.
  • the adhesive is utilized to bond water-proof membranes to low sloped roofing substrates.
  • the adhesive is designed to have a very high viscosity of from 200,000 to 300,000 centipoise.
  • the application of this adhesive requires the use of an extrusion applicator that extrudes the adhesive in the form of a plurality of beads of adhesive. The extruder is relatively large and expensive. Additionally, a weighted roller is necessary to ensure a good bond.
  • One aspect of the present disclosure is to provide a liquid, one
  • moisture-curable polyurethane adhesive comprising the reaction products of a polyisocyanate with a hydroxyl-terminated polybutadiene, a polyester polyol and a polyether diol in the presence of a catalyst; and the adhesive optionally including one or more components selected from the group consisting of a solvent, an acrylic polymer, a plasticizer, a tackifier, a filler, an UV marker, a defoamer, a rheology modifier and a flame retardant.
  • solvent is present it is in an amount of less than 50% by weight based on the total weight of the adhesive; preferably less than 30 wt %, more preferably less than 15 wt% and in some variations may be VOC generating solvent free.
  • a roof section comprising: a roofing membrane bonded to a roofing substrate by the cured reaction products of a liquid one component moisture-curable polyurethane adhesive comprising the reaction products of a polyisocyanate with a hydroxyl-terminated polybutadiene, a polyester polyol and a polyether diol in the presence of a catalyst; and the adhesive optionally including one or more components selected from the group consisting of a solvent, an acrylic polymer, a plasticizer, a tackifier, a filler, an UV marker, a defoamer, a rheology modifier and a flame retardant, wherein when said solvent is present it is in an amount of less than 30% by weight based on the total weight of the adhesive.
  • a method of bonding a roofing membrane to a roof substrate comprising the steps of: a) providing a liquid one component moisture-curable polyurethane adhesive comprising the reaction products of a polyisocyanate with a hydroxyl-terminated polybutadiene, a polyester polyol and a polyether diol in the presence of a catalyst; and the adhesive optionally including one or more components selected from the group consisting of a solvent, an acrylic polymer, a plasticizer, a tackifier, a filler, an UV marker, a defoamer, a rheology modifier and a flame retardant, wherein when the solvent is present it is in an amount of less than 30% by weight based on the total weight of the adhesive; b) applying the adhesive composition to one or both of a roof substrate and a roofing membrane; c) allowing the adhesive to develop a skin; and d) positioning the roofing membrane onto the roof substrate and applying sufficient pressure
  • Figure 1 is a cross sectional, schematic view showing one embodiment of a roof deck with a roofing membrane adhesively bonded thereto.
  • first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms.
  • “One or more”, as used herein, relates to at least one and comprises 1 , 2, 3, 4, 5, 6, 7, 8, 9 or more of the referenced species.
  • “at least one” means one or more, i.e. 1 , 2, 3, 4, 5, 6, 7, 8, 9 or more.
  • “At least one”, as used herein in relation to any component, refers to the number of chemically different molecules, i.e. to the number of different types of the referenced species, but not to the total number of molecules.
  • “at least one polyol” means that at least one type of molecule falling within the definition for a polyol is used but that also two or more different polyol types falling within this definition can be present but does not mean that only one type of said polyol is necessarily present.
  • the term“molecular weight” refers to the average number molecular weight Mn, if not explicitly stated otherwise.
  • the number average molecular weight M n can be calculated based on end group analysis (OH numbers according to DIN EN ISO 4629, free NCO content according to EN ISO 1 1909) or can be determined by gel permeation chromatography according to DIN 55672 with THF as the eluent. If not stated otherwise, all given molecular weights are those determined by gel permeation chromatography.
  • the weight average molecular weight M w can be determined by GPC, as described for M n .
  • NCO content refers to the NCO content as determined according to EN
  • the present disclosure provides an adhesive composition
  • a one part liquid polyurethane moisture-curable adhesive formed by reaction of a polyisocyanate, preferably methylene diphenyl diisocyanate (MDI), with a combination of polyols comprising hydroxyl terminated polybutadiene, a polyester polyol, and a polyether diol.
  • MDI methylene diphenyl diisocyanate
  • the one part adhesive can optionally further comprise other
  • a liquid adhesive is an adhesive that is a flowable liquid at room temperature.
  • the adhesive does not foam and is not a foamable polyurethane adhesive.
