US20130274401A1 - Adhesive compositions and methods - Google Patents

Adhesive compositions and methods Download PDF

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US20130274401A1
US20130274401A1 US13/864,095 US201313864095A US2013274401A1 US 20130274401 A1 US20130274401 A1 US 20130274401A1 US 201313864095 A US201313864095 A US 201313864095A US 2013274401 A1 US2013274401 A1 US 2013274401A1
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adhesive composition
polyurethane adhesive
mol
aliphatic polycarbonate
certain embodiments
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Scott D. Allen
Vahid Sendijarevic
James O'Connor
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Saudi Aramco Technologies Co
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Novomer Inc
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Assigned to ENERGY, UNITED STATES DEPARTMENT OF reassignment ENERGY, UNITED STATES DEPARTMENT OF CONFIRMATORY LICENSE (SEE DOCUMENT FOR DETAILS). Assignors: Novomer, Inc
Publication of US20130274401A1 publication Critical patent/US20130274401A1/en
Assigned to NOVOMER, INC. reassignment NOVOMER, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: O'CONNOR, JAMES, SENDIJAREVIC, VAHID, ALLEN, SCOTT D.
Priority to US14/720,242 priority patent/US20150344751A1/en
Assigned to SAUDI ARAMCO TECHNOLOGIES COMPANY reassignment SAUDI ARAMCO TECHNOLOGIES COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NOVOMER, INC.
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    • 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
    • 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
    • C08G18/089—Reaction retarding agents
    • 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
    • C08G18/28—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
    • 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
    • C08G18/44—Polycarbonates
    • 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
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • 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
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives
    • 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
    • C08G2170/00—Compositions for adhesives
    • C08G2170/80—Compositions for aqueous adhesives
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C

Definitions

  • This invention pertains to the field of polymers. More particularly, the invention pertains to polyurethane adhesives incorporating aliphatic polycarbonate polyols obtained via copolymerization of epoxides and carbon dioxide. Polyurethane adhesives are used for creating adhesive films as well as joining two substrates to one another.
  • Polyurethanes adhesives are a unique urethanes product group that vary widely in composition and are used in many different applications and market segments.
  • Typical product forms include reactive types such as 1-component, 2-component and hot-melt compositions, as well as non-reactive types such as solvent-borne, water-borne and hot-melt compositions, among others.
  • Polyurethane adhesives are normally defined as those adhesives that contain a number of urethane groups in the molecular backbone of a polymer comprising the adhesive or which are formed during use, regardless of the chemical composition of the rest of the chain.
  • a typical urethane adhesive may contain, in addition to urethane linkages, aliphatic and aromatic hydrocarbons, esters, ethers, amides, urea and allophonate groups.
  • An isocyanate group reacts with the hydroxyl groups of a polyol to form the repeating urethane linkage. Isocyanates will react with water to form a urea linkage and carbon dioxide as a by-product.
  • Linear polyurethane adhesives may be obtained by using compounds with two reactive groups such as diisocyanates and diols.
  • polyols with three or more hydroxyl groups i.e. a functionality of 3 or more
  • isocyanates with three or more isocyanate groups are reacted with a polyol
  • the resulting polymer is crosslinked.
  • crosslinking reactions may occur. Often, excess isocyante in the composition reacts with atmospheric water or moisture contained in the substrate.
  • One component adhesives are usually viscous liquid isocyanate-terminated pre-polymers at room temperature. They set by reaction of the free isocyantes groups with atmospheric moisture or with moisture contained in the substrate to form poly urea groups. They typically do not require mixing with other components before curing.
  • the prepolymers are prepared by reacting an excess of isocyanate with polyols. If the functionality of the prepolymer is greater than two the cured film will be chemically crosslinked.
  • Two component polyurethane adhesive compositions generally comprise components that are liquids or pastes at room temperature before they are mixed together.
  • the first component of the composition comprises a polyol and other ingredients, such as chain extenders, catalysts, blocking agents and other additives as desired.
  • the second component comprises monomeric, polymeric or prepolymeric polyisocyanate.
  • the two components of the adhesive are fully mixed together and the composition is then applied to a substrate.
  • the mixed composition then initiates cure and develops bonding strength while transforming into a solid form.
  • the curing reaction takes place between the free isocyanate groups and the active hydrogens from the polyol.
  • the isocyanates and polyols employed may have a functionality of two or higher to provide crosslinking in the adhesive.
  • Reactive hot melt adhesives are characterized as a readily meltable polyisocyanate polyurethane (NCO preppolymer) which is usually solid or highly viscous at room temperature. They set both physically by cooling and chemically by reaction with atmospheric moisture. Depending on the formulation, reactive polyurethane hot-melt adhesives cure to form elastomsers with flexible to hard properties and tough adhesive layers.
  • the prepolymers typically have a low free isocyanate content.
  • Non reactive solvent borne and water borne adhesives typically consist of a hydroxyl terminated polyurethane dissolved in a solvent.
  • the polyurethanes are usually obtained by reacting a diol with a diisocyanate.
  • the polymer solutions are applied to both substrate surfaces to be bonded, some time is allowed for the solvents to evaporate and the surfaces are bonded together, at which point interdiffusions of the polymer chains will occur.
  • Non-reactive hot melt adhesives typically consist of linear chains that are solid at room temperature and are often used in the lamination of textiles although they have many other applications. They usually consist of hydroxyl-terminated polyurethanes that form the adhesive bond by cooling from the molten state. In some cases these are also known as thermoplastic polyurethane adhesives.
  • the present invention encompasses polyurethane adhesives comprising polyisocyanates and aliphatic polycarbonate polyols derived from the copolymerization of CO 2 with one or more epoxides.
  • the aliphatic polycarbonate polyol chains contain a primary repeating unit having a structure:
  • such aliphatic polycarbonate chains are derived from the copolymerization of carbon dioxide with one or more epoxide substrates. Such copolymerizations are exemplified in published PCT application WO 2010/028362, the entirety of which is incorporated herein by reference.
  • the aliphatic polycarbonate chains are derived from ethylene oxide, propylene oxide, or optionally substituted C 3-30 aliphatic epoxides, or mixtures of two or more of these.
  • the aliphatic polycarbonate chains have a number average molecular weight (Mn) less than about 20,000 g/mol. In certain embodiments, the aliphatic polycarbonate polyols have a functional number of between about 1.8 and about 6.
  • the present invention encompasses isocyanate-terminated prepolymers comprising a plurality of epoxide-CO 2 -derived polyol segments linked via urethane bonds formed from reaction with polyisocyanate compounds.
  • the invention comprises a process for bonding two substrates together by contacting the adhesive composition of the invention with at least one of the substrates and contacting the substrates together along a portion to which the adhesive was applied, and allowing the adhesive to cure thereby bonding the substrates together.
  • Certain compounds of the present invention can comprise one or more asymmetric centers, and thus can exist in various stereoisomeric forms, e.g., enantiomers and/or diastereomers.
  • inventive compounds and compositions thereof may be in the form of an individual enantiomer, diastereomer or geometric isomer, or may be in the form of a mixture of stereoisomers.
  • the compounds of the invention are enantiopure compounds.
  • mixtures of enantiomers or diastereomers are provided.
  • certain compounds, as described herein may have one or more double bonds that can exist as either the Z or E isomer, unless otherwise indicated.
  • the invention additionally encompasses the compounds as individual isomers substantially free of other isomers and alternatively, as mixtures of various isomers, e.g., racemic mixtures of enantiomers.
  • this invention also encompasses compositions comprising one or more compounds.
  • isomers includes any and all geometric isomers and stereoisomers.
  • “isomers” include cis- and trans-isomers, E- and Z-isomers, R- and S-enantiomers, diastereomers, (D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixtures thereof, as falling within the scope of the invention.
  • a stereoisomer may, in some embodiments, be provided substantially free of one or more corresponding stereoisomers, and may also be referred to as “stereochemically enriched.”
  • a particular enantiomer may, in some embodiments be provided substantially free of the opposite enantiomer, and may also be referred to as “optically enriched.”
  • “Optically enriched,” as used herein, means that the compound or polymer is made up of a significantly greater proportion of one enantiomer. In certain embodiments the compound is made up of at least about 90% by weight of a preferred enantiomer. In other embodiments the compound is made up of at least about 95%, 98%, or 99% by weight of a preferred enantiomer.
  • Preferred enantiomers may be isolated from racemic mixtures by any method known to those skilled in the art, including chiral high pressure liquid chromatography (HPLC) and the formation and crystallization of chiral salts or prepared by asymmetric syntheses.
  • HPLC high pressure liquid chromatography
  • Jacques, et al. Enantiomers, Racemates and Resolutions (Wiley Interscience, New York, 1981); Wilen, S. H., et al., Tetrahedron 33:2725 (1977); Eliel, E. L. Stereochemistry of Carbon Compounds (McGraw-Hill, NY, 1962); Wilen, S. H. Tables of Resolving Agents and Optical Resolutions p. 268 (E. L. Eliel, Ed., Univ. of Notre Dame Press, Notre Dame, Ind. 1972).
  • epoxide refers to a substituted or unsubstituted oxirane.
  • substituted oxiranes include monosubstituted oxiranes, disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstituted oxiranes.
  • Such epoxides may be further optionally substituted as defined herein.
  • epoxides comprise a single oxirane moiety.
  • epoxides comprise two or more oxirane moieties.
  • polymer refers to a molecule of high relative molecular mass, the structure of which comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass.
  • a polymer is comprised of substantially alternating units derived from CO 2 and an epoxide (e.g., poly(ethylene carbonate).
  • epoxide e.g., poly(ethylene carbonate).
  • a polymer of the present invention is a copolymer, terpolymer, heteropolymer, block copolymer, or tapered heteropolymer incorporating two or more different epoxide monomers. With respect to the structural depiction of such higher polymers, the convention of showing enchainment of different monomer units separated by a slash may be used herein
  • halo and “halogen” as used herein refer to an atom selected from fluorine (fluoro, —F), chlorine (chloro, —Cl), bromine (bromo, —Br), and iodine (iodo, —I).
  • aliphatic or “aliphatic group”, as used herein, denotes a hydrocarbon moiety that may be straight-chain (i.e., unbranched), branched, or cyclic (including fused, bridging, and spiro-fused polycyclic) and may be completely saturated or may contain one or more units of unsaturation, but which is not aromatic. Unless otherwise specified, aliphatic groups contain 1-40 carbon atoms. In certain embodiments, aliphatic groups contain 1-20 carbon atoms. In certain embodiments, aliphatic groups contain 3-20 carbon atoms. In certain embodiments, aliphatic groups contain 1-12 carbon atoms. In certain embodiments, aliphatic groups contain 1-8 carbon atoms.
  • aliphatic groups contain 1-6 carbon atoms. In some embodiments, aliphatic groups contain 1-5 carbon atoms, in some embodiments, aliphatic groups contain 1-4 carbon atoms, in some embodiments aliphatic groups contain 1-3 carbon atoms, and in some embodiments aliphatic groups contain 1 or 2 carbon atoms.
  • Suitable aliphatic groups include, but are not limited to, linear or branched, alkyl, alkenyl, and alkynyl groups, and hybrids thereof such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.
  • heteroaliphatic refers to aliphatic groups wherein one or more carbon atoms are independently replaced by one or more atoms selected from the group consisting of oxygen, sulfur, nitrogen, or phosphorus. In certain embodiments, one to six carbon atoms are independently replaced by one or more of oxygen, sulfur, nitrogen, or phosphorus. Heteroaliphatic groups may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and include saturated, unsaturated or partially unsaturated groups.
  • bivalent C 1-8 (or C 1-3 ) saturated or unsaturated, straight or branched, hydrocarbon chain”, refers to bivalent alkyl, alkenyl, and alkynyl, chains that are straight or branched as defined herein.
  • cycloaliphatic refers to a saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic ring systems, as described herein, having from 3 to 12 members, wherein the aliphatic ring system is optionally substituted as defined above and described herein.
  • Cycloaliphatic groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, norbornyl, adamantyl, and cyclooctadienyl.
  • the cycloalkyl has 3-6 carbons.
  • cycloaliphatic also include aliphatic rings that are fused to one or more aromatic or nonaromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the radical or point of attachment is on the aliphatic ring.
  • the term “3- to 7-membered carbocycle” refers to a 3- to 7-membered saturated or partially unsaturated monocyclic carbocyclic ring.
  • the term “3- to 8-membered carbocycle” refers to a 3- to 8-membered saturated or partially unsaturated monocyclic carbocyclic ring.
  • the terms “3- to 14-membered carbocycle” and “C 3-14 carbocycle” refer to a 3- to 8-membered saturated or partially unsaturated monocyclic carbocyclic ring, or a 7- to 14-membered saturated or partially unsaturated polycyclic carbocyclic ring.
  • alkyl refers to saturated, straight- or branched-chain hydrocarbon radicals derived from an aliphatic moiety containing between one and six carbon atoms by removal of a single hydrogen atom. Unless otherwise specified, alkyl groups contain 1-12 carbon atoms. In certain embodiments, alkyl groups contain 1-8 carbon atoms. In certain embodiments, alkyl groups contain 1-6 carbon atoms. In some embodiments, alkyl groups contain 1-5 carbon atoms, in some embodiments, alkyl groups contain 1-4 carbon atoms, in some embodiments alkyl groups contain 1-3 carbon atoms, and in some embodiments alkyl groups contain 1-2 carbon atoms.
  • alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, sec-pentyl, iso-pentyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-decyl, n-undecyl, dodecyl, and the like.
  • alkenyl denotes a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon double bond by the removal of a single hydrogen atom. Unless otherwise specified, alkenyl groups contain 2-12 carbon atoms. In certain embodiments, alkenyl groups contain 2-8 carbon atoms. In certain embodiments, alkenyl groups contain 2-6 carbon atoms. In some embodiments, alkenyl groups contain 2-5 carbon atoms, in some embodiments, alkenyl groups contain 2-4 carbon atoms, in some embodiments alkenyl groups contain 2-3 carbon atoms, and in some embodiments alkenyl groups contain 2 carbon atoms. Alkenyl groups include, for example, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl, and the like.
  • alkynyl refers to a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon triple bond by the removal of a single hydrogen atom. Unless otherwise specified, alkynyl groups contain 2-12 carbon atoms. In certain embodiments, alkynyl groups contain 2-8 carbon atoms. In certain embodiments, alkynyl groups contain 2-6 carbon atoms. In some embodiments, alkynyl groups contain 2-5 carbon atoms, in some embodiments, alkynyl groups contain 2-4 carbon atoms, in some embodiments alkynyl groups contain 2-3 carbon atoms, and in some embodiments alkynyl groups contain 2 carbon atoms. Representative alkynyl groups include, but are not limited to, ethynyl, 2-propynyl (propargyl), 1-propynyl, and the like.
  • alkoxy refers to an alkyl group, as previously defined, attached to the parent molecule through an oxygen atom.
  • alkoxy include but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, and n-hexoxy.
  • acyl refers to a carbonyl-containing functionality, e.g., —C( ⁇ O)R, wherein R is hydrogen or an optionally substituted aliphatic, heteroaliphatic, heterocyclic, aryl, heteroaryl group, or is a substituted (e.g., with hydrogen or aliphatic, heteroaliphatic, aryl, or heteroaryl moieties) oxygen or nitrogen containing functionality (e.g., forming a carboxylic acid, ester, or amide functionality).
  • acyloxy refers to an acyl group attached to the parent molecule through an oxygen atom.
  • aryl used alone or as part of a larger moiety as in “aralkyl”, “aralkoxy”, or “aryloxyalkyl”, refers to monocyclic and polycyclic ring systems having a total of five to 20 ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains three to twelve ring members.
  • aryl may be used interchangeably with the term “aryl ring”.
  • aryl refers to an aromatic ring system which includes, but is not limited to, phenyl, biphenyl, naphthyl, anthracyl and the like, which may bear one or more substituents.
  • aryl is a group in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenantriidinyl, or tetrahydronaphthyl, and the like.
  • the terms “6- to 10-membered aryl” and “C 6-10 aryl” refer to a phenyl or an 8- to 10-membered polycyclic aryl ring.
  • heteroatom refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen.
  • Heteroaryl groups include, without limitation, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, benzofuranyl and pteridinyl.
  • heteroaryl and “heteroar-”, as used herein, also include groups in which a heteroaromatic ring is fused to one or more aryl, cycloaliphatic, or heterocyclyl rings, where the radical or point of attachment is on the heteroaromatic ring.
  • Nonlimiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-1,4-oxazin-3(4H)-one.
  • heteroaryl group may be mono- or bicyclic.
  • heteroaryl may be used interchangeably with the terms “heteroaryl ring”, “heteroaryl group”, or “heteroaromatic”, any of which terms include rings that are optionally substituted.
  • heteroarylkyl refers to an alkyl group substituted by a heteroaryl, wherein the alkyl and heteroaryl portions independently are optionally substituted.
  • the term “5- to 10-membered heteroaryl” refers to a 5- to 6-membered heteroaryl ring having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8- to 10-membered bicyclic heteroaryl ring having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • the term “5- to 12-membered heteroaryl” refers to a 5- to 6-membered heteroaryl ring having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8- to 12-membered bicyclic heteroaryl ring having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • heterocycle As used herein, the terms “heterocycle”, “heterocyclyl”, “heterocyclic radical”, and “heterocyclic ring” are used interchangeably and refer to a stable 5- to 7-membered monocyclic or 7-14-membered polycyclic heterocyclic moiety that is either saturated or partially unsaturated, and having, in addition to carbon atoms, one or more, preferably one to four, heteroatoms, as defined above.
  • nitrogen includes a substituted nitrogen.
  • the nitrogen in a saturated or partially unsaturated ring having 0-3 heteroatoms selected from oxygen, sulfur or nitrogen, the nitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl), or + NR (as in N-substituted pyrrolidinyl).
  • the term “3- to 7-membered heterocyclic” refers to a 3- to 7-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • the term “3- to 12-membered heterocyclic” refers to a 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or a 7- to 12-membered saturated or partially unsaturated polycyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • a heterocyclic ring can be attached to its pendant group at any heteroatom or carbon atom that results in a stable structure and any of the ring atoms can be optionally substituted.
  • saturated or partially unsaturated heterocyclic radicals include, without limitation, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl.
  • heterocycle refers to an alkyl group substituted by a heterocyclyl, wherein the alkyl and heterocyclyl portions independently are optionally substituted.
  • partially unsaturated refers to a ring moiety that includes at least one double or triple bond.
  • partially unsaturated is intended to encompass rings having multiple sites of unsaturation, but is not intended to include aryl or heteroaryl moieties, as herein defined.
  • compounds of the invention may contain “optionally substituted” moieties.
  • substituted whether preceded by the term “optionally” or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent.
  • an “optionally substituted” group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position.
  • Combinations of substituents envisioned by this invention are preferably those that result in the formation of stable or chemically feasible compounds.
  • stable refers to compounds that are not substantially altered when subjected to conditions to allow for their production, detection, and, in certain embodiments, their recovery, purification, and use for one or more of the purposes disclosed herein.
  • Suitable monovalent substituents on a substitutable carbon atom of an “optionally substituted” group are independently halogen; —(CH 2 ) 0-4 R ⁇ ; —(CH 2 ) 0-4 OR ⁇ ; —O—(CH 2 ) 0-4 C(O)OR ⁇ ; —(CH 2 ) 0-4 —CH(OR ⁇ ) 2 ; —(CH 2 ) 0-4 SR ⁇ ; —(CH 2 ) 0-4 Ph, which may be substituted with R ⁇ ; —(CH 2 ) 0-4 O(CH 2 ) 0-1 Ph which may be substituted with R ⁇ ; —CH ⁇ CHPh, which may be substituted with R ⁇ ; NO 2 ; —CN; —N 3 ; —(CH 2 ) 0-4 N(R ⁇ ) 2 ; —(CH 2 ) 0-4 N(R ⁇ )C(O)R ⁇ ; —
  • Suitable monovalent substituents on R ⁇ are independently halogen, —(CH 2 ) 0-2 R ⁇ , -(haloR ⁇ ), —(CH 2 ) 0-2 OH, —(CH 2 ) 0-2 OR ⁇ , —(CH 2 ) 0-2 CH(OR ⁇ ) 2 ; —O(haloR ⁇ ), —CN, —N 3 , —(CH 2 ) 0-2 C(O)R ⁇ , —(CH 2 ) 0-2 C(O)OH, —(CH 2 ) 0-2 C(O)OR ⁇ , —(CH 2 ) 0-4 C(O)N(R ⁇ ) 2 ; —(CH 2 ) 0-2 SR ⁇ , —(CH 2 ) 0-2 SH, —(CH 2 ) 0-2 NH
  • Suitable divalent substituents on a saturated carbon atom of an “optionally substituted” group include the following: ⁇ O, ⁇ S, ⁇ NNR* 2 , ⁇ NNHC(O)R*, ⁇ NNHC(O)OR*, ⁇ NNHS(O) 2 R*, ⁇ NR*, ⁇ NOR*, —O(C(R* 2 )) 2-3 O—, or —S(C(R* 2 )) 2-3 S—, wherein each independent occurrence of R* is selected from hydrogen, C 1-6 aliphatic which may be substituted as defined below, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • Suitable divalent substituents that are bound to vicinal substitutable carbons of an “optionally substituted” group include: —O(CR* 2 ) 2-3 O—, wherein each independent occurrence of R* is selected from hydrogen, C 1-6 aliphatic which may be substituted as defined below, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • Suitable substituents on the aliphatic group of R* include halogen, —R ⁇ , —(haloR ⁇ ), —OH, —OR ⁇ , —O(haloR ⁇ ), —CN, —C(O)OH, —C(O)OR ⁇ , —NH 2 , —NHR ⁇ , —NR ⁇ 2 , or —NO 2 , wherein each R ⁇ is unsubstituted or where preceded by “halo” is substituted only with one or more halogens, and is independently C 1-4 aliphatic, —CH 2 Ph, —O(CH 2 ) 0-1 Ph, or a 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • Suitable substituents on a substitutable nitrogen of an “optionally substituted” group include —R ⁇ , —NR ⁇ 2 , —C(O)R ⁇ , —C(O)OR ⁇ , —C(O)C(O)R ⁇ , —C(O)CH 2 C(O)R ⁇ , —S(O) 2 R ⁇ , —S(O) 2 NR ⁇ 2 , —C(S)NR ⁇ 2 , —C(NH)NR ⁇ 2 , or —N(R ⁇ )S(O) 2 R ⁇ ; wherein each R ⁇ is independently hydrogen, C 1-6 aliphatic which may be substituted as defined below, unsubstituted —OPh, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or, notwithstanding the definition above, two independent occurrence
  • Suitable substituents on the aliphatic group of R ⁇ are independently halogen, —R ⁇ , -(haloR ⁇ ), —OH, —OR ⁇ , —O(haloR ⁇ ), —CN, —C(O)OH, —C(O)R ⁇ , —NH 2 , —NHR ⁇ , —NR ⁇ 2 , or —NO 2 , wherein each R ⁇ is unsubstituted or where preceded by “halo” is substituted only with one or more halogens, and is independently C 1-4 aliphatic, —CH 2 Ph, —O(CH 2 ) 0-1 Ph, or a 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
  • radical or “optionally substituted radical” is sometimes used.
  • “radical” means a moiety or functional group having an available position for attachment to the structure on which the substituent is bound. In general the point of attachment would bear a hydrogen atom if the substituent were an independent neutral molecule rather than a substituent.
  • the terms “radical” or “optionally-substituted radical” in this context are thus interchangeable with “group” or “optionally-substituted group”.
  • head-to-tail refers to the regiochemistry of adjacent repeating units in a polymer chain.
  • PPC poly(propylene carbonate)
  • head-to-tail ratio refers to the proportion of head-to-tail linkages to the sum of all other regiochemical possibilities.
  • H:T head-to-tail ratio
  • alkoxylated means that one or more functional groups on a molecule (usually the functional group is an alcohol, amine, or carboxylic acid, but is not strictly limited to these) has appended to it a hydroxy-terminated alkyl chain.
  • Alkoxylated compounds may comprise a single alkyl group or they may be oligomeric moieties such as hydroxyl-terminated polyethers.
  • Alkoxylated materials can be derived from the parent compounds by treatment of the functional groups with epoxides.
  • FIG. 1 shows the hardness and tensile strength of an adhesive composition of the present invention in comparison to adhesive formulations based on commercial polyester or polycarbonate polyols.
  • FIG. 2 shows a spider graph showing several properties of an adhesive composition of the present invention in comparison to adhesive formulations based on commercial polycarbonate polyols.
  • FIG. 3 shows the adhesion to a range of substrates of an adhesive composition of the present invention.
  • FIG. 4 shows the strength retention at elevated temperatures of an adhesive composition of the present invention in comparison to adhesive formulations based on commercial polyester or polycarbonate polyols.
  • FIG. 5 shows the solvent resistance of an adhesive composition of the present invention in comparison to adhesive formulations based on commercial polyester or polycarbonate polyols.
  • FIG. 6 shows the chemical resistance profile of an adhesive composition of the present invention.
  • FIG. 7 shows the transparency of polyurethane composition of the present invention in comparison to formulations based on commercial polycarbonate polyols.
  • FIG. 8 shows the strength and elongation of several blended adhesive formulations of the present invention.
  • the present invention encompasses polymer compositions comprising aliphatic polycarbonate chains cross-linked or chain extended through urethane linkages.
  • these polymer compositions comprise polyurethane adhesives.
  • the polyurethane compositions of the present invention are derived by combining two compositions: a first composition comprising one or more isocyanate compounds optionally containing diluents, solvents, coreactants and the like, and a second composition comprising one or more aliphatic polycarbonate polyols optionally with additional reactants, solvents, catalysts, or additives. These compositions may be formulated separately and then combined or all components of the finished polyurethane composition may be combined in a single step. Before fully describing these compositions, the polyols and isocyanates from which they are formulated will be more fully described.
  • compositions of the present invention comprise aliphatic polycarbonate polyols derived from the copolymerization of one or more epoxides and carbon dioxide.
  • suitable polyols, as well as methods of making them are disclosed in PCT publication WO2010/028362 the entirety of which is incorporated herein by reference.
  • the aliphatic polycarbonate polyols used have a high percentage of reactive end groups.
