WO2016007157A1 - Adhésif polyuréthane ayant des propriétés de barrière améliorées - Google Patents

Adhésif polyuréthane ayant des propriétés de barrière améliorées Download PDF

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Publication number
WO2016007157A1
WO2016007157A1 PCT/US2014/046074 US2014046074W WO2016007157A1 WO 2016007157 A1 WO2016007157 A1 WO 2016007157A1 US 2014046074 W US2014046074 W US 2014046074W WO 2016007157 A1 WO2016007157 A1 WO 2016007157A1
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Prior art keywords
isocyanate reactive
component
curable composition
polyisobutylene
reactive compound
Prior art date
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PCT/US2014/046074
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English (en)
Inventor
Yongxia Wang
Laxmisha SRIDHAR
Hans-Georg Kinzelmann
Olaf Lammerschop
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Henkel IP & Holding GmbH
Henkel Ag & Co.Kgaa
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Priority to PCT/US2014/046074 priority Critical patent/WO2016007157A1/fr
Publication of WO2016007157A1 publication Critical patent/WO2016007157A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B32B5/20—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material foamed in situ
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/60—Polyamides or polyester-amides
    • C08G18/603—Polyamides
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays

Definitions

  • the present disclosure relates generally to a polyurethane polyisobutylene hybrid oligomers and polymers (polyisobutylene grafted polyurethane polymer and polyisobutylene grafted polyurethane oligomer are used interchangeably herein) with improved water vapor barrier properties.
  • the present disclosure also relates generally to a polyurethane polyisobutylene curable hybrid adhesive with improved water vapor barrier properties.
  • the present disclosure also relates to a process to make a polyurethane polyisobutylene hybrid adhesive, oligomers and polymers.
  • Curable polyurethane materials are well known and widely used in preparation of adhesives, coatings, sealants, foams and elastomers.
  • the water vapor barrier properties of known polyurethane materials are not as good as other types of polymers such as PET, PE, PP, and EVA.
  • PET, PE, PP, and EVA There remains a need for a polyurethane composition with improved barrier properties in the market.
  • hybrid polymers polyurethane polyisobutylene hybrid oligomers or polymers having an architecture of one or more pendent polyisobutylene moieties grafted on to a polyurethane backbone
  • hybrid polymers are structurally different from known urethane oligomers and polymers and provide new and different cured networks with new and different properties. Cured products of these hybrid polymers have potential advantages over conventional polyurethane materials such as superior gas and moisture barrier properties and improved wetting and/or adhesion to low surface energy substrates.
  • One embodiment provides a hybrid polymer with improved water vapor barrier properties. It is prepared from an anhydride-functional polyisobutylene component; an isocyanate reactive component; and a polyisocyanate component.
  • One embodiment provides a one-pot process to make a hybrid polymer with improved water vapor barrier properties by first reacting an anhydride-functional polyisobutylene component with an isocyanate reactive component; and then reacting with a polyisocyanate component.
  • One embodiment provides a one-part curable composition comprising the hybrid polymer.
  • the hybrid polymer retains isocyanate functionality to provide the composition with the ability to cure on exposure to moisture.
  • One embodiment provides an intermediate isocyanate reactive compound A with functional moieties such as -OH, -NH, -NH2, -SH, -COOH, and combinations thereof prepared from an anhydride-functional polyisobutylene component and an isocyanate reactive component.
  • functional moieties such as -OH, -NH, -NH2, -SH, -COOH, and combinations thereof prepared from an anhydride-functional polyisobutylene component and an isocyanate reactive component.
  • One embodiment provides a two-part curable compositions comprising a first part (A) comprising the intermediate isocyanate reactive compound A, and a second part (B) comprising a polyisocyanate component The composition cures when the two parts are mixed.
  • One embodiment provides a one-part curable composition comprising the intermediate isocyanate reactive compound A and a stoichiometrically excess amount of polyisocyanate component.
  • the composition cures when exposed to moisture.
  • One embodiment provides an adhesive, a coating, a sealant, a resin, a thermoplastic polyurethane, an elastomer, a thermoset, or a foam prepared from the hybrid polymer or the curable compositions.
  • the adhesive can be a two-part reactive adhesive, a one-part moisture cure adhesive, a reactive hot melt adhesive, a hot melt adhesive, or a pressure sensitive adhesive.
  • the disclosed compounds include any and all isomers and stereoisomers.
  • the disclosed materials and processes may be alternately formulated to comprise, consist of, or consist essentially of, any appropriate components, moieties or steps herein disclosed.
  • the disclosed materials and processes may additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any components, materials, ingredients, adjuvants, moieties, species and steps used in the prior art compositions or that are otherwise not necessary to the achievement of the function and/or objective of the present disclosure.
  • the word "about” is used herein it is meant that the amount or condition it modifies can vary some beyond the stated amount so long as the function and/or objective of the disclosure are realized.
  • Figure 1 illustrates one possible exemplary reaction of an anhydride functional polyisobutylene component and a polyol isocyanate reactive component to form one or both variations (a and/or b) of intermediate isocyanate reactive compound A.
  • Figure 2 illustrates one possible exemplary reaction of an anhydride functional polyisobutylene component and an amine isocyanate reactive component to form an intermediate isocyanate reactive compound A.
  • Figure 3 illustrates one possible exemplary reaction of an anhydride functional polyisobutylene component and a thiol isocyanate reactive component to form one or both variations (a and/or b) of intermediate isocyanate reactive compound A.
  • Figure 4 illustrates one possible exemplary reaction of an anhydride functional polyisobutylene component and an aminoalcohol isocyanate reactive component to form one or both variations (a and/or b) of intermediate isocyanate reactive compound A.
  • Figure 5 illustrates one possible exemplary reaction of an anhydride functional polyisobutylene component and an aminoalcohol isocyanate reactive component to form an intermediate isocyanate reactive compound A.
  • Alcohol refers to the molecule comprising at least one -OH group.
  • an alcohol can comprise a plurality of -OH groups.
  • Alkyl or “alkane” refers to a hydrocarbon chain or group containing only single bonds between the chain carbon atoms.
  • the alkane can be a straight hydrocarbon chain or a branched hydrocarbon group.
  • the alkane can be cyclic.
  • the alkane can contain 1 to 20 carbon atoms, advantageously 1 to 10 carbon atoms and more advantageously 1 to 6 carbon atoms. In some embodiments the alkane can be substituted.
  • alkanes include methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl and decyl.
  • alkenyl or “alkene” refers to a hydrocarbon chain or group containing one or more double bonds between the chain carbon atoms.
  • the alkenyl can be a straight hydrocarbon chain or a branched hydrocarbon group.
  • the alkene can be cyclic.
  • the alkene can contain 1 to 20 carbon atoms, advantageously 1 to 10 carbon atoms and more advantageously 1 to 6 carbon atoms.
  • the alkene can be an allyl group.
  • the alkene can contain one or more double bonds that are conjugated. In some embodiments the alkene can be substituted.