  • the adhesive can be formulated with traditional levels of solvents. However, the adhesive works well when formulated with very low solvent levels of less than 50% by weight based on the total weight of the adhesive, preferably less than 30 wt %, more preferably less than 15 wt% and in some variations may be solvent free so that the VOC solvent levels in the adhesive can be very low.
  • the presently disclosed adhesive composition can crosslink and cure when exposed to moisture.
  • the adhesive composition can provide an adhesive of very low viscosity that is easily applied with a mop or roller by unskilled labor and without the need for heavy or expensive equipment.
  • the amount of catalyst used allows for control of the curing, providing a cured adhesive with desirable strength in an appropriate amount of time.
  • the cured adhesive has good strength for bonding one surface of a roofing membrane material to the surface of a roof deck or roof deck material.
  • Useful roofing membrane roofing materials include thermoplastics such as polyvinyl chloride (PVC) membranes, copolymer alloys (CPA), chlorinated polyethylene (CPE), ethylene interpolymer (EIP), nitrile alloys (NBP), polyisobutylene (PIB), thermoplastic olefin (TPO) and synthetic rubber elastomeric materials such as ethylene propylene diene terpolymer (EPDM).
  • thermoplastics such as polyvinyl chloride (PVC) membranes, copolymer alloys (CPA), chlorinated polyethylene (CPE), ethylene interpolymer (EIP), nitrile alloys (NBP), polyisobutylene (PIB), thermoplastic olefin (TPO) and synthetic rubber elastomeric materials such as ethylene propylene diene terpolymer (EPDM).
  • the adhesive 2 is applied to a surface of the roof deck 4 or more typically to a surface of a roof membrane 6, 8.
  • the adhesive is allowed to surface cure and form a thin skin with uncured liquid adhesive between the skin and the roof membrane.
  • the skin forms in about twenty minutes although this can be adjusted as needed.
  • the roof membrane with skinned over adhesive can be placed onto the roof deck. Since the adhesive has a non-liquid and non-tacky skin, it resists sticking to the roof deck and the membrane can be easily repositioned by workers. Further, the skinned over adhesive allows the roof membrane to be easily moved and handled without leaving uncured adhesive on workers or the staging area.
  • the roof membrane is desirably positioned onto the roof deck with the skinned adhesive adjacent the roof deck surface, light pressure on the top of the membrane causes the adhesive skin to break thereby exposing the liquid adhesive beneath the skin and permitting the adhesive to penetrate and wet the roof deck to allow for good adhesion of the membrane to the roof deck.
  • the thin skin formation during curing while maintaining an active adhesive underneath that can be released upon the breaking of the skin following minimal pressure is what allows for the disclosed adhesive to be used in a single sided application method.
  • the adhesive can initially be applied to the roof deck and allowed to initially cure forming a skin.
  • the roofing membrane is positioned over the skinned adhesive.
  • the adhesive 2 can be used to bond an extension 12 of one roof membrane 6 to another roof membrane 8 at, for example, the seam 10. Although not shown in Figure 1 there is typically adhesive 2 in the seam area. Naturally, the adhesive 2 can be used to join different roofing membranes or portions of the same roofing membrane in other situations into a unitary structure. If the skin is too thin the membrane can be difficult to handle without breaking the skin. If the skin is too thick or the adhesive dries completely the bond strength will be lower than desired.
  • the membrane can no longer be adjusted without disrupting the adhesive bond and breaking the roofing membrane and or roof deck.
  • the adhesive can be applied to a surface of the roofing membrane or roof deck.
  • the roofing membrane is placed on the roof deck immediately, with liquid adhesive therebetween and the adhesive is allowed to cure, bonding the roofing membrane to the roof deck.
  • This method allows adjustment of the membrane substrates with respect to each other, however the bond strength between the first and second substrates may undesirably be lower than if a skin is allowed to form on the adhesive before overlaying membranes.
  • the one-component, moisture curable adhesive is typically prepared by reacting a mixture comprising a polyisocyanate, a hydroxyl terminated polybutadiene, and optionally one or both of a polyester polyol and a polyether diol.
  • the formulation can optionally further comprise at least one additive, for example, an acrylic polymer, a plasticizer, a tackifier, a filler, a coloring agent, a catalyst, a solvent, a defoamer, rheology modifier (typically polymeric MDI), a flame retardant, a UV marker and mixtures thereof.