  • Such reactive end-groups are typically hydroxyl groups, but other reactive functional groups may be present if the polyols are treated to modify the chemistry of the end groups, such modified materials may terminate in amino groups, thiol groups, alkene groups, carboxylate groups, isocyanate groups, silyl groups, epoxy groups and the like.
  • the term ‘aliphatic polycarbonate polyol’ includes both traditional hydroxy-terminated materials as well as these end-group modified compositions.
  • At least 90% of the end groups of the polycarbonate polyol used are reactive end groups. In certain embodiments, at least 95%, at least 96%, at least 97% or at least 98% of the end groups of the polycarbonate polyol used are reactive end groups. In certain embodiments, more than 99%, more than 99.5%, more than 99.7%, or more than 99.8% of the end groups of the polycarbonate polyol used are reactive end groups. In certain embodiments, more than 99.9% of the end groups of the polycarbonate polyol used are reactive end groups.
  • At least 90% of the end groups of the polycarbonate polyol used are —OH groups. In certain embodiments, at least 95%, at least 96%, at least 97% or at least 98% of the end groups of the polycarbonate polyol used are —OH groups. In certain embodiments, more than 99%, more than 99.5%, more than 99.7%, or more than 99.8% of the end groups of the polycarbonate polyol used are —OH groups. In certain embodiments, more than 99.9% of the end groups of the polycarbonate polyol used are —OH groups.
  • the aliphatic polycarbonate polyols used in the present invention have an OH# greater than about 20. In certain embodiments, the aliphatic polycarbonate polyols utilized in the present invention have an OH# greater than about 40. In certain embodiments, the aliphatic polycarbonate polyols have an OH# greater than about 50, greater than about 75, greater than about 100, or greater than about 120.
  • the aliphatic polycarbonate polyol compositions have a substantial proportion of primary hydroxyl end groups. These are the norm for compositions comprising poly(ethylene carbonate), but for polyols derived from the copolymerization of substituted epoxides with CO 2 , it is common for some or most of the chain ends to consist of secondary hydroxyl groups. In certain embodiments, such polyols are treated to increase the proportion of primary —OH end groups. This may be accomplished by reacting the secondary hydroxyl groups with reagents such as ethylene oxide, reactive lactones, and the like.
  • the aliphatic polycarbonate polyols are treated with beta lactones, caprolactone and the like to introduce primary hydroxyl end groups. In certain embodiments, the aliphatic polycarbonate polyols are treated with ethylene oxide to introduce primary hydroxyl end groups.
  • aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and one or more epoxides. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and ethylene oxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and propylene oxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and 1,2-butene oxide and/or 1,2-hexene oxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and cyclohexene oxide.
  • aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and cyclopentene oxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and 3-vinyl cyclohexene oxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and 3-ethyl cyclohexene oxide.
  • aliphatic polycarbonate chains comprise a terpolymer of carbon dioxide and ethylene oxide along with one or more additional epoxides selected from the group consisting of propylene oxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3-vinyl cyclohexene oxide, 3-ethyl cyclohexene oxide, cyclopentene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers, styrene oxides, and epoxides of higher alpha olefins.
  • such terpolymers contain a majority of repeat units derived from ethylene oxide with lesser amounts of repeat units derived from one or more additional epoxides. In certain embodiments, terpolymers contain about 50% to about 99.5% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than about 60% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 75% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 80% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 85% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 90% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 95% ethylene oxide-derived repeat units.
  • the aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and propylene oxide along with one or more additional epoxides selected from the group consisting of ethylene oxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3-vinyl cyclohexene oxide, cyclopentene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers, styrene oxides, and epoxides of higher alpha olefins.
  • additional epoxides selected from the group consisting of ethylene oxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3-vinyl cyclohexene oxide, cyclopentene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers, styrene oxides, and epoxides of higher
  • such terpolymers contain a majority of repeat units derived from propylene oxide with lesser amounts of repeat units derived from one or more additional epoxides. In certain embodiments, terpolymers contain about 50% to about 99.5% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 60% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 75% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 80% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 85% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 90% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 95% propylene oxide-derived repeat units.
  • aliphatic polycarbonate chains have a number average molecular weight (M n ) in the range of 500 g/mol to about 250,000 g/mol.
  • aliphatic polycarbonate chains have an M n less than about 100,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n less than about 70,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n less than about 50,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n between about 500 g/mol and about 40,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n less than about 25,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n between about 500 g/mol and about 20,000 g/mol.
  • aliphatic polycarbonate chains have an M n between about 500 g/mol and about 10,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n between about 500 g/mol and about 5,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n between about 1,000 g/mol and about 5,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n between about 5,000 g/mol and about 10,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n between about 500 g/mol and about 1,000 g/mol.
  • aliphatic polycarbonate chains have an M n between about 1,000 g/mol and about 3,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n of about 5,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n of about 4,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n of about 3,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n of about 2,500 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n of about 2,000 g/mol.
  • aliphatic polycarbonate chains have an M n of about 1,500 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n of about 1,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n of about 750 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M n of about 500 g/mol.
  • the aliphatic polycarbonate polyols used are characterized in that they have a narrow molecular weight distribution. This can be indicated by the polydispersity indices (PDI) of the aliphatic polycarbonate polymers.
  • aliphatic polycarbonate compositions have a PDI less than 3.
  • aliphatic polycarbonate compositions have a PDI less than 2.
  • aliphatic polycarbonate compositions have a PDI less than 1.8.
  • aliphatic polycarbonate compositions have a PDI less than 1.5.
  • aliphatic polycarbonate compositions have a PDI less than 1.4.
  • aliphatic polycarbonate compositions have a PDI between about 1.0 and 1.2.
  • aliphatic polycarbonate compositions have a PDI between about 1.0 and 1.1.
  • the aliphatic polycarbonate polyols used do not have a narrow PDI, this can be the case if, for example, a polydisperse chain transfer agent is used to initiate an epoxide CO 2 copolymerization, or if a plurality of aliphatic polycarbonate polyol compositions with different PDIs are blended.
  • aliphatic polycarbonate compositions have a PDI greater than 3.
  • aliphatic polycarbonate compositions have a PDI greater than 2.
  • aliphatic polycarbonate compositions have a PDI greater than 1.8.
  • aliphatic polycarbonate compositions have a PDI greater than 1.5.
  • aliphatic polycarbonate compositions have a PDI greater than 1.4.
  • aliphatic polycarbonate compositions of the present invention comprise substantially alternating polymers containing a high percentage of carbonate linkages and a low content of ether linkages. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 85% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 90% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 91% or greater.
  • aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 92% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 93% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 94% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 95% or greater.
  • aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 96% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 97% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 98% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 99% or greater.
  • aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 99.5% or greater. In certain embodiments, the percentages above exclude ether linkages present in polymerization initiators or chain transfer agents and refer only to the linkages formed during epoxide CO 2 copolymerization.
  • aliphatic polycarbonate compositions of the present invention are characterized in that they contain essentially no ether linkages either within the polymer chains derived from epoxide CO 2 copolymerization or within any polymerization initiators, chain transfer agents or end groups that may be present in the polymer. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that they contain, on average, less than one ether linkage per polymer chain within the composition. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that they contain essentially no ether linkages.
  • an aliphatic polycarbonate is derived from mono-substituted epoxides (e.g. such as propylene oxide, 1,2-butylene oxide, epichlorohydrin, epoxidized alpha olefins, or a glycidol derivative)
  • the aliphatic polycarbonate is characterized in that it is regioregular.
  • Regioregularity may be expressed as the percentage of adjacent monomer units that are oriented in a head-to-tail arrangement within the polymer chain.
  • aliphatic polycarbonate chains in the inventive polymer compositions have a head-to-tail content higher than about 80%.
  • the head-to-tail content is higher than about 85%. In certain embodiments, the head-to-tail content is higher than about 90%. In certain embodiments, the head-to-tail content is greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94%, or greater than about 95%. In certain embodiments, the head-to-tail content of the polymer is as determined by proton or carbon-13 NMR spectroscopy.
  • compositions of the present invention comprise aliphatic polycarbonate polyols having a structure P1:
  • R 1 , R 2 , R 3 , and R 4 are, at each occurrence in the polymer chain, independently selected from the group consisting of —H, fluorine, an optionally substituted C 1-30 aliphatic group, and an optionally substituted C 1-40 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R 1 , R 2 , R 3 , and R 4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms;
  • Y is, at each occurrence, independently —H, a reactive group (as defined hereinabove), or a site of attachment to any of the chain-extending moieties or isocyanates described in the classes and subclasses herein;
  • n is at each occurrence, independently an integer from about 2 to about 50;
  • x and y are each independently an integer from 0 to 6, where the sum of x and y is between 2 and 6.
  • the multivalent moiety is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N
  • polyfunctional chain transfer agent having two or more sites from which epoxide/CO 2 copolymerization can occur.
  • such copolymerizations are performed in the presence of polyfunctional chain transfer agents as exemplified in published PCT application WO/2009056220.
  • such copolymerizations are performed as exemplified in US 2011/0245424.
  • such copolymerizations are performed as exemplified in Green Chem. 2011, 13, 3469-3475.
  • a polyfunctional chain transfer agent has a formula:
  • x, and y is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains in the inventive polymer compositions are derived from the copolymerization of one or more epoxides with carbon dioxide in the presence of such polyfunctional chain transfer agents as shown in Scheme 2:
  • aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with a structure P2:
  • n is as defined above and described in the classes and subclasses herein.
  • the dihydric alcohol is derived from a dihydric alcohol, the dihydric alcohol comprises a C 2-40 diol.
  • the dihydric alcohol is selected from the group consisting of: 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol, 2-methyl-2,4-pentane diol, 2-ethyl-1,3-hexane diol, 2-methyl-1,3-propane diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-
  • dihydric alcohol is selected from the group consisting of: diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly(ethylene glycol), such as those having number average molecular weights of from 220 to about 2000 g/mol, dipropylene glycol, tripropylene glycol, and higher poly(propylene glycol) such as those having number average molecular weights of from 234 to about 2000 g/mol.
  • the dihydric alcohol comprises an alkoxylated derivative of a compound selected from the group consisting of: a diacid, a diol, or a hydroxy acid.
  • the alkoxylated derivatives comprise ethoxylated or propoxylated compounds.
  • the dihydric alcohol comprises a polymeric diol.
  • a polymeric diol is selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether polycarbonates, polycarbonate-copolyesters, polyoxymethylene polymers, and alkoxylated analogs of any of these.
  • the polymeric diol has an average molecular weight less than about 2000 g/mol.
  • these >2 functional polyols are a component of a polyol mixture containing predominantly polyols with two hydroxyl groups. In certain embodiments, these >2 functional polyols are less than 20% of the total polyol mixture by weight. In certain embodiments, these >2 functional polyols are less than 10% of the total polyol mixture. In certain embodiments, these >2 functional polyols are less than 5% of the total polyol mixture. In certain embodiments, these >2 functional polyols are less than 2% of the total polyol mixture.
  • the aliphatic polycarbonate chains in polymer compositions of the present invention comprise aliphatic polycarbonate chains where the moiety
  • such aliphatic polycarbonate chains have the structure P3:
  • n is as defined above and described in classes and subclasses herein.
  • triol is derived from a triol, the triol is selected from the group consisting of: glycerol, 1,2,4-butanetriol, 2-(hydroxymethyl)-1,3-propanediol; hexane triols, trimethylol propane, trimethylol ethane, trimethylolhexane, 1,4-cyclohexanetrimethanol, pentaerythritol mono esters, pentaerythritol mono ethers, and alkoxylated analogs of any of these.
  • alkoxylated derivatives comprise ethoxylated or propoxylated compounds.
  • alkoxylated derivative is derived from an alkoxylated derivative of a trifunctional carboxylic acid or trifunctional hydroxy acid.
  • alkoxylated derivatives comprise ethoxylated or propoxylated compounds.
  • the polymeric triol is selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether polycarbonates, polyoxymethylene polymers, polycarbonate-copolyesters, and alkoxylated analogs of any of these.
  • the alkoxylated polymeric triols comprise ethoxylated or propoxylated compounds.
  • aliphatic polycarbonate chains in polymer compositions of the present invention comprise aliphatic polycarbonate chains where the moiety
  • aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P4:
  • n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P5:
  • n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonates of the present invention comprise a combination of bifunctional chains (e.g. polycarbonates of formula P2) in combination with higher functional chains (e.g. one or more polycarbonates of formulae P3 to P5).
  • aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P6:
  • n is as defined above and described in classes and subclasses herein. In such instances,
  • polyesters are derived from a polyester.
  • such polyesters have a molecular weight less than about 2000 g/mol.
  • a hydroxy acid is an alpha-hydroxy acid.
  • a hydroxy acid is selected from the group consisting of: glycolic acid, DL-lactic acid, D-lactic acid, L-lactic, citric acid, and mandelic acid.
  • a hydroxy acid is a beta-hydroxy acid.
  • a hydroxy acid is selected from the group consisting of: 3-hydroxypropionic acid, DL 3-hydroxybutryic acid, D-3 hydroxybutryic acid, L-3-hydroxybutyric acid, DL-3-hydroxy valeric acid, D-3-hydroxy valeric acid, L-3-hydroxy valeric acid, salicylic acid, and derivatives of salicylic acid.
  • a hydroxy acid is a ⁇ - ⁇ hydroxy acid.
  • a hydroxy acid is selected from the group consisting of: of optionally substituted C 3-20 aliphatic ⁇ - ⁇ hydroxy acids and oligomeric esters.