  • Alkoxy refers to the structure -OR, wherein R is hydrocarbyl.
  • Alkyne or “alkynyl” refers to a hydrocarbon chain or group containing one or more triple bonds between the chain carbon atoms.
  • the alkyne can be a straight hydrocarbon chain or a branched hydrocarbon group.
  • the alkyne can be cyclic.
  • the alkyne can contain 1 to 20 carbon atoms, advantageously 1 to 10 carbon atoms and more advantageously 1 to 6 carbon atoms.
  • the alkyne can contain one or more triple bonds that are conjugated. In some embodiments the alkyne can be substituted.
  • Amine refers to a molecule comprising at least one -NHR group wherein R can be a covalent bond, H, hydrocarbyl or polyether. In some embodiments an amine can comprise a plurality of -NHR groups.
  • Aryl or “Ar” refers to a monocyclic or multicyclic aromatic group. The cyclic rings can be linked by a bond or fused. The aryl can contain from 6 to about 30 carbon atoms; advantageously 6 to 12 carbon atoms and in some embodiments 6 carbon atoms. Exemplary aryls include phenyl, biphenyl and naphthyl. In some embodiments the aryl is substituted.
  • Ester refers to the structure R-C(O)-O-R' where R and R' are independently selected hydrocarbyl groups with or without heteroatoms.
  • the hydrocarbyl groups can be substituted or unsubstituted.
  • Halogen or "halide” refers to an atom selected from fluorine, chlorine, bromine and iodine.
  • Hetero refers to one or more heteroatoms in a structure. Exemplary heteroatoms are independently selected from N, O and S.
  • Heteroaryl refers to a monocyclic or multicyclic aromatic ring system wherein one or more ring atoms in the structure are heteroatoms. Exemplary heteroatoms are independently selected from N, O and S. The cyclic rings can be linked by a bond or fused.
  • the heteroaryl can contain from 5 to about 30 carbon atoms; advantageously 5 to 12 carbon atoms and in some embodiments 5 to 6 carbon atoms.
  • heteroaryls include furyl, imidazolyl, pyrimidinyl, tetrazolyl, thienyl, pyridyl, pyrrolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, thiazolyl, quinolinyl and isoquinolinyl.
  • the heteroaryl is substituted.
  • Hydrocarbyl refers to a group containing carbon and hydrogen atoms.
  • the hydrocarbyl can be linear, branched, or cyclic group.
  • the hydrocarbyl can be alkyl, alkenyl, alkynyl or aryl. In some embodiments, the hydrocarbyl is substituted.
  • (Meth)acrylate refers to acrylate and methacrylate.
  • Oligomer refers to a defined, small number of repeating monomer units such as 2-5,000 units, and advantageously 0- ,000 units which have been polymerized to form a molecule. Oligomers are a subset of the term polymer.
  • Polyether refers to polymers which contain multiple ether groups (each ether group comprising an oxygen atom connected top two hydrocarbyl groups) in the main polymer chain.
  • the repeating unit in the polyether chain can be the same or different.
  • Exemplary polyethers include homopolymers such as polyoxymethy!ene, polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetrahydrofuran, and copolymers such as poly(ethylene oxide co propylene oxide), and EO tipped polypropylene oxide.
  • Polyester refers to polymers which contain multiple ester linkages.
  • a polyester can be either linear or branched.
  • Polymer refers to any polymerized product greater in chain length and molecular weight than the oligomer. Polymers can have a degree of polymerization of about 20 to about 25000. As used herein polymer includes oligomers and polymers.
  • Substituted refers to the presence of one or more substituents on a molecule in any possible position.
  • Useful substituents are those groups that do not significantly diminish the disclosed reaction schemes.
  • Exemplary substituents include, for example, H, halogen, (meth)acrylate, epoxy, oxetane, urea, urethane, N3, NCS, CN, NCO, NO2, NX 1 X 2 , OX 1 , C(X 1 ) 3 , C(halogen) 3l COOX 1 , SX ⁇ Si(OX 1 )iX 2 3- i, alkyl, alcohol, alkoxy; wherein X 1 and X 2 each independently comprise H, alkyl, alkenyl, alkynyl or aryl and I is an integer from 0 to 3.
  • thiol refers to a molecule comprising at least one -SH group. In some embodiments a thiol can comprise a plurality of -SH groups.
  • hybrid polymer includes both hybrid oligomers and hybrid polymers.
  • the polyurethane polyisobutylene hybrid polymer is prepared from 1 ) an anhydride functional polyisobutylene component, 2) an isocyanate reactive component, and 3) a polyisocyanate component.
  • One embodiment describes a cured composition prepared from 1) an anhydride functional polyisobutylene component, 2) an isocyanate reactive component, and 3) a polyisocyanate component.
  • polyisobutylenesuccinic anhydride is polyisobutylenesuccinic anhydride (PIBSA).
  • PIBSA polyisobutylenesuccinic anhydride
  • SA succinic anhydride
  • Z can be selected from a linear or branched, substituted or unsubstituted, alkane or aikene portion having 0 to 10 carbon atoms.
  • anhydride functional polyisobutylene component encompasses a single PIBSA or a mixture of two or more PIBSAs.
  • PIBSA can be represented by the following structures:
  • PIBSA has a maximum molecular weight (Mn) of about 500,000 and a preferred molecular weight of 50,000 or less, and a more preferred molecular weight of 5,000 or less.
  • PIBSA lower molecular weight (about 2300 Mn or less) PIBSA is available commercially from suppliers such as Texas Petrochemicals Group, and Soltex Inc. Synthetic procedures for manufacture of higher molecular weight (about 2300 w or more) PIBSA are known. See, for example, United States Patent No. 4169836, the contents of which are incorporated by reference in their entirety.
  • an isocyanate reactive compound is a compound containing functional moieties that will react with an isocyanate moiety.
  • the isocyanate reactive component can be a single compound comprising an alcohol moiety, an amine moiety, a thiol moiety, or a compound with a combination of these moieties.
  • the isocyanate reactive component can be a mixture of compounds with each compound comprising one or more moieties independently selected from alcohol, amine, thiol and aminoalcohol.
  • the isocyanate reactive component can be an alcohol.
  • the alcohol is a polyol.
  • a polyol is understood to be a compound containing more than one OH group in the molecule.
  • a polyol can further have other functionalities on the molecule.
  • the term "polyol" encompasses a single polyol or a mixture of two or more polyols.
  • Some suitable polyol components include aliphatic alcohols containing 2 to 8 OH groups per molecule.
  • the OH groups may be both primary and secondary.
  • Some suitable aliphatic alcohols include, for example, ethylene glycol, propylene glycol, butane-1 ,4-diol, pentane-1 ,5-diol, hexane-1 ,6-diol, heptane-1 ,7-diol, octane-1 ,8-diol and higher homologs or isomers thereof which the expert can obtain by extending the hydrocarbon chain by one CH2 group at a time or by introducing branches into the carbon chain.