  • the adhesive is preferably free of oligomers or polymers containing siloxy (-SiRnY3-n, where R is alkyl and Y is a hydrolysable group) groups.
  • siloxy -SiRnY3-n, where R is alkyl and Y is a hydrolysable group
  • the uncured liquid adhesive according to the present disclosure has a solids level of 85 to 100% by weight.
  • solids refer to adhesive composition components that are non-volatile but not necessarily in solid form at room temperature.
  • 77 °F preferably has a viscosity at 77 °F of 14,000 centipoise or less, more preferably from 1 ,000 to 5,500 centipoise at 77 °F.
  • the polyisocyanate utilized in the present disclosure can comprise any polyisocyanate known to one of skill in the art.
  • Useful polyisocyanates include monomeric diisocyanates such as diphenylmethane diisocyanate (MDI); toluene diisocyanate; 1 ,4-diisocyanatobenzene (PPDI); 2,4'-diphenylmethane diisocyanate; 1 ,5- naphthalene diisocyanate; bitolylene diisocyanate; 1 ,3-xylene diisocyanate; p-TMXDI; 1 ,6-diisocyanato-2,4,4-trimethylhexane; CHDI; BDI; HqC ⁇ I; IPDI; H12MDI, HDI and the like.
  • polyisocyanates include modified forms of these monomeric diisocyanates such as allophanate modified MDI or carbodiimide modified MDI or polymeric MDI.
  • the polyisocyanate component can comprise a mixture of these known polyisocyanates.
  • the polyisocyanate is MDI, modified MDI or a combination thereof.
  • the hydroxyl-terminated polybutadiene can comprise known liquid polybutadiene polyols.
  • Useful hydroxyl-terminated polybutadienes include the polyBD family available from Total Cray Valley of Exton PA. including, for example, polyBD R45HTLO, polyBD R45V, and polyBD R20LM
  • the polyester polyol is preferably a liquid, linear aliphatic polyester polyol.
  • Useful polyester polyols include diois having a functionality of 2 and triols having a functionality of three and combinations thereof.
  • Useful polyesters will typically have a weight average (Mw) molecular weight in the range of about 250 to about 5,000 g/mol/mole.
  • Some polyester polyols useful in the composition include those that are the reaction product of neopentyl glycol, diethylene glycol, ethylene glycol, propylene glycol and/or 1 ,6-hexanediol reacted with adipic acid, dodecanedioic acid and/or phthalic acid.
  • Useful polyester polyols include Stepanpol® PC-107-110, Rucoflex S 107-110,
  • Stepanpol PC-107P-55 Stepanpol PC-1015P-120, Stepanpol PC-105P-110, Stepanpol PC-201-165, andStepanpol PC-1011P-210.
  • Dimer fatty acid based polyester polyols such as the Priplast polyols available from Croda International Pic are also useful. Useful dimer fatty acid based polyester polyols include Priplast 1830 and Priplast 1900. While the dimer fatty acid based polyester polyol can be used in combination with hydroxyl terminated
  • polybutadiene polyols in some embodiments it is also possible to replace some or all of the hydroxyl-terminated polybutadiene component with dimer fatty acid based polyester polyol.
  • Polyether polyols useful in the composition include diois having a functionality of 2 and triols having a functionality of three and combinations thereof polyether polyols will typically have a molecular weight in the range of 250-10,000 gm/mole.
  • Useful polyether polyols include polyethylene glycol, polypropylene glycol, polydiethylene glycol, polyTHF polyol, polycarbonate polyol, and carprolactone based polyol.
  • Useful polyether polyols include PPG 725, PPG 1000, PPG 2000, PPG 4000, PTMEG 625, PTMEG 1000, PTMEG 2000, PTMEG 3000, Pluracol 1718, Pluracol GP 430, Pluracol 4156, and Pluracol 1135L
  • the adhesive composition can optionally comprise at least one acrylic polymer additive.
  • Acrylic polymers useful in the composition can be either a reactive polymer or non-reactive polymer.
  • a reactive polymer comprises groups such as carboxylic acid, amine, thiol and hydroxyl that react with other components of the composition.
  • a non-reactive acrylic polymer does not include groups that are reactive with other composition components.
  • One useful reactive acrylic polymer is Resiflow® LF available from Estron Chemical, Calvert City KY.