  • a hydroxy acid is selected from the group consisting of:
  • aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P7:
  • n is as defined above and described in classes and subclasses herein, and y′ is an integer from 1 to 5 inclusive.
  • R 1 , R 2 , R 3 , R 4 , Y, and n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P8:
  • phthalic acid is selected from the group consisting of: phthalic acid, isophthalic acid, terephthalic acid, maleic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid.
  • each R is independently an optionally substituted C 1-20 aliphatic group or an optionally substituted aryl group and k is 0, 1, or 2.
  • R 1 , R 2 , R 3 , R 4 , Y, and n is as defined above and described in classes and subclasses herein.
  • phosphorous-containing molecule selected from the group consisting of:
  • R has a formula —P(O)(R)— where R is an optionally substituted C 1-20 aliphatic group or an optionally substituted aryl group and k is 0, 1, or 2.
  • phosphorous-containing molecule selected from the group consisting of:
  • R d is as defined above.
  • R is an optionally substituted C 1-20 aliphatic group or an optionally substituted aryl group.
  • R x is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains comprise:
  • Y, and n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • —Y, R x , and n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains comprise
  • —Y, and n are is as defined above and described in classes and subclasses herein; and each independently represents a single or double bond.
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • R x , —Y and n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • aliphatic polycarbonate chains comprise
  • n is as defined above and described in classes and subclasses herein.
  • aliphatic polycarbonate chains comprise
  • ethylene glycol is selected from the group consisting of: ethylene glycol; diethylene glycol, triethylene glycol, 1,3propane diol; 1,4butane diol, hexylene glycol, 1,6hexane diol, propylene glycol, dipropylene glycol, tripropylene glycol, and alkoxylated derivatives of any of these.
  • polycarbonates comprising repeat units derived from two or more epoxides, such as those represented by structures P2f through P2r, depicted above
  • the structures drawn may represent mixtures of positional isomers or regioisomers that are not explicitly depicted.
  • the polymer repeat unit adjacent to either end group of the polycarbonate chains can be derived from either one of the two epoxides comprising the copolymers.
  • the terminal repeat units might be derived from either of the two epoxides and a given polymer composition might comprise a mixture of all of the possibilities in varying ratios.
  • the ratio of these end-groups can be influenced by several factors including the ratio of the differ rent epoxides used in the polymerization, the structure of the catalyst used, the reaction conditions used (i.e temperature pressure, etc.) as well as by the timing of addition of reaction components.
  • the drawings above may show a defined regiochemistry for repeat units derived from substituted epoxides, the polymer compositions will, in some cases, contain mixtures of regioisomers.
  • the regioselectivity of a given polymerization can be influenced by numerous factors including the structure of the catalyst used and the reaction conditions employed. To clarify, this means that the composition represented by structure P2r above, may contain a mixture of several compounds as shown in the diagram below.
  • This diagram shows the isomers graphically for polymer P2r, where the structures below the depiction of the chain show each regio- and positional isomer possible for the monomer unit adjacent to the chain transfer agent and the end groups on each side of the main polymer chain.
  • Each end group on the polymer may be independently selected from the groups shown on the left or right while the central portion of the polymer including the chain transfer agent and its two adjacent monomer units may be independently selected from the groups shown.
  • the polymer composition comprises a mixture of all possible combinations of these. In other embodiments, the polymer composition is enriched in one or more of these.
  • the aliphatic polycarbonate polyol is selected from the group consisting of Q1, Q2, Q3, Q4, Q5, Q6, and mixtures of any two or more of these.
  • the aliphatic polycarbonate polyol is selected from the group consisting of:
  • Poly(ethylene carbonate) of formula Q1 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene carbonate) of formula Q1 having an average molecular weight number of about 500 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene carbonate) of formula Q1 having an average molecular weight number of about 1,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene carbonate) of formula Q1 having an average molecular weight number of about 2,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene carbonate) of formula Q1 having an average molecular weight number of about 3,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 500 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 1,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 2,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;
  • Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 3,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydispersity index less than about 1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of about 500 g/mol, a polydispersity index less than about 1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of about 1,000 g/mol, a polydispersity index less than about 1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 11), a polydispersity index less than about 1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene-co-propylene carbonate) of formula Q3 having an average molecular weight number of about 3,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 4 and about 16), a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 500 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 1,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 2,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 3,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups.
  • Poly(propylene carbonate) of formula Q5 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;
  • Poly(propylene carbonate) of formula Q5 having an average molecular weight number of about 500 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;
  • Poly(propylene carbonate) of formula Q5 having an average molecular weight number of about 1,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;
  • Poly(propylene carbonate) of formula Q5 having an average molecular weight number of about 2,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;
  • Poly(propylene carbonate) of formula Q5 having an average molecular weight number of about 3,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydispersity index less than about 1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 500 g/mol, a polydispersity index less than about 1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 1,000 g/mol, a polydispersity index less than about 1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 11), a polydispersity index less than about 1.25, at least 90% carbonate linkages, and at least 98% —OH end groups;
  • Poly(ethylene-co-propylene carbonate) of formula Q6 having an average molecular weight number of about 3,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups;
  • the embedded chain transfer agent in certain embodiments, the embedded chain transfer agent
  • polymeric diol or higher polyhydric alcohol is a moiety derived from a polymeric diol or higher polyhydric alcohol.
  • polymeric alcohols are polyether or polyester polyols.
  • polyether polyol comprising ethylene glycol or propylene glycol repeating units (—OCH 2 CH 2 O—, or —OCH 2 CH(CH 3 )O—) or combinations of these.
  • ethylene glycol or propylene glycol repeating units —OCH 2 CH 2 O—, or —OCH 2 CH(CH 3 )O—
  • polyester polyol comprising the reaction product of a diol and a diacid, or a material derived from ring-opening polymerization of one or more lactones.
  • R q is at each occurrence in the polymer chain independently —H or —CH 3 ;
  • R a is —H, or —CH 3 ;
  • q and q′ are independently an integer from about 0 to about 40;
  • n is as defined above and in the examples and embodiments herein.
  • an aliphatic polycarbonate polyol is selected from the group consisting of:
  • aliphatic polycarbonate polyols comprise compounds conforming to structure Q7, the moiety
  • polyether polyol such as those typically used in the formulation of polyurethane compositions.
  • an aliphatic polycarbonate polyol is selected from the group consisting of:
  • were aliphatic polycarbonate polyols comprise compounds conforming to structure Q8, the moiety
  • polyester polyol such as those typically used in the formulation of polyurethane compositions.
  • compositions of the present invention comprise higher polymers derived from reactions with isocyanate reagents.
  • the purpose of these isocyanate reagents is to react with the reactive end groups on the aliphatic polycarbonate polyols to form higher molecular weight structures through chain extension and/or cross-linking.
  • the isocyanate reagents comprise two or more isocyanate groups per molecule.
  • the isocyanate reagents are diisocyanates.
  • the isocyanate reagents are higher polyisocyanates such as triisocyanates, tetraisocyanates, isocyanate polymers or oligomers, and the like, which are typically a minority component of a mix of predominately diisocyanates.
  • the isocyanate reagents are aliphatic polyisocyanates or derivatives or oligomers of aliphatic polyisocyanates.
  • the isocyanates are aromatic polyisocyanates or derivatives or oligomers of aromatic polyisocyanates.
  • the compositions may comprise mixtures of any two or more of the above types of isocyanates.
  • isocyanate reagents usable for the production of the polyurethane adhesive include aliphatic, cycloaliphatic and aromatic diisocyanate compounds.
  • Suitable aliphatic and cycloaliphatic isocyanate compounds include, for example, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 4,4,′-dicyclohexylmethane diisocyanate, 2,2′-diethylether diisocyanate, hydrogenated xylylene diisocyanate, and hexamethylene diisocyanate-biuret.
  • the aromatic isocyanate compounds include, for example, p-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenyl diisocyanate, 2,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 3,3′-methyleneditolylene-4,4′-diisocyanate, tolylenediisocyanate-trimethylolpropane adduct, triphenylmethane triisocyanate, 4,4′-diphenylether diisocyanate, tetrachlorophenylene diisocyanate, 3,3′-dichloro-4,4′-diphenylmethane diisocyanate, and triisocyanate phenylthiophosphate.
  • MDI 4,4′-diphenyl diisocyanate
  • the isocyanate compound employed comprises one or more of: 4,4′-diphenylmethane diisocyanate, 1,6-hexamethylene hexamethylene diisocyanate and isophorone diisocyanate.
  • the isocyanate compound employed is 4,4′-diphenylmethane diisocyanate.
  • the above-mentioned diisocyanate compounds may be employed alone or in mixtures of two or more thereof.
  • an isocyanate reagent is selected from the group consisting of: 1,6-hexamethylaminediisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4′methylene-bis(cyclohexyl isocyanate) (H 12 MDI), 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI), diphenylmethane-4,4′-diisocyanate (MDI), diphenylmethane-2,4′-diisocyanate (MDI), xylylene diisocyanate (XDI), 1,3-Bis(isocyanatomethyl)cyclohexane (H6-XDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate (TMXD), m-tetramethylxylylene diisocyanate (TMXD
  • an isocyanate reagent is selected from the group consisting of 4,4′-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate and isophorone diisocyanate.
  • an isocyanate reagent is 4,4′-diphenylmethane diisocyanate.
  • an isocyanate reagent is 1,6-hexamethylene diisocyanate.
  • an isocyanate reagent is isophorone diisocyanate.
  • Isocyanates suitable for certain embodiments of the present invention are available commercially under various trade names.
  • suitable commercially available isocyanates include materials sold under trade names: Desmodur® (Bayer Material Science), Tolonate® (Perstorp), Takenate® (Takeda), Vestanat® (Evonik), Desmotherm® (Bayer Material Science), Bayhydur® (Bayer Material Science), Mondur (Bayer Material Science), Suprasec (Huntsman Inc.), Lupranate® (BASF), Trixene (Baxenden), Hartben® (Benasedo), Ucopol® (Sapici), and Basonat® (BASF).
  • isocyanates suitable for certain embodiments of the present invention are sold under the trade name Lupranate® (BASF).
  • BASF isocyanates
  • the isocyanates are selected from the group consisting of the materials shown in Table 1, and typically from the subset of this list that are between 1.95 and 2.1 functional isocyanates:
  • isocyanates suitable for certain embodiments of the present invention are sold under the trade name Desmodur® available from Bayer Material Science.
  • the isocyanates are selected from the group consisting of the materials shown in Table 2, and typically from the subset of this list that are between 1.95 and 2.1 functional isocyanates:
  • Desmodur ® 2460 M Monomeric diphenylmethane diisocyanate with high 2,4′- isomer content
  • Desmodur ® 44 M A monomeric diphenylmethane-4,4′-diisocyanate (MDI).
  • Desmodur ® 44 MC Desmodur 44 MC Flakes is a monomeric diphenylmethane-4,4′- diisocyanate (MDI).
  • Desmodur ® CD-S is a modified isocyanate based on diphenylmethane-4,4′-diisocyanate.
  • Desmodur ® D XP 2725 Hydrophilically modified polyisocyanate
  • Desmodur ® DA-L Hydrophilic aliphatic polyisocyanate based on hexamethylene diisocyanate
  • Desmodur ® DN Aliphatic polyisocyanate of low volatility
  • Desmodur ® E 1160 Aromatic polyisocyanate prepolymer based on toluene diisocyanate Desmodur ® E 1361 BA
  • Desmodur ® E 1361 MPA/X Aromatic polyisocyanate prepolymer based on toluene diisocyanate
  • Desmodur ® E 14 Aromatic polyisocyanate prepolymer based on toluene diisocyan
  • Desmodur ® E 1660 Aromatic polyisocyanate prepolymer based on toluene diisocyanate.
  • Desmodur ® E 1750 PR Polyisocyanate prepolymer based on toluene diisocyanate
  • Desmodur ® E 20100 Modified polyisocyanate prepolymer based on diphenylmethane diisocyanate.
  • Desmodur ® E 21 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI).
  • Desmodur ® E 22 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate.
  • Desmodur ® E 2200/76 Desmodur E 2200/76 is a prepolymer based on (MDI) with isomers.
  • Desmodur ® E 23 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI).
  • Desmodur ® E 29 Polyisocyanate prepolymer based on diphenylmethane diisocyanate.
  • Desmodur ® E 305 is a largely linear aliphatic NCO prepolymer based on hexamethylene diisocyanate.
  • Desmodur ® E 3265 MPA/SN Aliphatic polyisocyanate prepolymer based on hexamethylene diisocyanate (HDI)
  • Desmodur ® E 3370 Aliphatic polyisocyanate prepolymer based on hexamethylene diisocyanate
  • Desmodur ® E XP 2605 Polyisocyanate prepolymer based on toluene diisocyanate and diphenylmethan diisocyanate
  • Desmodur ® E XP 2605 Polyisocyanate prepolymer based on toluene diisocyanate and diphenylmethan diisocyanate
  • Desmodur ® E XP 2715 Aromatic polyisocyanate prepolymer based on 2,4′- diphenylmethane diisocyanate (2
  • Desmodur ® E XP 2726 Aromatic polyisocyanate prepolymer based on 2,4′- diphenylmethane diisocyanate (2,4′-MDI)
  • Desmodur ® E XP 2727 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate.