  • higher alcohols such as, for example, glycerol, trimethylol propane, pentaerythritol and oligomeric ethers of the substances mentioned either individually or in the form of mixtures of two or more of the ethers mentioned with one another.
  • Some suitable polyols include the reaction products of low molecular weight polyhydric alcohols with alkylene oxides, so-called polyether polyols.
  • the alkylene oxides preferably contain 2 to 4 carbon atoms.
  • Some reaction products of this type include, for example, the reaction products of ethylene glycol, propylene glycol, the isomeric butane diols, hexane diols or 4,4'-dihydroxydiphenyl propane with ethylene oxide, propylene oxide or butylene oxide or mixtures of two or more thereof.
  • polyhydric alcohols such as glycerol, trimethylol ethane or trimethylol propane, pentaerythritol or sugar alcohols or mixtures of two or more thereof
  • alkylene oxides mentioned to form polyether polyols are also suitable.
  • products of the addition of only a few mol ethylene oxide and/or propylene oxide per mol or of more than one hundred mol ethylene oxide and/or propylene oxide onto low molecular weight polyhydric alcohols may be used.
  • Other polyether polyols are obtainable by condensation of, for example, glycerol or pentaerythritol with elimination of water.
  • Some suitable polyols include those polyols obtainable by polymerization of tetrahydrofuran.
  • the polyethers are reacted in known manner by reacting the starting compound containing a reactive hydrogen atom with alkylene oxides, for example ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran or epichlorohydrin or mixtures of two or more thereof.
  • alkylene oxides for example ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran or epichlorohydrin or mixtures of two or more thereof.
  • Suitable starting compounds are, for example, water, ethylene glycol, 1 ,2- or 1 ,3- propylene glycol, 1 ,4- or 1 ,3-butylene glycol, hexane-1 ,6-diol, octane-1 ,8-diol, neopentyl glycol, 1 ,4-hydroxymethyl cyclohexane, 2-methyl propane-1 ,3-diol, glycerol, trimethylol propane, hexane-1 ,2,6-triol, butane-1 ,2,4-triol, trimethylol ethane, pentaerythritol, mannitol, sorbitol, methyl glycosides, sugars, phenol, isononylphenol, resorcinol, hydroquinone, 1 ,2,2- or 1 ,1 ,2-tris-(hydroxyphenyl)-ethane, ammonia, methyl
  • Some suitable polyols include diol EO/PO block copolymers, EO-tipped polypropylene glycols, or alkoxylated bisphenol A.
  • polyether polyols modified by vinyl polymers. These polyols can be obtained, for example, by polymerizing styrene or acrylonitrile or mixtures thereof in the presence of polyetherpolyol.
  • polyester polyols include polyester polyols.
  • polyester polyols obtained by reacting low molecular weight alcohols, more particularly ethylene glycol, diethylene glycol, neopentyl glycol, hexanediol, butanediol, propylene glycol, glycerol or trimethylol propane, with caprolactone.
  • polyester polyols are 1 ,4-hydroxymethyl cyclohexane, 2- methyl propane-1 ,3-diol, butane-1 ,2,4-triol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol.
  • polyester polyols obtained by polycondensation.
  • dihydric and/or trihydric alcohols may be condensed with less than the equivalent quantity of dicarboxylic acids and/or tricarboxylic acids or reactive derivatives thereof to form polyester polyols.
  • Suitable dicarboxylic acids are, for example, adipic acid or succinic acid and higher homologs thereof containing up to 16 carbon atoms, unsaturated dicarboxylic acids, such as maleic acid or fumaric acid, cyclohexane dicarboxylic acid (CHDA), and aromatic dicarboxylic acids, more particularly the isomeric phthalic acids, such as phthalic acid, isophthalic acid or terephthalic acid.
  • Citric acid and trimellitic acid are also suitable tricarboxylic acids. The acids mentioned may be used individually or as mixtures of two or more thereof.
  • Polyester polyols of at least one of the dicarboxylic acids mentioned and glycerol which have a residual content of OH groups are suitable.
  • Suitable alcohols include but not limited to propylene glycol, butane diol, pentane diol, hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexanedimethanol (CHDM), 2-methyl-1 ,3-propanediol (MPDiol), or neopentyl glycol or isomers or derivatives or mixtures of two or more thereof.
  • CHDM cyclohexanedimethanol
  • MPDiol 2-methyl-1 ,3-propanediol
  • High molecular weight polyester polyols may be used in the second synthesis stage and include, for example, the reaction products of polyhydric, preferably dihydric, alcohols (optionally together with small quantities of trihydric alcohols) and polybasic, preferably dibasic, carboxylic acids.
  • polyhydric preferably dihydric, alcohols (optionally together with small quantities of trihydric alcohols)
  • polybasic preferably dibasic, carboxylic acids.
  • the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters with alcohols preferably containing 1 to 3 carbon atoms may also be used (where possible).
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic or heterocyclic or both. They may optionally be substituted, for example by alkyl groups, alkenyl groups, ether groups or halogens.
  • Suitable polycarboxylic acids are, for example, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylene tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer fatty acid or trimer fatty acid or mixtures of two or more thereof. Small quantities of monofunctional fatty acids may optionally be present in the reaction mixture.
  • the polyester polyol may optionally contain a small number of terminal carboxyl groups.
  • Polyesters obtainable from lactones, for example based on e-caprolactone (also known as “polycaprolactones”), or hydroxycarboxylic acids, for example ⁇ -hydroxycaproic acid, may also be used.
  • Polyester polyols of oleochemica! origin may also be used.
  • Oleochemical polyester polyols may be obtained, for example, by complete ring opening of epoxidized triglycerides of a fatty mixture containing at least partly olefinically unsaturated fatty acids with one or more alcohols containing 1 to 12 carbon atoms and subsequent partial transesterification of the triglyceride derivatives to form alkyl ester polyols with 1 to 12 carbon atoms in the alkyl group.
  • Some suitable polyols include C36 dimer diols and derivatives thereof.
  • Some suitable polyols include castor oil and derivatives thereof.
  • Suitable polyols include fatty polyols, for example the products of hydroxylation of unsaturated or polyunsaturated natural oils, the products of hydrogenations of unsaturated and polyunsaturated polyhydroxy natural oils, polyhydroxyl esters of alkyl hydroxy! fatty acids, polymerized natural oils, soybean polyols, and alkylhydroxylated amides of fatty acids.
  • polystyrene resin examples include the hydroxy functional polybutadienes known, for example, by the commercial name of "Poly-bd” available from Sartomer Company Inc. Exton, PA.
  • polystyrene resin examples include polyisobutylene polyols.
  • polyacetal polyols include polyacetal polyols.
  • Polyacetal polyols are understood to be compounds obtainable by reacting glycols, for example diethylene glycol or hexanediol or mixtures thereof, with formaldehyde. Polyacetal polyols may also be obtained by polymerizing cyclic acetals.
  • Some suitable polyols include polycarbonate polyols.