  • the adhesive composition can optionally comprise at least one plasticizer additive.
  • Plasticizers useful in the composition include, for example, liquid plasticizers based on phthalate, adipate, sebacate or trimelliate chemistry.
  • One useful plasticizer is diisodecyl phthalate (DIDP).
  • the adhesive composition can optionally comprise at least one tackifier additive.
  • Tackifiers useful in the composition include natural and petroleum-derived materials and combinations thereof as described in C.W. Paul,“Hot Melt Adhesives,” in Adhesion Science and Engineering-2, Surfaces, Chemistry and Applications, M.
  • Useful tackifier for the adhesive composition of the invention includes natural and modified rosin, aromatic tackifier or mixtures thereof.
  • Useful natural and modified rosins include gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, resinates, and polymerized rosin; glycerol and pentaerythritol esters of natural and modified rosins, including, for example as the glycerol ester of pale, wood rosin, the glycerol ester of hydrogenated rosin, the glycerol ester of polymerized rosin, the pentaerythritol ester of hydrogenated rosin, and the phenolic- modified pentaerythritol ester of rosin.
  • rosins and rosin derivatives examples include Sylvalite RE 110L, Sylvares RE 115, and Sylvares RE 104 available from Kraton Corporation; Dertocal 140 from DRT; Limed Rosin No.1 ,GB-120, and Pencel C from Arakawa Chemical.
  • One exemplary natural and modified rosin is a rosin ester tackifier such as KE-100, available from Arakawa Chemical Co.
  • Another exemplary rosin ester tackifier is a Komotac 2110 from Komo Resins.
  • Exemplary aromatic tackifiers include styrenic monomers, styrene, alpha-methyl styrene, vinyl toluene, methoxy styrene, tertiary butyl styrene,
  • aromatic tackifiers are alpha-methyl styrene types such as Kristalex 3100, Kristalex 5140 or Hercolite 240, all available from Eastman Chemical Co.
  • Preferred tackifiers include liquid tackifiers such as wingtac 10 available from Cray Valley and Sylvatac RE 40, Sylvatac RE 25, Sylvalite RE 10L, and Sylvares TR A25 available from Kraton Corporation.
  • the adhesive composition can optionally comprise at least one filler additive.
  • Fillers useful in the composition include, for example, lithopone, zirconium silicate, hydroxides, such as hydroxides of calcium, aluminum, magnesium, iron and the like, diatomaceous earth, carbonates, such as sodium, potassium, calcium, and magnesium carbonates, oxides, such as zinc, magnesium, chromic, cerium, zirconium and aluminum oxides, clay, nanosilica, fumed silicas, silicas that have been surface treated with a silane or silazane such as the AEROSIL products available from Evonik Industries, silicas that have been surface treated with an acrylate or methacrylate such as AEROSIL R7200 or R71 1 available from Evonik Industries, precipitated silicas, untreated silicas, graphite, synthetic fibers and mixtures thereof.
  • filler can be employed in concentrations effective to provide desired properties in the uncured composition and cured reaction products.
  • the adhesive composition can optionally comprise a coloring agent additive.
  • Coloring agents can be beneficial to allow for inspection of the applied adhesive composition.
  • a coloring agent for example a pigment or dye, can be used to provide a desired color beneficial to the intended application.
  • Exemplary coloring agents include titanium dioxide, carbon black, C.l. Pigment Blue 28, C.l. Pigment Yellow 53 and phthalocyanine blue BN.
  • the composition can optionally include at least one UV marker. UV markers fluoresce when exposed to certain levels and wavelengths of radiation allowing. When added to the adhesive composition the UV marker allows testing for the presence of adhesive using UV light.
  • UV marker additives useful in the composition include, for example TINOPAL available from BASF, UVITEX available from Huntsman, Benetex OB, Lunatex OB, or Scanning Compound No.5
  • the adhesive composition can optionally comprise at least one catalyst.
  • catalysts include bismuth compounds such as bismuth carboxylate; organic tin catalysts such as dimethyltin dineodecanoate, dibutyltin oxide and dibutyltin diacetate; titanium alkoxides (TYZOR® types, available from DuPont); amines such as bis (2-morpholinoethyl) ether, 2,2'-Dimorpholino Diethyl Ether (DMDEE) and triethylene diamine; zirconium complexes (KAT XC6212, K-KAT XC-A209 available from King Industries, Inc ); aluminum chelates (K-KAT 5218, K-KAT 4205 available from King Industries, Inc.), KR types (available from Kenrich Petrochemical, Inc.); and other organometal!ic compounds based on Zn, Co, Ni, and Fe and the like.