  • Desmodur ® E XP 2762 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI).
  • Desmodur ® H Monomeric aliphatic diisocyanate
  • Desmodur ® HL Aromatic/aliphatic polyisocyanate based on toluylene diisocyanate/hexamethylene diisocyanate
  • Desmodur ® I Monomeric cycloaliphatic diisocyanate.
  • Desmodur ® PF is a modified diphenyl-methane-4,4′-diisocyanate (MDI).
  • Desmodur ® PL 350 Blocked aliphatic polyisocyanate based on HDI
  • TDI toluene diisocyanate
  • Desmodur ® VKS 10 is a mixture of diphenylmethane-4,4′- diisocyanate (MDI) with isomers and higher functional Desmodur ® VKS 20
  • Desmodur VKS 20 is a mixture of diphenylmethane-4,4′- diisocyanate (MDI) with isomers and higher functional Desmodur ® VKS 20 F
  • Desmodur VKS 20 F is a mixture of diphenylmethane-4,4′- diisocyanate (MDI) with isomers and higher functional Desmodur ® VKS 70
  • Desmodur VKS 70 is a mixture of diphenylmethane-4,4′- diisocyanate (MDI) with isomers and homologues.
  • Desmodur ® VP LS 2397 is a linear prepolymer based on polypropylene ether glycol and diphenylmethane diisocyanate Desmodur ® W Monomeric cycloaliphatic diisocyanate Desmodur ® W/1 Monomeric cycloaliphatic diisocyanate Desmodur ® XP 2404
  • Desmodur XP 2404 is a mixture of monomeric polyisocyanates
  • Desmodur ® XP 2406 Aliphatic polyisocyanate prepolymer based on isophorone diisocyanate
  • Desmodur ® XP 2489 Aliphatic polyisocyanate Desmodur ® XP 2505
  • Desmodur XP 2505 is a prepolymer containing ether groups based on diphenylmethane-4,4′-diisocyanates (MDI) with Desmodur ® XP 2551 Aromatic polyisocyanate based on diphenylmethan
  • Desmodur ® XP 2580 Aliphatic polyisocyanate based on hexamethylene diisocyanate
  • Desmodur ® XP 2599 Aliphatic prepolymer containing ether groups and based on hexamethylene-1,6-diisocyanate (HDI)
  • Desmodur ® XP 2617 Desmodur XP 2617 is a largely linear NCO prepolymer based on hexamethylene diisocyanate.
  • Desmodur ® XP 2665 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI).
  • Desmodur ® XP 2675 Aliphatic polyisocyanate (highly functional HDI trimer)
  • Desmodur ® XP 2679 Aliphatic polyisocyanate (HDI allophanate trimer)
  • Desmodur ® XP 2714 Silane-functional aliphatic polyisocyanate based on hexamethylene diisocyanate
  • Desmodur ® XP 2730 Low-viscosity, aliphatic polyisocyanate (HDI uretdione)
  • Desmodur ® XP 2731 Aliphatic polyisocyanate (HDI allophanate trimer)
  • Desmodur ® XP 2742 Modified aliphatic Polyisocyanate (HDI-Trimer), contains SiO2- nanoparticles
  • isocyanates suitable for certain embodiments of the present invention are sold under the trade name Tolonate® (Perstorp).
  • the isocyanates are selected from the group consisting of the materials shown in Table 3, and typically from the subset of this list that are between 1.95 and 2.1 functional isocyanates:
  • Tolonate TM D2 a blocked aliphatic polyisocyanate, supplied at 75% solids in aromatic solvent Tolonate TM HDB a viscous solvent-free aliphatic polyisocyanate Tolonate TM HDB-LV a solvent free low viscosity aliphatic polyisocyanate Tolonate TM HDB 75 B an aliphatic polyisocyanate, supplied at 75% solids in methoxy propyl acetate Tolonate TM HDB 75 an aliphatic polyisocyanate, supplied at 75% solids BX Tolonate TM HDT a medium viscosity, solvent-free aliphatic polyisocyanate Tolonate TM HDT-LV is a solvent free low viscosity aliphatic polyisocyanate Tolonate TM HDT-LV2 a solvent free, very low viscosity aliphatic polyisocyanate Tolonate TM HDT 90 an aliphatic polyis
  • isocyanates suitable for certain embodiments of the present invention are sold under the trade name Mondur® available from Bayer Material Science.
  • the isocyanates are selected from the group consisting of the materials shown in Table 4, and typically from the subset of this list that are between 1.95 and 2.1 functional isocyanates:
  • MONDUR 445 TDI/MDI blend polyisocyanate blend of toluene diisocyanate and polymeric diphenylmethane diisocyanate; NCO weight 44.5-45.2%
  • MONDUR 448 modified polymeric diphenylmethane diisocyanate (pMDI) prepolymer NCO weight 27.7%; viscosity 140 mPa ⁇ s @ 25° C.; equivalent weight 152; functionality 2.2
  • MONDUR 582 polymeric diphenylmethane diisocyanate (pMDI); binder for composite wood products and as a raw material in adhesive formulations; NCO weight 31.0%; viscosity 200 mPa ⁇ s @ 25° C.
  • MONDUR 1437 modified diphenylmethane diisocyanate mMDI
  • isocyanate-terminated polyether prepolymer NCO weight 10.0%; viscosity 2,500 mPa ⁇ s @ 25° C.; equivalent weight 420; functionality 2 MONDUR 1453 modified diphenylmethane diisocyanate (mMDI); isocyanate-terminated polyether prepolymer based on polypropylene ether glycol (PPG); NCO weight 16.5%; viscosity 600 mPa ⁇ s @ 25° C.; equivalent weight 254; functionality 2 MONDUR 1515 modified polymeric diphenylmethane diisocyanate (pMDI) prepolymer; used in the production of rigid polyurethane foams, especially for the appliance industry; NCO weight 30.5%; viscosity 350 mPa ⁇ s @ 25° C.
  • MONDUR 1522 modified monomeric 4,4-diphenylmethane diisocyanate (mMDI); NCO weight 29.5%; viscosity 50 mPa ⁇ s @ 25° C.; equivalent weight 143; functionality 2.2 MONDUR MA-2300 modified monomeric MDI, allophanate-modified 4,4′-diphenylmethane diisocyanate (mMDI); NCO weight 23.0%; viscosity 450 mPa ⁇ s @ 25° C.; equivalent weight 183; functionality 2.0 MONDUR MA 2600 modified monomeric MDI, allophanate-modified 4,4′-diphenylmethane diisocyanate (mMDI); NCO weight 26.0%; viscosity 100 mPa ⁇ s @ 25° C.; equivalent weight 162; functionality 2.0 MONDUR MA 2601 aromatic diisocyanate blend, allophanate-modified 4,4′-diphenylmethane diisocyanate (MDI) blended with polymeric
  • MDI diphenylmethane 4,4′-diisocyanate
  • MONDUR MR polymeric diphenylmethane diisocyanate (pMDI); NCO weight 31.5%; viscosity 200 mPa ⁇ s @ 25° C.; equivalent weight 133; functionality 2.8 MONDUR MR LIGHT polymeric diphenylmethane diisocyanate (pMDI); NCO weight 31.5%; viscosity 200 mPa ⁇ s @ 25° C.; equivalent weight 133; functionality 2.8 MONDUR MR-5 polymeric diphenylmethane diisocyanate (pMDI); NCO weight 32.5%; viscosity 50 mPa ⁇ s @ 25° C.; equivalent weight 129; functionality 2.4 MONDUR MRS 2,4′ rich polymeric diphenylmethane diisocyanate (pMDI); NCO weight 31.5%; viscosity 200 mPa ⁇ s @ 25° C.; equivalent weight 133; functionality2.6 MONDUR MRS 2 2,4′ rich polymeric diphenylmethane
  • one or more of the above-described isocyanate compositions is provided in a formulation typical of a mixture known in the art of polyurethane adhesives manufacture.
  • Such mixtures may comprise prepolymers formed by the reaction of a molar excess of one or more isocyanates with reactive molecules comprising reactive functional groups such as alcohols, amines, thiols, carboxylates and the like.
  • reactive functional groups such as alcohols, amines, thiols, carboxylates and the like.
  • These mixtures may also comprise solvents, surfactants, stabilizers, and other additives known in the art.
  • the composition of the adhesive might comprise a blocked isocyante. Such mixtures do not react under normal conditions, even in the presence of water. Instead curing is triggered by heating.
  • the present invention encompasses prepolymers comprising isocyanate-terminated epoxide CO 2 -derived polyols.
  • isocyanate-terminated prepolymers comprise a plurality of epoxide-CO 2 -derived polyol segments linked via urethane bonds formed from reaction with polyisocyanate compounds.
  • a prepolymer of the present invention is the result of a reaction between one or more of the aliphatic polycarbonate polyols described above with a stoichiometric excess of any one or more of the diisocyanates described herein.
  • the degree of polymerization of these prepolymers i.e. the average number of polyol segments contained in the prepolymer chains
  • prepolymers comprise compounds conforming to a formula:
  • the black rectangles ⁇ represent the carbon skeleton of the diisocyanate, R 1 , R 2 , R 3 , R 4 , n, x, and y, are as defined above and in the classes and subclasses herein.
  • prepolymers comprise compounds conforming to a formula:
  • each open rectangle, ⁇ represents a polyol moiety each of which may be the same or different, and ⁇ , is as defined above and in the classes and subclasses herein.
  • some of the polyol moieties are derived from one or more of the aliphatic polycarbonate polyols as defined herein, while other of the polyol moieties may be derived from other polyols such as polyether or polyester polyols as described herein.
  • prepolymers comprise chains conforming to the formula:
  • R 1 , R 2 , R 3 , R 4 , and n are as defined above and in the classes and subclasses herein.
  • a prepolymer may be formed by reacting a stoichiometric excess of polyol with a limited amount of isocyanate.
  • the inventive prepolymer has —OH end groups and contains two or more polyol units connected by urethane linkages.
  • such prepolymers conform to a structure:
  • ⁇ , ⁇ , and Q are as defined above and in the classes and subclasses herein.
  • such prepolymers have structures conforming to:
  • R 1 , R 2 , R 3 , R 4 , and n are as defined above and in the classes and subclasses herein.
  • compositions of the present invention can include one or more of the aliphatic polycarbonate polyols described in Section I above. Additional aliphatic polycarbonate polyols suitable for the formulation of such mixtures of the present invention are disclosed in WO 2010/028362.
  • these mixtures comprise the aliphatic polycarbonate polyols in combination with one or more additional polyols and/or one or more additives.
  • the additional polyols are selected from the group consisting of: polyester polyols, in some cases based on adipic acid and various diols; polyether polyols; and/or polycaprolactone polyols.
  • the mixtures comprise additional reactive small molecules known as chain extenders such as amines, alcohols, thiols or carboxylic acids that participate in bond-forming reactions with isocyanates.
  • additives are selected from the group consisting of: solvents, fillers, clays, blocking agents, stabilizers, thixotropes, plasticizers, compatibilizers, colorants, UV stabilizers, flame retardants, and the like.
  • the mixtures of the present invention comprise aliphatic polycarbonate polyols as described above in combination with one or more additional polyols such as are traditionally used in polyurethane adhesive compositions.
  • additional polyols may comprise up to about 95 weight percent of the total polyol content with the balance of the polyol mixture made up of one or more aliphatic polycarbonate polyols described in Section I above and in the examples and specific embodiments herein.
  • the additional polyols are selected from the group consisting of polyether polyols, polyester polyols, polystyrene polyols, polyether-carbonate polyols, polyether-ester carbonates, butane diol adipate polyols, ethylene glocol adipate polyols, hexane diol adipate polyols, polycaprolactone polyols, polycarbonate polyols, polytetramethylene ether glycol (PTMEG) polyols, EO/PO polyether polyols, and mixtures of any two or more of these.
  • PTMEG polytetramethylene ether glycol
  • mixtures of the present invention comprise or derived from a mixture of one or more aliphatic polycarbonate polyols as described herein and one or more other polyols selected from the group consisting of materials available commercially under the trade names: Voranol® (Dow), SpecFlex® (Dow), Tercarol® (Dow), Caradol® (Shell), Hyperliter®, Acclaim® (Bayer Material Science), Ultracel® (Bayer Material Science), Desmophen® (Bayer Material Science), Arcol® (Bayer Material Science), Stepanpol® (Stepan), Terate® (Invista), Terol® (oxid), Agrol® (BioBased Technologies), BiOH® (Cargil), HB® (Honey Bee), Polycin® (Vertellus), Poly-BD® (Cray Valley) and Krasol® (Cray Valley).
  • the mixtures of the present invention contain polyether polyols, polyester polyols, and/or polycaprolactone polyols in combination with one or more aliphatic polycarbonate polyols as described herein.
  • such polyols are characterized in that they have an Mn between about 500 and about 10,000 g/mol. In certain embodiments, such polyols have an Mn between about 500 and about 5,000 g/mol. In certain embodiments, such polyols have an Mn between about 1,500 and about 25,000 g/mol.
  • mixtures of the present invention contain polyether polyols, polyester polyols, and/or polycaprolactone polyols in combination with one or more aliphatic polycarbonate polyols as described herein.
  • such polyols are characterized in that they have a functionality between 1.9 and 2.5.