  • Polycarbonate polyols may be obtained, for example, by reacting diols, such as propylene glycol, butane-1 ,4-diol or hexane-1 ,6-diol, diethylene glycol, triethylene glycol or tetraethylene glycol or mixtures of two or more thereof, with diaryl carbonates, for example diphenyl carbonate, or phosgene.
  • diols such as propylene glycol, butane-1 ,4-diol or hexane-1 ,6-diol
  • diethylene glycol triethylene glycol or tetraethylene glycol or mixtures of two or more thereof
  • diaryl carbonates for example diphenyl carbonate, or phosgene.
  • polystyrene resin examples include polyamide polyols.
  • polystyrene resins include polyacrylates containing OH groups. These polyacrylates may be obtained, for example, by polymerizing ethylenically unsaturated monomers bearing an OH group. Such monomers are obtainable, for example, by esterification of ethylenically unsaturated carboxylic acids and dihydric alcohols, the alcohol generally being present in a slight excess. Ethylenically unsaturated carboxylic acids suitable for this purpose are, for example, acrylic acid, methacrylic acid, crotonic acid or maleic acid.
  • Corresponding OH-functional esters are, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3- hydroxypropyl acrylate or 3-hydroxypropyl methacrylate or mixtures of two or more thereof .
  • the isocyanate reactive component can be a compound comprising an amine moiety.
  • the amine moieties can be primary amine moieties, secondary amine moieties, or combinations of both.
  • the compound comprises two or more amine moieties independently selected from primary amine moieties and secondary amine moieties (polyamine).
  • the compound can be represented by a structure selected from HRN-Z and HRN-Z-NRH where Z is a hydrocarbyl group having 1 to 20 carbon atoms and R can be a covalent bond, H, hydrocarbyl, heterohydrocarbyl or polyether.
  • Z is a straight or branched alkane or a straight or branched polyether.
  • Z can be a heterohydrocarbyl group.
  • Z can be a polymeric and/or oligomeric backbone. Such polymehc/oligomeric backbone can contain ether, ester, urethane, acrylate linkages.
  • R is H.
  • polyamine refers to a compound contains more than one -NHR group where R can be a covalent bond, H, hydrocarbyl, heterohydrocarbyl.
  • Suitable amine compounds include but are not limited to aliphatic polyamines, arylaliphatic polyamines, cycloaliphatic polyamines, aromatic polyamines, heterocyclic polyamines, polyalkoxypolyamines, and combinations thereof.
  • the alkoxy group of the polyalkoxypolyamines is an oxyethylene, oxypropylene, oxy-l,2-butylene, oxy- 1,4-butylene or a co-polymer thereof.
  • aliphatic polyamines include, but are not limited to
  • EDA Ethylenediamine
  • DETA diethylenetriamine
  • TETA triethylenetetramine
  • TMDA trimethyl hexane diamine
  • H DA hexamethylenediamine
  • N3-Amine N,N'-l,2-ethanediylbis-l,3- propanediamine
  • N4-amine dipropylenetriamine
  • arylaliphatic polyamines include, but are not limited to m- xylylenediamine (mXDA), and p- xylylenediamine.
  • cycloaliphatic polyamines include, but are not limited to 1 ,3-bisaminocyclohexylamine (1 ,3-BAC), isophorone diamine (IPDA), and 4,4'- methylenebiscyclohexanamine.
  • aromatic polyamines include, but are not limited to diethyltoluenediamine (DETDA), m-phenylenediamine, diaminodiphenylmethane (DDM), and diaminodiphenylsulfone (DDS).
  • heterocyclic polyamines include, but are not limited to N-aminoethylpiperazine (NAEP), and 3,9-bis(3-aminopropyl) 2,4,8, 10-tetraoxaspiro(5,5)undecane.
  • polyalkoxypolyamines where the alkoxy group is an oxyethylene, oxypropylene, oxy- 1 ,2- butylene, oxy-l,4-butylene or a co-polymer thereof include, but are not limited to 4,7- dioxadecane-l,10-diamine, 1- propanamine,2, l-ethanediyloxy))bis(diaminopropylated diethylene glycol).
  • Suitable commercially available polyetheramines include those sold by Huntsman under the Jeffamine trade name.
  • Suitable polyether diamines include Jeffamines in the D, SD, ED, XTJ, and DR series.
  • Suitable polyether triamines include Jeffamines in the T and ST series.
  • Suitable commercially available polyamines also include aspartic ester-based amine-functional resins (Bayer), dimer diamines (Uniqema, Priamine), Versalink amines from Air Products.
  • the amine compound may include other functionalities in the molecule.
  • the amine compound encompasses a single compound or a mixture of two or more amine compounds.
  • the isocyanate reactive component can be a thiol.
  • the thiol comprises two or more -SH moieties (polythiol).
  • the thiol comprises at least one -SH moiety and at least another functional moiety selected from -OH, -NH, -NH2, -COOH, or epoxide.
  • the thiol can be represented by the structure HS-Z-SH where Z is a hydrocarbyl group, a
  • Z is a straight or branched alkane or a straight or branched polyether.
  • suitable thiols include but are not limited to pentaerythritol tetra-(3-mercaptopropionate) (PETMP), pentaerythritol tetrakis(3- mercaptobutylate) (PET B), trimethylolpropane tri-(3- mercaptopropionate) (TMPMP), glycol di-(3-mercaptopropionate) (GDMP),
  • PTMA pentaerythritol tetramercaptoacetate
  • TPMA trimethylolpropane trimercaptoacetate
  • GDMA glycol dimercaptoacetate
  • ETMP 700 ethoxylated trimethylpropane tri(3-mercapto-propionate) 700
  • ETMP 1300 propylene glycol 3- mercaptopropionate 800
  • PPGMP 800 propylene glycol 3-mercaptopropionate 2200
  • PPGMP 2200 pentaerythritol tetrakis(3-mercaptobutanoate)
  • KarenzMT PE-1 from Showa Denko
  • soy polythiols Mercaptanized Soybean Oil
  • the isocyanate reactive component can be a compound comprising an aminoalcohol moiety.
  • an aminoalcohol moiety comprises at least one amino moiety and at least one hydroxyl moiety.
  • the amine group is terminal to the aminoalcohol compound molecule.
  • the amine group is a secondary amino group on the chain of the aminoalcohol compound molecule.
  • the aminoalcohol compound includes a terminal primary amine and a secondary amine.
  • the aminoalcohol compound can be represented by one of the following structures: HO-Z-NH-Z-OH or H 2 N-Z-NH-Z-OH or H 2 N-Z-(OH)2 where Z is a hydrocarbyl group and/or an heterohydrocarbyl having 1 to 50 carbon atoms.
  • Z is a straight or branched alkane or a straight or branched polyether.
  • Z contains cycloaliphatic moiety or aryl moiety.
  • aminoalcohols include but are not limited to diethanolamine, dipropanolamine, 3- amino-1 ,2-propanediol, 2-amino-1 ,3-propane diol, 2-amiono-2-methyl-1 ,3-propanediol, diisopropanolamine.