  • One preferred catalyst is 2,2’ dimorpholinodiethyl ether (DMD
  • the composition can optionally include at least one solvent, provided it is at a level of less than 50%, typically less than 30%, preferably less than 15% and most preferably less than 1% by weight based on total adhesive weight.
  • solvent examples include acetone, methyl ethyl ketone (MEK), toluene, xylene, hexane, heptane, and oxsol 100 (parachlorobenzotrifluoride or PCBTF).
  • the composition can optionally include at least one defoamer.
  • Defoamers useful in the composition include polysiloxane emulsion.
  • Other defoamers are available from BYK-Chemie GMBH and include BYK 067.
  • the composition can optionally include at least one rheology modifier.
  • Rheology modifiers useful to modify viscosity of the final adhesive composition are known in the art.
  • the composition can optionally include at least one flame retardant additive.
  • Flame retardant additives useful in the composition include Celltech FR-50, Celltech FR-62, Celltech FR-52, Celltech FR-52, Exolit OP 560, Exolit OP 550,
  • Procedural Example A one-component, moisture curable adhesive composition according to the present disclosure was prepared as follows. A mixture of 7.0 g of hydroxyl terminated polybutadiene (Poly bd® R-45HTLO), 31 g of polyester polyol (Stepanpol® PC-107-110), 9 g of polyether diol (Poly G® 55-28), and 30 g of diisocyanate (4,4 -MDI) was prepared and reacted at 140 °F to 160 °F for 2 hours until the NCO% was constant at about 7.2% indicating completion of the reaction.
  • Poly bd® R-45HTLO hydroxyl terminated polybutadiene
  • Steppanpol® PC-107-110 polyester polyol
  • 9 g of polyether diol Poly G® 55-28
  • diisocyanate 4,4 -MDI
  • reaction additives were added to the mixture, including 0.28 g of acrylic polymer (Resiflow® LF), 7.61 g of plasticizer (diisodecyl phthalate (DIDP)), and 0.2 g of silicone defoamer (BYK® 067).
  • the resulting solution was then cooled to room temperature and 15 g of toluene was added along with 0.08 g of the catalyst 2,2’ dimorpholinodiethyl ether (DMDEE).
  • DMDEE dimorpholinodiethyl ether
  • the solution was mixed for another 10 minutes.
  • the finished product is a liquid, one-component, moisture curable adhesive composition having a viscosity of 1230 cPs at 77°F.
  • compositions, A-J were prepared using the process of Example 1.
  • the compositions are presented in the Tables below. % values are weight % based on total adhesive weight and are rounded to the nearest 0.1 %.
  • compositions, K-O were prepared using the process below and the components and the amounts shown in the following table.
  • Weight % values are based on total adhesive weight and are rounded to the nearest 0.1%.
  • a mixture of hydroxyl terminated polybutadiene (Poly bd® R-45HTLO), polyester polyol (Rucoflex S 107-110), polyether diol (Poly G® 55-28), acrylic additive (Resiflow), DIDP and Uvitex OB was prepared and dried under vacuum for 90 minutes at a temperature of 140°F to 160°F.
  • Diisocyanate (Mondur M) was added and reacted at 140 °F to 160 °F for 2 hours to form a reaction product.
  • the reaction product was cooled to about 130°F and catalyst (2,2’ dimorpholinodiethyl ether DMDEE) and silicone defoamer (BYK® 067) was added.
  • Rubinate 1820 was added and mixed under vacuum. Cool below 100°F, add toluene and mix.
  • the one-component, moisture curable adhesive compositions prepared according to the present disclosure performed well in adhering a roofing membrane to a roof deck material in several tests.
  • the lower the viscosity of the adhesive the easier it is to spread during application onto the roof deck and the membrane material; however it also permits for more absorption of the adhesive into the roof deck material and thus must not be made too low.
  • higher amounts of catalyst improve the speed at which the adhesive achieves its final strength.
  • the ability to apply the adhesive as a single sided application doubles the coverage and the ability to have a high solids content of 85 to 100% results in a net 3-4 fold increase in the coverage area per unit.