  • such polyols are characterized in that they have a functionality between 1.95 and 2.2.
  • such polyols have a functionality greater than 2.5, in which cases such high-functionality polyols typically compromise a minority of the overall polyol formulation.
  • Polyester polyols that may be present include those which can be obtained by known methods, for example, polyester polyols can be based on the reaction of adipic acid or succinic acid (or their corresponding reactive derivatives or anhydrides) with various diols including, butanediol (BDO), hexanediol (HDO), and ethylene glycol (EG), propane diol (PDO).
  • BDO butanediol
  • HDO hexanediol
  • EG propane diol
  • Polyether polyols that may be present include those which can be obtained by known methods, for example, polyether polyols can be produced by anionic polymerization with alkali hydroxides such as sodium hydroxide or potassium hydroxide or alkali alcoholates, such as sodium methylate, sodium ethylate, or potassium ethylate or potassium isopropylate as catalysts and with the addition of at least one initiator molecule containing 2 to 8, preferably 2, reactive hydrogens or by cationic polymerization with Lewis acids such as antimony pentachloride, boron trifluoride etherate, etc., or bleaching earth as catalysts from one or more alkylene oxides with 2 to 4 carbons in the alkylene radical.
  • alkali hydroxides such as sodium hydroxide or potassium hydroxide or alkali alcoholates, such as sodium methylate, sodium ethylate, or potassium ethylate or potassium isopropylate
  • alkylene oxide such as 1,3-propylene oxide, 1,2- and 2,3butylene oxide, amylene oxides, styrene oxide, and preferably ethylene oxide and 1,2-propylene oxide and mixtures of these oxides.
  • the polyalkylene polyether polyols may be prepared from other starting materials such as tetrahydrofuran and alkylene oxide-tetrahydrofuran mixtures; epihalohydrins such as epichlorohydrin; as well as aralkylene oxides such as styrene oxide.
  • the polyalkylene polyether polyols may have either primary or secondary hydroxyl groups, preferably secondary hydroxyl groups from the addition of propylene oxide onto an initiator because these groups are slower to react.
  • polyether polyols include polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polytetramethylene glycol, block copolymers, for example, combinations of polyoxypropylene and polyoxyethylene glycols, poly-1,2-oxybutylene and polyoxyethylene glycols, poly-1,4-tetramethylene and polyoxyethylene glycols, and copolymer glycols prepared from blends or sequential addition of two or more alkylene oxides.
  • the polyalkylene polyether polyols may be prepared by any known process such as, for example, the process disclosed by Wurtz in Encyclopedia of Chemical Technology, Vol. 7, pp. 257-262, published by Interscience Publishers, Inc. (1951) or in U.S. Pat.
  • Polyethers which are preferred include the alkylene oxide addition products of polyhydric alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,2-butanediol, 1,5-pentanediol, 1,6hexanediol, 1,7-heptanediol, hydroquinone, resorcinol glycerol, glycerine, 1,1,1-trimethylol-propane, 1,1,1-trimethylolethane, pentaerythritol, 1,2,6-hexanetriol, a-methyl glucoside, sucrose, and sorbitol.
  • polyhydric alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,2-butanediol, 1,5-pentanediol, 1,6hexanediol, 1,7-heptanediol, hydroquinon
  • polyhydric alcohol compounds derived from phenol such as 2,2-bis(4-hydroxyphenyl)-propane, commonly known as Bisphenol A.
  • Suitable organic amine initiators which may be condensed with alkylene oxides include aromatic amines-such as aniline, N-alkylphenylene-diamines, 2,4′-, 2,2′-, and 4,4′-methylenedianiline, 2,6- or 2,4-toluenediamine, vicinal toluenediamines, o-chloroaniline, p-aminoaniline, 1,5-diaminonaphthalene, methylene dianiline, the various condensation products of aniline and formaldehyde, and the isomeric diaminotoluenes; and aliphatic amines such as mono-, di-, and trialkanolamines, ethylene diamine, propylene diamine, diethylenetriamine, methylamine, triisopropanolamine, 1,
  • Preferable amines include monoethanolamine, vicinal toluenediamines, ethylenediamines, and propylenediamine.
  • Yet another class of aromatic polyether polyols contemplated for use in this invention are the Mannich-based polyol an alkylene oxide adduct of phenol/formaldehyde/alkanolamine resin, frequently called a “Mannich” polyol such as disclosed in U.S. Pat. Nos. 4,883,826; 4,939,182; and 5,120, 815.
  • additional polyols comprise from about 5 weight percent to about 95 weight percent of the total polyol content with the balance of the polyol mixture made up of one or more aliphatic polycarbonate polyols described in Section I above and in the examples and specific embodiments herein. In certain embodiments, up to about 75 weight percent of the total polyol content of the mixture is aliphatic polycarbonate polyol. In certain embodiments, up to about 50 weight percent of the total polyol content of the mixture is aliphatic polycarbonate polyol.
  • up to about 40 weight percent, up to about 30 weight percent, up to about 25 weight percent, up to about 20 weight percent, up to about 15 weight percent, or up to about 10 weight percent of the total polyol content of the mixture is aliphatic polycarbonate polyol. In certain embodiments, at least about 5 weight percent of the total polyol content of the mixture is aliphatic polycarbonate polyol. In certain embodiments, at least about 10 weight percent of the total polyol content of the mixture is aliphatic polycarbonate polyol. In certain embodiments, at least about 15 weight percent, at least about 20 weight percent, at least about 25 weight percent, at least about 40 weight percent, or at least about 50 weight percent, of the total polyol content of the mixture is aliphatic polycarbonate polyol.
  • the mixtures of the present invention include one or more small molecules reactive toward isocyanates.
  • reactive small molecules included in the inventive mixtures comprise low molecular weight organic molecules having one or more functional groups selected from the group consisting of alcohols, amines, carboxylic acids, thiols, and combinations of any two or more of these.
  • the mixtures of the present invention include one or more alcohols. In certain embodiments, the mixtures include polyhydric alcohols.
  • reactive small molecules included in the inventive mixtures comprise dihydric alcohols.
  • the dihydric alcohol comprises a C 2-40 diol.
  • the polyol compound is selected from aliphatic and cycloaliphatic polyol compounds, for example, ethylene glycol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,2-propylene glycol, 1,3-butane diol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, 1,8-octane diol, 1,9-nonane diol, 1,10-decane diol, neopentyl glycol, 3-methyl-1,5-pentane diol, 3,3-dimethylolheptane, 1,4-cyclohexane diol, 1,4-cyclohexane
  • the chain extender is selected from the group consisting of: 1,4-cyclohexanediethanol, isosorbide, glycerol monoesters, glycerol monoethers, trimethylolpropane monoesters, trimethylolpropane monoethers, pentaerythritol diesters, pentaerythritol diethers, and alkoxylated derivatives of any of these.
  • the above-mentioned chain-extending compounds may be used alone or in a mixture of two or more thereof.
  • a reactive small molecule included in the inventive mixtures comprises a dihydric alcohol selected from the group consisting of: diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly(ethylene glycol), such as those having number average molecular weights of from 220 to about 2000 g/mol, dipropylene glycol, tripropylene glycol, and higher poly(propylene glycols) such as those having number average molecular weights of from 234 to about 2000 g/mol.
  • a reactive small molecule included in the inventive mixtures comprises an alkoxylated derivative of a compound selected from the group consisting of: a diacid, a diol, or a hydroxy acid.
  • the alkoxylated derivatives comprise ethoxylated or propoxylated compounds.
  • a reactive small molecule included in the inventive mixtures comprises a polymeric diol.
  • a polymeric diol is selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether polycarbonates, polycarbonate-copolyesters, and alkoxylated analogs of any of these.
  • the polymeric diol has an average molecular weight less than about 2000 g/mol.
  • a reactive small molecule comprises a hydroxy-carboxylic acid having the general formula (HO) x Q(COOH) y , wherein Q is a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x and y are each integers from 1 to 3.
  • a coreactant comprises a diol carboxylic acid.
  • a coreactant comprises a bis(hydroxylalkyl) alkanoic acid.
  • a coreactant comprises a bis(hydroxylmethyl) alkanoic acid.
  • the diol carboxylic acid is selected from the group consisting of 2,2bis-(hydroxymethyl)-propanoic acid (dimethylolpropionic acid, DMPA) 2,2-bis(hydroxymethyl) butanoic acid (dimethylolbutanoic acid; DMBA), dihydroxysuccinic acid (tartaric acid), and 4,4′-bis(hydroxyphenyl) valeric acid.
  • a coreactant comprises an N,N-bis(2-hydroxyalkyl)carboxylic acid.
  • a reactive small molecule comprises a polyhydric alcohol comprising one or more amino groups. In certain embodiments, a reactive small molecule comprises an amino diol. In certain embodiments, a reactive small molecule comprises a diol containing a tertiary amino group.
  • an amino diol is selected from the group consisting of: diethanolamine (DEA), N-methyldiethanolamine (MDEA), N-ethyldiethanolamine (EDEA), N-butyldiethanolamine (BDEA), N,N-bis(hydroxyethyl)- ⁇ -amino pyridine, dipropanolamine, diisopropanolamine (DIPA), N-methyldiisopropanolamine, Diisopropanol-p-toluidine, N,N-Bis(hydroxyethyl)-3-chloroaniline, 3-diethylaminopropane-1,2-diol, 3-dimethylaminopropane-1,2-diol and N-hydroxyethylpiperidine.
  • DEA diethanolamine
  • MDEA N-methyldiethanolamine
  • EDEA N-ethyldiethanolamine
  • BDEA N-butyldiethanolamine
  • a coreactant comprises a diol containing a quaternary amino group.
  • a coreactant comprising a quaternary amino group is an acid salt or quaternized derivative of any of the amino alcohols described above.
  • a reactive small molecule is selected from the group consisting of: inorganic or organic polyamines having an average of about 2 or more primary and/or secondary amine groups, polyalcohols, ureas, and combinations of any two or more of these.
  • a reactive small molecule is selected from the group consisting of: diethylene triamine (DETA), ethylene diamine (EDA), meta-xylylenediamine (MXDA), aminoethyl ethanolamine (AEEA), 2-methyl pentane diamine, and the like, and mixtures thereof.
  • reactive small molecule is selected from the group consisting of: hydrazine, substituted hydrazines, hydrazine reaction products, and the like, and mixtures thereof.
  • a reactive small molecule is a polyalcohol including those having from 2 to 12 carbon atoms, preferably from 2 to 8 carbon atoms, such as ethylene glycol, diethylene glycol, neopentyl glycol, butanediols, hexanediol, and the like, and mixtures thereof.
  • Suitable ureas include urea and its derivatives, and the like, and mixtures thereof.
  • reactive small molecules containing at least one basic nitrogen atom are selected from the group consisting of: mono-, bis- or polyalkoxylated aliphatic, cycloaliphatic, aromatic or heterocyclic primary amines, N-methyl diethanolamine, N-ethyl diethanolamine, N-propyl diethanolamine, N-isopropyl diethanolamine, N-butyl diethanolamine, N-isobutyl diethanolamine, N-oleyl diethanolamine, N-stearyl diethanolamine, ethoxylated coconut oil fatty amine, N-allyl diethanolamine, N-methyl diisopropanolamine, N-ethyl diisopropanolamine, N-propyl diisopropanolamine, N-butyl diisopropanolamine, cyclohexyl diisopropanolamine, N,N-diethoxylaniline, N,N-diethoxyl toluidine, N,N-
  • chain-extending agents are compounds that contain two amino groups.
  • chain-extending agents are selected from the group consisting of: ethylene diamine, 1,6-hexamethylene diamine, and 1,5-diamino-1-methyl-pentane.
  • no catalysts are used in the mixtures.
  • a conventional catalyst comprising an amine compound or tin compound can be employed to promote the reaction. These embodiments are most commonly found in reactive extrusion methods of polyurethane adhesive production. Any suitable urethane catalyst may be used, including tertiary amine compounds and organometallic compounds may be used.
  • Exemplary tertiary amine compounds include triethylenediamine, N-methylmorpholine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, tetramethylethylenediamine, 1-methyl-4-dimethylaminoethylpiperazine, 3-methoxy-N-dimethylpropylamine, N-ethylmorpholine, diethylethanolamine, N-cocomorpholine, N,N-dimethyl-N′,N′-dimethyl isopropylpropylenediamine, N,N-diethyl-3-diethylaminopropylamine and dimethylbenzylamine.
  • organometallic catalysts include organomercury, organolead, organoferric and organotin catalysts, with organotin catalysts being preferred among these.
  • Suitable tin catalysts include stannous chloride, tin salts of carboxylic acids such as dibutyltin dilaurate, as well as other organometallic compounds such as are disclosed in U.S. Pat. No. 2,846,408.
  • a catalyst for the trimerization of polyisocyanates, resulting in a polyisocyanurate, such as an alkali metal alkoxide may also optionally be employed herein. Such catalysts are used in an amount which measurably increases the rate of polyurethane or polyisocyanurate formation.
  • the catalysts comprise tin based materials.
  • tin catalysts are selected from the group consisting of: di-butyl tin dilaurate, dibutylbis(laurylthio)stannate, dibutyltinbis(isooctylmercapto acetate) and dibutyltinbis(isooctylmaleate), tin octanoate and mixtures of any two or more of these.
  • catalysts included in the mixtures comprise tertiary amines.