  • the aminoalcohol compound encompasses a single compound or a mixture of two or more aminoalcohol compounds.
  • the polyisocyanate component can be any compound having more than one isocyanate group.
  • polyisocyanate encompasses diisocyanate, polymeric isocyanates, and isocyanate-term inated oligomers and polymers.
  • isocyanates include ,5-naphthylene diisocyanate, 2,4- or 4,4 - diphenylmethane diisocyanate (MDl), hydrogenated MDI (HMDI), xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), 4,4'-diphenyl dimethyl-methane diisocyanate, di- and tetraalkylene diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1 ,3-phenylene diisocyanate, 1 ,4-phenylene diisocyanate, the isomers of toluene diisocyanate (TDI), 1-methyl-2,4-diisocyanatocyclohexane, 1 ,6-diiso-cyanato- 2,2,4-trimethyl hexane, 1 ,6-di
  • diisocyanates phosphorus-containing diisocyanates, 4,4'-diisocyanatophenyl perfluoroethane, tetramethoxybutane- ,4-diisocyanate, butane-1 ,4-diisocyanate, hexane-1 ,6-di isocyanate (HDI), dicyclohexylmethane diisocyanate, cyclo-hexane-1 ,4- diisocyanate, ethylene diisocyanate, phthalic acid-bis-isocyanatoethyl ester;
  • HDI dicyclohexylmethane diisocyanate
  • cyclo-hexane-1 ,4- diisocyanate ethylene diisocyanate
  • phthalic acid-bis-isocyanatoethyl ester phthalic acid-bis-isocyanatoethyl ester
  • diisocyanates containing reactive halogen atoms such as 1-chloromethylphenyl-2,4- diisocyanate, 1-bromomethylphenyl-2,6-diisocyanate or 3,3 ⁇ bis-chloromethylether4,4'- diphenyl diisocyanate.
  • Suitable isocyanates include aromatic polyisocyanates such as methylene triphenyl triisocyanate (MIT). Aromatic diisocyanates are characterized by the fact that the isocyanate group is positioned directly on the benzene ring. Suitable aromatic diisocyanates include 2,4- or 4,4'-diphenyl methane diisocyanate (MDI), the isomers of toluene diisocyanate (TDI) and naphthalene-1 ,5-diisocyanate (NDI). [078] Some suitable isocyanates include isocyanate terminated oligomers and prepolymers. Such prepolymers are formed by reacting excess amount of
  • polyisocyanate with a polyol, a polyamine, polythiol, or the combination of them.
  • Sulfur-containing polyisocyanates are obtained, for example, by reaction of 2 mol hexamethylene diisocyanate with 1 mol thiodiglycol or dihydroxydihexyl sulfide.
  • Other suitable diisocyanates are, for example, trimethyl hexamethylene diisocyanate, 1 ,4-diisocyanatobutane, 1 ,12-diisocyanatododecane and dimer fatty acid diisocyanate.
  • Suitable diisocyanates are the tetramethylene diisocyanate, hexamethylene
  • Aliphatic polyisocyanates with two or more isocyanate functionality formed by biuret linkage, uretdione linkage, allophanate linkage, and/or by trimerization are suitable.
  • Suitable at least trifunctional isocyanates are polyisocyanates formed by trimerization or oligomerization of diisocyanates or by reaction of diisocyanates with polyfunctional compounds containing hydroxyl or amino groups.
  • Isocyanates suitable for the production of trimers are the diisocyanates mentioned above, the trimerization products of HDI, MDI, TDI or IPDI being particularly preferred.
  • Blocked, reversibly capped polyisocyanates such as 1 ,3,5-tris-[6-(1- methylpropylideneaminoxycarbonylamino)-hexyl]-2,4,6-trix- ohexahydro-1 ,3,5-triazine, are also suitable.
  • polymeric isocyanates formed, for example, as residue in the distillation of diisocyanates are also suitable for use.
  • the polymeric MDI obtainable from the distillation residue in the distillation of MDI is suitable.
  • the polyisocyanate component encompasses a single polyisocyanate or the mixture of two or more polyisocyanates.
  • Polyisobutylene grafted polyurethane polymer and/or oligomer and curable compositions comprising such
  • the polyurethane polyisobutylene hybrid polymer can be prepared from the anhydride functional polyisobutylene component, the isocyanate reactive component, and the poly isocyanate component using a number of reaction schemes.
  • solvent is used in the reaction to modify viscosity of the reactants.
  • the solvent can optionally be removed after reaction using conventional processes if desired.
  • the reaction is carried out in the absence of solvent.
  • anhydride-functional polyisobutylene component, the isocyanate reactive component and the polyisocyanate component are combined to form a functional polyurethane polyisobutylene hybrid polymer.
  • the amount of polyisocyanate used to form the polyurethane polyisobutylene hybrid polymer will depend on the desired properties of the hybrid polymer. A deficiency of polyisocyanate (based on equivalents of polyisocyanate : isocyanate reactive components) will provide a fully reacted hybrid polymer with little or no isocyanate functionality. An excess of polyisocyanate (based on equivalents of polyisocyanate : isocyanate reactive
  • the isocyanate functionality can react with an external initiator, for example
  • the isocyanate functional polyurethane polyisobutylene hybrid polymer can be maintained under sealed conditions for commercially useful periods of time such as months.
  • the polyurethane polyisobutylene hybrid polymer can be prepared from about 10 - 90 % by weight of an anhydride functional polyisobutylene, 0.1 - 90 % by weight of an isocyanate reactive component, and 1 - 80 % by weight of a polyisocyanate component.
  • the polyurethane polyisobutylene hybrid oligomer or polymer has a maximum molecular weight of about 1 ,000,000 and a preferred molecular weight of about 500,000 or less, and a more preferred molecular weight of 100 to 100,000. Unless otherwise specified all molecular weights are on a number average basis (Mn) as measured by gel permeation chromatography (GPC) or size exclusion chromatography (SEC).
  • the polyurethane polyisobutylene hybrid oligomer or polymer can be a liquid, a paste or a solid. If solid, the polyurethane polyisobutylene hybrid oligomer or polymer can be formed in a convenient shape such as a film. Preferably, the polyurethane polyisobutylene hybrid oligomer or polymer is a viscous liquid or paste. Viscosity of liquid or paste polyurethane polyisobutylene hybrid oligomer or polymers can range from 10 centipoise (cPs) to about 100,000 poise (P) at 121 °C. Viscosity can be measured by standard methods such as, for example, Brookfield viscometer or rheometer. As used herein a liquid will flow under gravity at room temperature (about 70°F); a paste may or may not flow under gravity at room temperature but can be pumped; and a solid will not flow under gravity at room temperature and cannot be pumped at room temperature.
  • cPs centipo
  • the polyurethane polyisobutylene hybrid polymer can be used as the basis for a resin, a thermoplastic, a hot melt adhesive, a pressure sensitive adhesive, an elastomer or a foam.
  • the polyurethane polyisobutylene hybrid polymer can be used as the basis for part or all of a curable composition.