  • the increased square footage per gallon of the present adhesive reduces the cost for manufacturing, reduces the cost for freight, makes for easier transportation, and reduces labor all of which reduce the carbon footprint and makes the system more sustainable.
  • Example embodiments are provided so that this disclosure will be thorough and will fully convey the scope to those who are skilled in the art. Numerous specific details are set forth such as examples of specific components, devices, and methods, to provide a thorough understanding of embodiments of the present disclosure. It will be apparent to those skilled in the art that specific details need not be employed, that example embodiments may be embodied in many different forms and that neither should be construed to limit the scope of the disclosure. In some example embodiments, well-known processes, well-known device structures, and well-known technologies are not described in detail.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Un adhésif de polyuréthane durcissable à l'humidité à un constituant comprend les produits de réaction d'un polyisocyanate avec un polybutadiène à terminaison hydroxyle, et éventuellement des additifs et un polyol de polyester et/ou un polyéther diol. Dans certains modes de réalisation, l'adhésif peut être exempt de solvant et avoir une teneur en solides élevée supérieure ou égale à 85 %. L'adhésif trouve une utilisation dans la liaison de membranes de toiture à des substrats d'accueil de toiture. Il est efficace et ne nécessite pas d'équipement spécialisé en vue de son application. Il peut être appliqué uniquement sur la membrane de toiture, uniquement sur le substrat de toiture ou sur les deux selon les besoins. Dans certaines applications, l'adhésif durcit initialement en formant un revêtement mince sous lequel se trouve un adhésif liquide, ce qui permet une manipulation aisée de la membrane de toiture sur le substrat de toit. Une fois correctement positionné, une légère pression rompt le revêtement et étale l'adhésif entre la membrane de toiture et le substrat de toiture lie la membrane au substrat.
PCT/US2019/053157 2018-09-26 2019-09-26 Composition adhésive de polyuréthane durcissable à l'humidité à un constituant pour des applications de toiture WO2020069132A2 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111378413A (zh) * 2020-04-22 2020-07-07 湖北回天新材料股份有限公司 一种免底涂单组份聚氨酯密封胶及制备方法
CN113652192A (zh) * 2021-09-29 2021-11-16 苏州市陆氏新材料有限公司 一种pu胶黏剂的制备方法、pu胶黏剂及其应用于epdm粘结的方法
EP3932966A1 (fr) * 2020-06-30 2022-01-05 Henkel AG & Co. KGaA Composition adhésive pour lier des substrats polaires et non polaires
US11472988B2 (en) 2020-11-04 2022-10-18 Bmic Llc Adhesive formulations including at least one silyl modified polymer

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6305143B1 (en) * 1999-06-25 2001-10-23 Ashland Inc. Composite roof structures prepared using one-part moisture curing polyurethane foaming adhesive compositions containing a reversibly blocked catalyst
US20050246991A1 (en) * 2004-02-20 2005-11-10 Gang-Fung Chen One-part adhesive composition for adhering polymeric roofing membranes to roof deck substrates
WO2009070293A1 (fr) * 2007-11-28 2009-06-04 Quaker Chemical, Corp. Adhesif polyurethanne durcissant a l'humidite, a un composant
CN102906210B (zh) * 2010-03-16 2014-10-15 汉高公司 硅烷湿固化性热熔黏合剂
WO2018049375A1 (fr) * 2016-09-12 2018-03-15 Momentive Performance Materials Inc. Catalyseur sans étain pour le durcissement d'un polymère contenant un alcoxysilyle

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111378413A (zh) * 2020-04-22 2020-07-07 湖北回天新材料股份有限公司 一种免底涂单组份聚氨酯密封胶及制备方法
EP3932966A1 (fr) * 2020-06-30 2022-01-05 Henkel AG & Co. KGaA Composition adhésive pour lier des substrats polaires et non polaires
US11472988B2 (en) 2020-11-04 2022-10-18 Bmic Llc Adhesive formulations including at least one silyl modified polymer
US11718773B2 (en) 2020-11-04 2023-08-08 Bmic Llc Adhesive formulations for roofing applications and related methods
CN113652192A (zh) * 2021-09-29 2021-11-16 苏州市陆氏新材料有限公司 一种pu胶黏剂的制备方法、pu胶黏剂及其应用于epdm粘结的方法

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