  • catalysts included in the mixtures are selected from the group consisting of: DABCO, pentamethyldipropylenetriamine, bis(dimethylamino ethyl ether), pentamethyldiethylenetriamine, DBU phenol salt, dimethylcyclohexylamine, 2,4,6-tris(N,N-dimethylaminomethyl)phenol (DMT-30), triazabicyclodecene (TBD), N-methyl TBD, 1,3,5-tris(3-dimethylaminopropyl)hexahydro-s-triazine, ammonium salts and combinations or formulations of any of these.
  • Typical amounts of catalyst are 0.001 to 10 parts of catalyst per 100 parts by weight of total polyol in the mixture.
  • catalyst levels in the formulation when used, range between about 0.001 pph (weight parts per hundred) and about 3 pph based on the amount of polyol present in the mixture. In certain embodiments, catalyst levels range between about 0.05 pph and about 1 pph, or between about 0.1 pph and about 0.5 pph.
  • monofunctional components are added.
  • Suitable monfunctional components can include molecules having a single isocyanate-reactive functional group such as an alcohol, amine, carboxylic acid, or thiol.
  • a monofunctional component will serve as a chain termination which can be used to limit molecular weight or crosslinking if higher functionality species are used.
  • U.S. Pat. No. 5,545,706 illustrates the use of a monofunctional alcohol in a substantially linear polyurethane formulation.
  • the monofunctional alcohol can be any compound with one alcohol available for reaction with isocyanate such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, phenol and the like. Additionally, the monofunctional component can be added as a low molecular weight polymer that has been initiated by or reacted with the monofunctional alcohol.
  • the monofunctional alcohol can be a polyether such as polypropylene oxide or polyethylene oxide initiated with any of the monofunctional alcohols listed.
  • the monofunctional alcohol can be a polyester polymer where the monofunctional alcohol is added to the recipe.
  • the monofunctional alcohol can be a polycarbonate polymer such as polyethylene carbonate or polypropylene carbonate initiated with a monfunctional anion, such as halide, nitrate, azide, carboxylate, or a monohydr
  • the monofunctional component could be an isocyanate. Any monofunctional isocyanate could be added for this same function. Possible materials include phenyl isocyanate, naphthyl isocyanate, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, hexyl isocyanate, octyl isocyanate and the like.
  • mixtures of the present invention may optionally contain various additives as are known in the art of polyurethane adhesive technology.
  • additives may include, but are not limited to solvents, fillers, clays, blocking agents, stabilizers, thixotropes, plasticizers, compatibilizers, colorants, UV stabilizers, flame retardants, and the like.
  • the polyurethane adhesives or pre-polymers can be dispersed in a solvent which can include water or organic solvents known to those skilled in the art.
  • Suitable solvents can include aliphatic, aromatic, or halogenated hydrocarbons, ethers, esters, ketones, lactones, sulfones, nitriles, amides, nitromethane, propylene carbonate, dimethyl carbonate and the like.
  • Representative examples include, but are not limited to: acetone, acetonitrile, benzene, butanol, butyl acetate, g-butyrolactone, butyl caribitl acetate, carbitol acetate, chloroform, cyclohexane, 1,2-dichloromethane, dibasic ester, diglyme, 1,2-dimethoxyethane, dimethylacetamide, dimethylsulfoxide, dimethformamide, 1,4-dioxane, ethanol, ethyl acetate, ethyl ether, ethylene, glycol, hexane, hydroxylmethyl methacrylate, isopropyl acetate, methanol, methyl acetate, methyl amyl ketone, methyl isobutyl ketone, methylene chloride, methyl ethyl ketone, monoglyme, methyl methacrylate, propylene carbobonate, prop
  • fillers are well known to those skilled in the art and include carbon black, titanium dioxide, calcium carbonate, surface treated silicas, titanium oxide, fume silica, talc, aluminum trihydrate and the like.
  • fillers comprise carbon black.
  • more than one reinforcing filler may be used, of which one is carbon black and a sufficient amount of carbon black is used to provide the desired black color to the adhesive.
  • a reinforcing filler is used in sufficient amount to increase the strength of the adhesive and/or to provide thixotropic properties to the adhesive.
  • the amounts of filler or other additives will vary depending on the desired application.
  • clays are preferred clays.
  • Preferred clays useful in the invention include kaolin, surface treated kaolin, calcined kaolin, aluminum silicates and surface treated anhydrous aluminum silicates.
  • the clays can be used in any form which facilitates formulation of a pumpable adhesive.
  • the clay is in the form of pulverized powder, spray-dried beads or finely ground particles.
  • One or more blocking agents are utilized to provide an induction period between the mixing of the two parts of the adhesive composition and the initiation of the cure.
  • the addition of the blocking agents provides an induction period which causes a reduction in the curing rate immediately after mixing of the components of the adhesive.
  • the reduction in the curing rate results in lower initial tensile shear strengths and storage moduli immediately after mixing than those found in compositions that do not contain a blocking agent.
  • the adhesive quickly cures so that the tensile shear strength and storage modulus are similar to those produced by adhesives that do not contain the blocking agent.
  • thixotropes are well known to those skilled in the art and include hydroxyl containing compounds such as diethylene glycol, mono alkyl ethers, butanone oxime, methyl ethyle ketone oxime, nonylphenol, phenol and cresol; amine containing compounds such as caprolactam, diisopropyl amine, 1,2,4-triazole and 3,5-dimethylpyrazole; and aliphatic containing compounds such as dialkyl malonate.
  • hydroxyl containing compounds such as diethylene glycol, mono alkyl ethers, butanone oxime, methyl ethyle ketone oxime, nonylphenol, phenol and cresol
  • amine containing compounds such as caprolactam, diisopropyl amine, 1,2,4-triazole and 3,5-dimethylpyrazole
  • aliphatic containing compounds such as dialkyl malonate.
  • An adhesive of this invention may further comprise stabilizers which function to protect the adhesive composition from moisture, thereby inhibiting advancement and preventing premature crosslinking of the isocyanates in the adhesive formulation. Included among such stabilizers are diethylmalonate and alkylphenol alkylates.
  • the adhesive composition may further comprise a thixotrope.
  • thixotropes are well known to those skilled in the art and include alumina, limestone, talc, zinc oxides, sulfur oxides, calcium carbonate, perlite, slate flour, salt (NaCl), cyclodextrin and the like.
  • the thixotrope may be added to the adhesive of composition in a sufficient amount to give the desired rheological properties.
  • Adhesive compositions of the present invention may further comprise plasticizers so as to modify the rheological properties to a desired consistency.
  • plasticizers are well known in the art and preferable plasticizers include alkyl phthalates such as dioctylphthalate or dibutylphthalate, partially hydrogenated terpene commercially available as “HB-40”, trioctyl phosphate, epoxy plasticizers, toluene-sulfamide, chloroparaffins, adipic acid esters, castor oil, toluene and alkyl naphthalenes.
  • the amount of plasticizer in the adhesive composition is that amount which gives the desired rheological properties and/or which is sufficient to disperse any catalyst that may be present in the system.
  • the mixtures of the present invention comprise one or more suitable compatibilizers.
  • suitable compatibilizers are molecules that allow two or more nonmiscible ingredients to come together and give a homogeneous liquid phase. Many such molecules are known to the polyurethane industry, these include: amides, amines, hydrocarbon oils, phthalates, polybutyleneglycols, and ureas.
  • the mixtures of the present invention comprise one or more suitable colorants.
  • suitable colorants included titanium dioxide, iron oxides and chromium oxide.
  • Organic pigments originated from the azo/diazo dyes, phthalocyanines and dioxazines, as well as carbon black. Recent advances in the development of polyol-bound colorants are described in:
  • the mixtures of the present invention comprise one or more suitable UV stabilizers.
  • Polyurethanes based on aromatic isocyanates will typically turn dark shades of yellow upon aging with exposure to light.
  • a review of polyurethane weathering phenomena is presented in: Davis, A.; Sims, D. Weathering Of Polymers; Applied Science: London, 1983, 222-237.
  • Light protection agents such as hydroxybenzotriazoles, zinc dibutyl thiocarbamate, 2,6-ditertiary butylcatechol, hydroxybenzophenones, hindered amines and phosphites have been used to improve the light stability of polyurethanes. Color pigments have also been used successfully.
  • the mixtures of the present invention comprise one or more suitable flame retardants.
  • Flame retardants are often added to reduce flammability.
  • the choice of flame retardant for any specific polyurethane adhesive often depends upon the intended service application of that adhesive and the attendant flammability testing scenario governing that application. Aspects of flammability that may be influenced by additives include the initial ignitability, burning rate and smoke evolution.
  • the present invention encompasses polyurethane adhesives derived from one or more of aliphatic polycarbonate polyol compositions described above and in the specific embodiments and examples disclosed herein.
  • the polyurethane adhesive compositions comprise the reaction product of one or more isocyanates and a mixture containing one or more of the aliphatic polycarbonate polyol compositions defined above.
  • the present invention encompasses reactive one-component adhesives.
  • such one-component adhesives compositions are derived from a mixture containing one or more of the aliphatic polycarbonate polyol compositions as defined above and in the embodiments and examples herein.
  • the one-component adhesives are prepolymers made with one or more aliphatic polycarbonate polyols; these prepolymers typically have low isocyanate values and are produced by reacting an excess of isocyanate with a relatively high molecular weight polyol. These adhesives are typically cured with water which can be added or which is present in the atmosphere or the material being bonded.
  • MDI is the preferred isocyanate to react with one or more aliphatic polycarbonate polyols and optionally one or more other polyols as described above.
  • TDI and/or aliphatic isocyanates are used in place of, or in addition to, MDI.
  • the one component adhesives comprise 100% solids (e.g. no solvent is present at the time of application).
  • the one component adhesives formulations may be dissolved, dispersed, and/or emulsified in a solvent or water to reduce viscosity or otherwise improve the applicability of the one component adhesive in these applications.
  • catalysts are used. In certain embodiments catalysts are included in the formulation to increase the reaction rate of free isocyanate and water.
  • hydroxyethyl acrylate groups may be included in the aliphatic polycarbonate polyol, other polyols, and/or the derivative prepolymers to introduce ultraviolet light curing properties.
  • fatty acid groups and/or other molecules with unsaturation functionality may be included in the aliphatic polycarbonate polyol, other polyols, and/or the derivative prepolymers to enable cross linking via oxidation.
  • the 1-component adhesive mixture forms a final, cured polyurethane adhesive with the following composition:
  • the present invention encompasses reactive two-component adhesive compositions.
  • such two-component adhesive compositions are derived from a mixture containing one or more of the aliphatic polycarbonate polyols as defined above and in the embodiments and examples herein.
  • the two-component adhesives include prepolymers derived from one or more aliphatic polycarbonate polyols. These prepolymers can be produced with excess isocyanate and/or excess hydroxyl content and are then mixed with one or more of the isocyanates, aliphatic polycarbonate polyols, other polyols, and other components described above.
  • the two-component adhesives are formulated to an isocyanate index range of 90 to 150.
  • isocyanate indexes above 100 are used to increase hardness of the adhesive and to improve bonding to substrates, in particular those substrates with hydroxyl groups on their surfaces.
  • isocyanate indexes below 100 are used to produce softer and more flexible adhesives.
  • MDI is the preferred isocyanate used in the formulation of the two-component adhesives.
  • TDI is the preferred isocyanate used in the formulation of the two-component adhesives.
  • these isocyanates have a functionality greater than two, and may be polymeric.
  • other isocyanates are used, including aliphatic isocyanates in cases where resistance to ultraviolet light is a requirement.
  • polycarbonate polyol In certain embodiments only a single aliphatic polycarbonate polyol is used in the formulation of the two-component adhesive. In certain embodiments one or more polycarbonate polyols are mixed with one or more additional polyols as described above. In certain embodiments these polyols have molecular weights between 200 and 10,000 grams per mol, preferably between 300 and 5,000 grams per mol.
  • the two-component adhesives are formulated with isocyanates and/and or polyols which are 2.0 functional or lower.
  • the adhesives are formulated with isocyanates and/or polyols functionality greater than 2.0 (in other words, some degree of branching) to introduce cross-linking in the cured two-component adhesives.
  • the total level of crosslinking is relatively high to produce adhesives with high modulus, high hardness, and good tensile, shear stress, and peel strength properties.
  • the total level of crosslinking is relatively low to produce adhesives with greater elasticity.
  • the two-component adhesives are applied as 100% solids.
  • the two component adhesives may be dissolved, dispersed, and/or emulsified in a solvent or water to reduce viscosity or otherwise improve their applicability.
  • solvents such as acetone, methyl ethyl ketone, ethylacetate, toluene, or xylene are preferred.
  • no fillers are present in the two-component adhesives.
  • calcium carbonate, talc, clays, or the like are added as fillers to control rheology, reduce shrinkage, reduce cost, and/or for other reasons.
  • the two-component adhesives include thixotropic agents, flow agents, film-forming additives, and/or catalysts to achieve the processing and finished adhesives properties required.
  • the 2-component adhesive mixture forms a final, cured polyurethane adhesive with the following composition:
  • the present invention encompasses adhesives formulated from a polyol blend comprising one or more of the aliphatic polycarbonate polyol as described hereinabove, and one or more commercially available polyester or polyether polyols.
  • the aliphatic polycarbonate content of such blends ranges from about 10 to about 90%.