  • the curable composition can be a curable adhesive composition, a curable coating composition, a curable sealant composition, and a curable foam.
  • the curable compositions can be a storage stable single part composition that cures when exposed to defined conditions such as moisture or a multiple part composition where the parts are stored separately and react and cure when combined.
  • the curable composition can be a moisture reactive hot melt adhesive composition.
  • the curable hot melt adhesive composition can typically be free of water and/or solvent in either the solid (at room temperature) and/or molten form.
  • the curable composition can include up to 100% by weight of composition of polyurethane polyisobutylene hybrid polymer comprising residual isocyanate moieties.
  • the curable composition can also be in a solvent based form where polyurethane polyisobutylene hybrid polymer comprising residual isocyanate moieties is dissolved in a suitable solvent or solvent combinations.
  • suitable solvents include but not limited to ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, hexane, heptane, tetrahydrofuran, toluene, ethanol, and combinations thereof.
  • anhydride functional polyisobutylene component and the isocyanate reactive component are reacted to form an intermediate isocyanate reactive compound A.
  • the reaction opens the ring of the anhydride functional polyisobutylene component and, depending on ratio of anhydride functional polyisobutylene component to isocyanate reactive component in the reaction, the reaction condition, and the addition sequence isocyanate reactive component molecules are bonded to one or both ends of the opened ring.
  • Figure 1 shows an exemplary reaction of an anhydride functional polyisobutylene component and a polyol isocyanate reactive component to form intermediate isocyanate reactive compound A.
  • the exemplary intermediate isocyanate reactive compound A can be structure a and/or b depending on ratio of anhydride functional polyisobutylene component to isocyanate reactive component in the reaction.
  • Figure 2 shows an exemplary reaction of an anhydride functional polyisobutylene component and an amine isocyanate reactive component to form an exemplary intermediate isocyanate reactive compound A.
  • Figure 3 shows an exemplary reaction of an anhydride functional polyisobutylene component and a thiol isocyanate reactive component to form intermediate isocyanate reactive compound A.
  • the exemplary intermediate isocyanate reactive compound A can be structure a and/or b depending on ratio of anhydride functional polyisobutylene component to isocyanate reactive component in the reaction.
  • Figure 4 shows an exemplary reaction of an anhydride functional polyisobutylene component and an aminoalcohol isocyanate reactive component to form intermediate isocyanate reactive compound A.
  • the exemplary intermediate isocyanate reactive compound A can be structure a and/or b depending on ratio of anhydride functional polyisobutylene component to isocyanate reactive component in the reaction.
  • Figure 5 shows an exemplary reaction of an anhydride functional polyisobutylene component and an aminoalcohol isocyanate reactive component to form intermediate isocyanate reactive compound A.
  • the intermediate isocyanate reactive compound A is distinctively different from other functional polyisobutylenes. It has more than one isocyanate reactive group only at one end of the polyisobutylene chain. When reacted with polyisocyanates, this results in a polyurethane polybutylene hybrid polymer or a cured composition with pedant polyisobutylene arms on a polyurethane chain or polyurethane network.
  • the intermediate isocyanate reactive compound A has a maximum molecular weight of about 100,000 and a preferred molecular weight of about 500,000 or less, and a more preferred molecular weight of 100 to 100,000. Unless otherwise specified all molecular weights are on a number average basis (Mn) as measured by gel permeation chromatography (GPC) or size exclusion chromatography (SEC).
  • the intermediate isocyanate reactive compound A can be a liquid, a paste or a solid.
  • the intermediate isocyanate reactive compound A has a viscosity range from 0.1 centipoise (cps) to about 100,000 poise (P) at 121 °C. Viscosity can be measured by standard methods such as, for example, Brookfield viscometer or rheometer.
  • a liquid will flow under gravity at room temperature (about 70°F); a paste may or may not flow under gravity at room temperature but can be pumped; and a solid will not flow under gravity at room temperature and cannot be pumped at room temperature.
  • a process is disclosed to make an intermediate isocyanate reactive compound A by reacting an anhydride functional polyisobutylene with an isocyanate reactive component in bulk or in a solution.
  • intermediate isocyanate reactive compound A and the polyisocyanate component can be reacted to form the polyurethane polyisobutylene hybrid polymer, which can be used as a hot melt adhesive, a pressure sensitive adhesive, a resin, a foam, and a thermoplastic.
  • intermediate isocyanate reactive compound A, other isocyanate reactive component and the polyisocyanate component can be reacted to form the polyurethane polyisobutylene hybrid polymer, which can be used as a hot melt adhesive, a pressure sensitive adhesive, a resin, a foam, and a thermoplastic.
  • intermediate isocyanate reactive compound A and stoichiometric excess amount of polyisocyanate component can be reacted to form an isocyanate-terminated polyurethane polyisobutylene hybrid polymer, which can be used as a reactive hot melt adhesive, a reactive pressure sensitive adhesive, a reactive one-part liquid adhesive, all further crosslinkable when exposed to moisture.
  • intermediate isocyanate reactive compound A, other isocyanate reactive component and stoichiometric excess amount of polyisocyanate component can be reacted to form an isocyanate-terminated polyurethane polyisobutylene hybrid polymer, which can be used as a reactive hot melt adhesive, a reactive pressure sensitive adhesive, and a reactive one-part liquid adhesive, all further crosslinkable when exposed to moisture.
  • a curable composition is formed by from 10-98% by weight of an intermediate isocyanate reactive compound A and 1-90 % by weight of a polyisocyanate component.
  • intermediate isocyanate reactive compound A and stoichiometric excess amount of polyisocyanate component can be reacted to form an isocyanate-terminated polyurethane polyisobutylene hybrid polymer, which can be used with or without other isocyanates to form the isocyanate part of a multiple-part adhesive.
  • intermediate isocyanate reactive compound A, other isocyanate reactive component and stoichiometric excess amount of polyisocyanate component can be reacted to form an isocyanate-terminated polyurethane polyisobutylene hybrid polymer, which can be used with or without other isocyanates to form the isocyanate part of a multiple-part adhesive.
  • intermediate isocyanate reactive compound A is used with or without other isocyanate reactive component to form the Part A (isocyanate reactive component part) of a two part adhesive.
  • a curable composition in a two-component form is disclosed with Part A comprising intermediate isocyanate reactive compound A, and optionally an isocyanate reactive component; and Part B comprising a polyisocyanate component.
  • a curable composition in a two-component form is disclosed with Part A comprising intermediate isocyanate reactive compound A, and optionally an isocyanate reactive component; and Part B comprising a polyisocyanate component.
  • the curable composition of this embodiment further contains a solvent.
  • a curable composition in a two-component form based on 100% solids comprising up to 100% by weight of an intermediate isocyanate reactive compound A in Part A, and up to 100% by weight of a polyisocyanate component in Part B.
  • the mole ratio of Part A (isocyanate reactive component) to Part B (isocyanate component) is between 100:1 to 1 :100, preferably between 20:1 to 1 :20, even more preferably between 5:1 to 1 :5, and most preferably between 2:1 to 1 :2.
  • the curable compositions disclosed above can include a catalyst or cure- inducing component to modify speed of the initiated reaction.
  • Some suitable catalysts are those conventionally used in polyurethane reactions and polyurethane curing, including organometallic catalysts, organotin catalysts and amine catalysts.
  • Exemplary catalysts include DABCO T-12, DABCO crystalline, D DEE, DBU.
  • the curable composition can optionally include from about 0.01% to about 10% by weight of composition of one or more catalysts or cure-inducing components.
  • the curable composition can optionally include from about 0.05 % to about 3% by weight of composition of one or more catalysts or cure-inducing components.
  • the curable composition can optionally include filler.
  • fillers include, for example, lithopone, zirconium silicate, hydroxides, such as hydroxides of calcium, aluminum, magnesium, iron and the like, diatomaceous earth, carbonates, such as sodium, potassium, calcium, and magnesium carbonates, oxides, such as zinc, magnesium, chromic, cerium, zirconium and aluminum oxides, calcium clay, nanosilica, fumed silicas, silicas that have been surface treated with a silane or silazane such as the AEROSIL products available from Evonik Industries, silicas that have been surface treated with an acrylate or methacrylate such as AEROSIL R7200 or R711 available from Evonik Industries, precipitated silicas, untreated silicas, graphite, synthetic fibers and mixtures thereof.
  • AEROSIL products available from Evonik Industries
  • silicas that have been surface treated with an acrylate or methacrylate such as AEROSIL R7200 or R711 available
  • filler When used, filler can be employed in concentrations effective to provide desired properties in the uncured composition and cured reaction products and typically in concentrations of about 0% to about 90% by weight of composition, more typically 1 % to 30% by weight of composition of filler.
  • Suitable fillers include organoclays such as, for example, Cloisite nanoclay sold by Southern Clay Products and exfoliated graphite such as, for example, xGnP® graphene nanoplatelets sold by XG Sciences.
  • organoclays such as, for example, Cloisite nanoclay sold by Southern Clay Products and exfoliated graphite such as, for example, xGnP® graphene nanoplatelets sold by XG Sciences.
  • enhanced barrier properties are achieved with suitable fillers.
  • the curable composition can optionally include a thixotrope or rheology modifier.
  • the thixotropic agent can modify rheological properties of the uncured composition.
  • Some useful thixotropic agents include, for example, silicas, such as fused orfumed silicas, that may be untreated or treated so as to alter the chemical nature of their surface. Virtually any reinforcing fused, precipitated silica, fumed silica or surface treated silica may be used.
  • treated fumed silicas include polydimethylsiloxane-treated silicas, hexamethy!disilazane-treated silicas and other silazane or silane treated silicas.
  • Such treated silicas are commercially available, such as from Cabot Corporation under the tradename CAB-O-SIL ND-TS and Evonik Industries underthe tradename AEROSIL, such as AEROSIL R805.
  • AEROSIL such as AEROSIL R805.
  • untreated silicas include commercially available amorphous silicas such as AEROSIL 300, AEROSIL 200 and AEROSIL 130.
  • hydrous silicas include NIPSIL E150 and NIPSIL E200A manufactured by Japan Silica Kogya Inc.
  • the rheology modifier can be employed in concentrations effective to provide desired physical properties in the uncured composition and cured reaction products and typically in concentrations of about 0% to about 70% by weight of composition and advantageously in concentrations of about 0% to about 20% by weight of composition.
  • the filler and the rheology modifier can be the same.
  • the curable composition can optionally include an anti-oxidant.
  • an anti-oxidant include those available commercially from BASF under the tradename IRGANOX. When used, the antioxidant should be used in the range of about 0 to about 15 weight percent of curable composition, such as about 0.3 to about 1 weight percent of curable composition.
  • the curable composition can optionally include a reaction modifier.
  • a reaction modifier is a material that will increase or decrease reaction rate of the curable composition.
  • 8-hydroxyquinoline (8-HQ) and derivatives thereof such as 5- hydroxymethyl-8-hydroxyquinoline can be used to adjust the cure speed.
  • the reaction modifier can be used in the range of about 0.001 to about 15 weight percent of curable composition.
  • the curable composition can optionally contain a thermoplastic polymer.
  • the thermoplastic polymer may be either a functional or a non-functional thermoplastic.
  • suitable thermoplastic polymers include acrylic polymer, functional (e.g. containing reactive moieties such as -OH and/or -COOH) acrylic polymer, non-functional acrylic polymer, acrylic block copolymer, acrylic polymer having tertiary-alkyl amide functionality, polysiloxane polymer, polystyrene copolymer, polyvinyl polymer, divinylbenzene copolymer, polyetheramide, polyvinyl acetal, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride, methylene polyvinyl ether, cellulose acetate, styrene acrylonitrile, amorphous polyolefin, olefin block copolymer [OBC], polyolefin plastomer, thermoplastic urethane, polyacryl
  • the curable composition can optionally include one or more adhesion promoters that are compatible and known in the art.
  • adhesion promoters include amino silane, glycidyl silane, mercapto silane, isocyanato silane, vinyl silane, (meth)acrylate silane, and alkyl silane.
  • Common adhesion promoters are available from Momentive under the trade name Silquest or from Wacker Chemie under the trade name Geniosil. Silane terminated oligomers and polymers can also be used.
  • the adhesion promoter can be used in the range of about 0% to about 20% percent by weight of curable composition and advantageously in the range of about 0.1 % to about 15% percent by weight of curable composition.
  • the curable composition can optionally include one or more coloring agents.
  • a colored composition can be beneficial to allow for inspection of the applied composition.
  • a coloring agent for example a pigment or dye, can be used to provide a desired color beneficial to the intended application.
  • Exemplary coloring agents include titanium dioxide, C.I. Pigment Blue 28, C.I. Pigment Yellow 53 and phthalocyanine blue BN.
  • a fluorescent dye can be added to allow inspection of the applied composition under UV radiation.
  • the coloring agent will be present in amounts sufficient to allow observation or detection, for example about 0.002% or more by weight of total composition. The maximum amount is governed by considerations of cost, absorption of radiation and interference with cure of the composition. More desirably, the coloring agent may be present in amounts of up to about 20% by weight of total composition.
  • the curable composition can optionally include from about 0% to about 20% by weight, for example about 1% to about 20% by weight of composition of other additives known in the arts, such as tackifier, plasticizer, flame retardant, diluent, reactive diluent, moisture scavenger, and combinations of any of the above, to produce desired functional characteristics, providing they do not significantly interfere with the desired properties of the curable composition or cured reaction products of the curable composition.
  • additives known in the arts, such as tackifier, plasticizer, flame retardant, diluent, reactive diluent, moisture scavenger, and combinations of any of the above, to produce desired functional characteristics, providing they do not significantly interfere with the desired properties of the curable composition or cured reaction products of the curable composition.
  • the curable compositions can optionally include up to 80% by weight of the total weight of the curable composition of a suitable solvent.