  • Such blends can be formulated to provide a range of hardness or elasticity as shown in FIG. 8 .
  • the present invention encompasses adhesive compositions derived from a polyol blend comprising about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, or about 80% aliphatic polycarbonate polyol with the balance comprising a polyester polyol.
  • such blends comprise poly(butylane adipate) glycol as the polyester polyol.
  • the present invention encompasses adhesive compositions derived from a polyol blend comprising about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, or about 80% aliphatic polycarbonate polyol with the balance comprising a polyether polyol.
  • such blends comprise polyethylene glycol, or polypropylene glycol as the polyether polyol component.
  • the present invention encompasses reactive hot melt adhesives.
  • reactive hot melt adhesive compositions are derived from a mixture containing one or more of the aliphatic polycarbonate polyol compositions as defined above and in the embodiments and examples herein.
  • the hot-melt adhesives include prepolymers derived from one or more aliphatic polycarbonate polyols. These prepolymers can be produced with excess isocyanate and/or excess hydroxyl content and are then mixed with one or more of the isocyanates, aliphatic polycarbonate polyols, other polyols, and other components described above. In certain embodiments the molar ratio of isocyanate to polyol is between 1.5:1 and 4:1, preferably between 1.9:1 and 3:1, and often very near 2:1.
  • MDI is the preferred isocyanate to react with one or more aliphatic polyols and possibly one or more other polyols as described above.
  • TDI and/or aliphatic isocyanates are used in place of or in addition to MDI.
  • the reactive hot melt adhesive prepolymers are produced by reacting an excess of isocyanate with a relatively high molecular weight polyol. These prepolymers thus have an excess of isocyanate, or “free” isocyanate groups, which react with atmospheric moisture to improve the finished properties of the reactive hot melt adhesive. In certain embodiments the amount of free isocyant is about 1-5 percent by weight.
  • the polyols, isocyanates, and/or prepolymers comprising the primary components of the reactive hot melt adhesive are formulated such that the viscosity of the adhesive formulation is sufficiently low at the application temperature to enable efficient application to the substrate.
  • the reactive hot melt viscosity increases as it cools to rapidly provide good adhesive properties.
  • the reactive hot melt polyurethane adhesive mixture forms a final, cured polyurethane adhesive with the following composition:
  • the present invention encompasses non-reactive solvent-borne adhesives.
  • solvent-borne adhesives compositions are derived from one or more of the aliphatic polycarbonate polyol compositions as defined above and in the embodiments and examples herein.
  • the solvent-borne adhesives are produced by reacting one or more aliphatic polycarbonate polyols with one or more isocyanates and possibly with one or more additional polyols and/or all other additives described above to create higher molecular weight prepolymers and/or polyurethane adhesives. These high molecular weight polyurethanes are then dissolved in one or more solvents for application onto various substrates.
  • the solvent-borne adhesive is described as a one-component system. Additional fillers and performance enhancing additives may be included in the formulation.
  • solvent-borne cross-linkers are added to solvent-born polyurethane adhesives as described above to improve the strength and resistance of the finished adhesive.
  • the crosslinkers may be any combination of aliphatic polycarbonate polyols, additional polyols, and isocyanates described above and may also be other types of thermosetting components.
  • the solvent-borne adhesive is described as a two-component reactive system and are thus similar and/or equivalent to the two-component reactive adhesives described above, in the embodiments in which these systems are dissolved in one or more solvents.
  • the non-reactive solvent-borne adhesive mixture forms a final, cured polyurethane adhesive with the following composition:
  • the present invention encompasses reactive water-borne adhesives.
  • water-borne adhesives compositions are derived from a mixture containing one or more of the aliphatic polycarbonate polyol compositions as defined above and in the embodiments and examples herein.
  • the water-borne adhesives are produced by reacting one or more aliphatic polycarbonate polyols with one or more isocyanates and possibly with one or more additional polyols and/or all other additives described above to create higher molecular weight prepolymers and/or polyurethane adhesives, which are then dispersed in water and known as polyurethane dispersions (PUDs).
  • PODs polyurethane dispersions
  • they may contain low levels of solvents to help stabilize the polymers in water.
  • the solids content of the final PUD adhesive is in the range of 25-75%, preferably in the range of 35-50%.
  • the water-borne adhesives are formulated to be on the very high or low end of these ranges depending on viscosity requirements, other processing considerations, and finished adhesive properties required.
  • water-borne cross-linkers are added to water-born PUDs as described above to improve the performance of the finished adhesive.
  • the crosslinkers may be any combination of aliphatic polycarbonate polyols, additional polyols, and isocyanates described above and may also be other types of thermosetting components.
  • the water-borne adhesive is akin to the two-component reactive system described above (except it is dispersed in an aqueous system) in the embodiments in which these systems are dispersed or emulsified in water.
  • the non-reactive water-borne adhesive mixture forms a final, cured polyurethane adhesive with the following composition:
  • the present invention encompasses non-reactive hot melt adhesives.
  • non-reactive hot melt adhesives compositions are derived from a mixture containing one or more of the aliphatic polycarbonate polyol compositions as defined above and in the embodiments and examples herein.
  • non-reactive hot melt adhesives are produced by reacting one or more aliphatic polycarbonate polyols with one or more isocyanates and possibly with one or more additional polyols and/or all other additives described above to create higher molecular weight polymers and/or polyurethane adhesives. Additional fillers and performance enhancing additives may be included in the formulation.
  • the polyols, isocyanates, prepolymers and/or polyurethane adhesives comprising the primary components of the non-reactive hot melt adhesive are formulated such that the viscosity of the adhesive formulation is sufficiently low at the application temperature to enable efficient application to the substrate.
  • the non-reactive hot melt viscosity increases as it cools to rapidly provide good adhesive properties.
  • they are formulated to have melt viscosities between 25,000 and 500,000 mPa*s, more preferable between 50,000 to 250,000 mPa*s.
  • the non-reactive hot-melt adhesive mixture forms a final, cured polyurethane adhesive with the following composition:
  • any of the above reactive and non-reactive adhesive formulations are combined with other adhesive chemistries in hybrid systems.
  • the finished adhesives are urethane acrylic systems which can take a number of forms, including aqueous systems using water-dispersable isocyanates with PUDs and acrylic emulsion polymers, mixing acrylic and hydroxyl polyols to create co-polymerized resins, and the like.
  • vinyl-terminated acrylic polymers are used to improve impact resistance.
  • polyurethanes with acrylic functionality are also used in anaerobic or radiation-cured adhesives to increase toughness.
  • urethanes are combined with epoxy chemistries using amine curing systems to create fast-curing adhesives for structural and heavy duty applications.
  • Example 1 a series of reactive one-component adhesives were formulated and a qualitative assessment of their performance was completed.
  • a 620 Mw PPC diol with a measured OH # of 181 was formulated in a 1/2/1 equivalent ratio of polyol to isocyanate to chain extender to produce a prepolymer of ⁇ 7.5% NCO.
  • the required amount of 2,4/4,4-MDI was weighed into a 3 neck flask and heat to 80° C. The aliphatic polycarbonate polyol was heated up to 50° C. or slightly higher if the viscosity is too high to be easily pourable.
  • the polyol was added to the isocyanate with stirring at such a rate that the reaction temperature is maintained at approximately 80° C. After all the polyol was added, heating continued with stirring for an additional 3 hours.
  • the prepolymer was transferred to a bottle and seal under dry N 2 .
  • the prepolymer composition is shown below.
  • the percent NCO content was measured and compared to the theoretically calculated value and was shown to have good agreement.
  • the prepolymers are then subject to lap shear testing (Lap Shear Strength of Adhesively Bonded Metal Specimens ASTM D1002).
  • lap shear testing Lap Shear Strength of Adhesively Bonded Metal Specimens ASTM D1002.
  • One inch wide cold rolled steel plates are marked at the 1 ⁇ 2 “mark. 10 g of prepolymer is readied and 0.1 g of glass spacer beads are added and mixed in. The mix are then spread on 1 of the metal strips within the 1 ⁇ 2” by 1′′ area and the second strip is overlapped 1 ⁇ 2′′ to the first and then the two strips clamped together and left to cure at room temperature for 72 hour.
  • Three samples are prepared for each prepolymer. After curing for 72 hour, the test specimens are clamped in the Instron and separated.
  • Example 2 a series of reactive two-component adhesives were formulated and a qualitative assessment of their performance was completed.
  • a 620 Mw PPC diol with a measured OH # of 181 was formulated in two different formulations, a 1/2/1 and a 1/3.5/1 equivalent ratio of polyol to isocyanate to chain extender to produce a ⁇ 7% and a ⁇ 14% NCO prepolymer, respectively.
  • the required amount of 2,4/4,4-MDI was weighed into a 3 neck flask and heat to 80° C. The aliphatic polycarbonate polyol was heated up to 50° C. or slightly higher if the viscosity is too high to be easily pourable.
  • the polyol was added to the isocyanate with stirring at such a rate that the reaction temperature is maintained at approximately 80° C. After all the polyol was added, heating continued with stirring for an additional 3 hours.
  • the prepolymer was transferred to a bottle and seal under dry N 2 .
  • the prepolymer composition is shown below.
  • the percent NCO content was measured and compared to the theoretically calculated value and was shown to have good agreement.
  • the prepolymers are then subject to lap shear testing (Lap Shear Strength of Adhesively Bonded Metal Specimens ASTM D1002).
  • lap shear testing Lap Shear Strength of Adhesively Bonded Metal Specimens ASTM D1002.
  • One inch wide cold rolled steel plates are marked at the 1 ⁇ 2′′ mark.
  • 10 g of prepolymer and the equivalent amount of butanediol are mixed together, then 0.1 g of glass spacer beads are added and mixed and lastly 1 drop of tin catalyst (T-9) was added and mixed in.
  • T-9 tin catalyst
  • the mix are then spread on 1 of the metal strips within the 1 ⁇ 2′′ by 1′′ area and the second strip is overlapped 1 ⁇ 2′′ to the first and then the two strips clamped together and left to cure at room temperature for 72 hours.
  • Three samples are prepared for each prepolymer. After curing for 72 hour, the test specimens are clamped in the Instron and separated.
  • the objective was to determine performance of CO 2 -based poly(propylene-carbonate) diol (PPC diol) Novomer 58-076 in polyurethane adhesives.
  • a two-component adhesive was formulated with Novomer 58-076 polyol, 1,4-BD as a chain extender, and 4,4′-MDI isocyanate at MDI/Polyol/Chain extender equivalent ratio 2.02/1/1.
  • polyurethane adhesives were formulated using Eternacoll UH-50 polycarbonate polyol, 1,4-BD chain extender and 4,4′-MDI isocyanate and using Fomrez 44-160 polyester polyol, 1,4-BD chain extender and 4,4′-MDI isocyanate. All polyurethane systems were formulated at the same hard segment concentration.
  • the polyol and chain extender (previously degassed) were preheated at 70° C., weighed into Speed Mixer cup, benzoyl chloride added and all components were mixed via Speed Mixer (FlackTek Inc.) for 60 seconds at 2200 rpm (Component B). The mixture was conditioned for additional 15 minutes at 70° C.
  • Metal plates were conditioned at 120° C. Component A was added to Component B and all components mixed via Speed Mixer for 20 seconds at 2200 rpm. Immediately after mixing, about 0.075 g of the resin was placed in the center of overlapping area of each plate. Before gel time, two plates were joined via over-lapping area, closed with clamps and left to cure for 2 hours at 120° C. followed by 20 hours at 110° C. The samples were left to age at room conditions for 5 days prior to testing.
  • Two-component polyurethane adhesive was composed of Component A which was straight isocyanate 4,4′-MDI and Component B which was mixture of polyol, chain extender, and small amount of benzoyl chloride.
  • the gel time of Eternacoll UH-50-based system was too fast to handle in preparation of adhesive samples.
  • Benzoyl chloride was added in small amount to slightly increase the gel time.
  • Adhesive properties Postcuring time and temperature 20 hours at 110° C. 20 hours at 110° C. Adhesive properties, RT Load at Failure, N/mm 2 1850 ⁇ 266 1166 ⁇ 156 Tensile Energy to Break, in-lbf/in 3 27 ⁇ 4 17 ⁇ 2 Modulus, psi 188948 ⁇ 19184 181099 ⁇ 31962 Stress at Yield, psi 3542 ⁇ 164 3566 ⁇ 120 Strain at Yield, % 2.19 ⁇ 0.16 2.10 ⁇ 0.17 Adhesive properties, 70° C.
  • HM #1 A 620 Mw PPC diol was reacted at 120% theoretical with MM103 isocyanate and labeled HM #1. It was hard at RT but after more curing it was applied to bond two stirring sticks. It was still har at RT, but it was appropriately gummy for a hot melt adhesive at 250 F. Likewise, a higher 3000 Mw PPC diol was reacted with MM103 at 120% theory, called HM #2. It was applied to two stirring sticks, and this formulation, and the bonded wooden sticks were left in the oven overnight at 200 F.
  • the HM #1 stick bonded samples were evaluated on.
  • the 620 Mw PPC created a strong bond, moreover, where it had only coated one stick, the cured adhesive was extremely durable to screwdriver scraping.
  • the composition also adhered strongly to the wood of the stick.
  • the HM#2 stick was tough and strong at RT.
  • the bonded sticks had a very good bond at room temperature.

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