  • This type of adhesives is known as solvent-based adhesives.
  • the solvent is quickly evaporated away, for example by heated ovens, then a second substrate is laminated onto the curable composition coated side of the first substrate to form a laminated structure.
  • Cured reaction products of the disclosed curable compositions have lower moisture permeability than conventional polyurethanes and other adhesives.
  • the cured reaction products are also expected to be resistant to polar solvents and materials.
  • the disclosed compositions will be useful wherever these barrier properties are desirable.
  • Adhesive compositions disclosed herein can be used to bond articles together. Under appropriate conditions for the type of composition the adhesive composition is applied to a first article and a second article is disposed in contact with the adhesive composition applied to the first article. The adhesive composition is exposed to conditions to promote curing. Cured reaction products of the adhesive composition bond the first and second articles.
  • the disclosed adhesive compositions are useful for bonding articles composed of a wide variety of substrates (materials), including but not limited to flexible films such as plastic films, metal films, and metalized plastic films, wood, metal, polymeric plastics, glass and textiles. Other applications include adhesives for bonding electronic components in OLEDs and LCDs, bonding hand held electronic devices such as cell phones, bonding photovoltaics, conformal coatings such as for electronic components and adhesives for backbedding or glazing windows.
  • the polyurethane polyisobutylene hybrid polymer by itself or as part of a composition, is cured to provide cured reaction products.
  • the intermediate isocyanate reactive compound A used as part of a composition, is cured to provide cured reaction products.
  • Viscosity - viscosity was measured using a Brookfield digital viscometer with a Thermosel heating unit, small sample adapter, SC-27 spindle, and HT-2 sample chamber.
  • WVTR Water Vapor Transmission Rate
  • the testing parameters such as nitrogen flow rate and ExamMinutes (EC) are adjusted accordingly.
  • Reported value in the examples below is taken after the WVTR value is equilibrated.
  • a small defect-free section of a cured film from the below examples is selected.
  • the film is masked between two aluminum masks (Mocon part No. 032-072) with a 1cm 2 sample area.
  • the thickness of the tested sample is measured by a caliper and reported with the WVTR value below. Care is taken to avoid defects in the 1cm 2 testing area of the sample.
  • Isocyanate content (%NCO) is measured with a Mettler-Toledo DL 25 auto titrator.
  • DABCO T-12 is a high-boiling liquid dibutyltindilaurate organotin compound available from Air Products and Chemicals, Inc.
  • DABCO 33-LV catalyst available from Air Products and Chemicals, Inc.
  • Desmodur N-3900 is an aliphatic polyisocyanate available from Bayer Material Science LLC.
  • Desmophen F-207-60 a solvent-free moderately branched saturated polyester polyol resin available from Bayer Material Science LLC.
  • JEFFCAT DMDEE is an amine catalyst available from Huntsman.
  • Dovermulse H-2300 is a polyisobutylene succinic anhydride available from Dover Chemical.
  • Dynacoll 7250 is an amorphous polyester available from Evonik.
  • Dynacoll 7360 is a crystalline polyester available from Evonik.
  • Irganox 245 is an antioxidant available from BASF.
  • Irganox 1010 is an antioxidant available from BASF.
  • MDI is a 4,4' diphenylmethane diisocyanate available from Bayer as Mondur M.
  • PCA 9050 is a polyisobutylene succinic anhydride available from Soltex Inc.
  • PIBSA 1000 a 1000 MW polyisobutylenesuccinic anhydride available from Texas Petrochemicals.
  • PolyBD R20LM a low molecular weight hydroxyl terminated polybutadiene polyol resin available from Cray Valley.
  • Polycin D-290 is a castor oil based polyol available from Vertellus.
  • Pripol 2030 is a dimer diol polyol available from Croda.
  • TMXDI is tetramethyl xylylene diisocyanate available from CYTEC Industries.
  • Mondur MRS-4 is a polymeric MDI from Bayer Material Science LLC.
  • the mixture then was made into thin films with various thickness draw down bars.
  • the films were stored in a dessicator overnight and then cured at ambient condition generally for 14 days.
  • a bubble free area of the cured film was then selected for the water vapor transmission rate (WVTR) testing using a Mocon Permatran 3/30 instrument according to the testing method outlined previously.
  • WVTR water vapor transmission rate
  • the reaction mixture was made into thin films with various thickness draw down bars.
  • the films were stored in a dessicator overnight and then cured at ambient condition generally for 14 days.
  • a bubble free area of the cured film was then selected for the water vapor transmission rate (WVTR) testing using a Mocon Permatran 3/30 instrument according to the testing method outlined previously.
  • WVTR water vapor transmission rate
  • the reaction mixture was made into thin films with various thickness draw down bars.
  • the films were stored in a dessicator overnight and then cured at ambient condition generally for 14 days.
  • a bubble free area of the cured film was then selected for the water vapor transmission rate (WVTR) testing using a Mocon Permatran 3/30 instrument according to the testing method outlined previously.
  • WVTR water vapor transmission rate
  • the reaction mixture was made into thin films with various thickness draw down bars.
  • the films were stored in a dessicator overnight and then cured at ambient condition generally for 14 days.
  • a bubble free area of the cured film was then selected for the water vapor transmission rate (WVTR) testing using a Mocon Permatran 3/30 instrument according to the testing method outlined previously.
  • WVTR water vapor transmission rate
  • Comparative Example B Synthesis of conventional polyurethane.
  • the reaction mixture was made into thin films with various thickness draw down bars.
  • the films were stored in a dessicator overnight and then cured at ambient condition generally for 14 days.
  • a bubble free area of the cured film was then selected for the water vapor transmission rate (WVTR) testing using a Mocon Permatran 3/30 instrument according to the testing method outlined previously.
  • WVTR water vapor transmission rate
  • the mixture was then made into thin films with various thickness draw down bars.
  • the films were stored in a dessicator overnight and then cured at ambient condition generally for 14 days to cure.
  • a bubble free area of the film was then selected for water vapor transmission rate (WVTR) testing using a Mocon Permatran 3/33 instrument according to the testing method outlined previously.
  • WVTR water vapor transmission rate
  • DIPA diisopropanol amine
  • the mixture was then made into thin films with various thickness draw down bars.
  • the films were stored in a dessicator overnight and then cured at ambient condition generally for 14 days to cure.
  • a bubble free area of the film was then selected for water vapor transmission rate (WVTR) testing using a Mocon Permatran 3/33 instrument according to the testing method outlined previously.
  • WVTR water vapor transmission rate
  • the mixture was then made into thin films with various thickness draw down bars.
  • the films were stored in a dessicator overnight and then cured at ambient condition generally for 14 days to cure.
  • a bubble free area of the film was then selected for water vapor transmission rate (WVTR) testing using a Mocon Permatran 3/30 instrument according to the testing method outlined previously.
  • WVTR water vapor transmission rate
  • PIBSA 1000 (205g, 200mmol) in toluene (600ml_). The mixture was stirred to dissolve PIBSA in toluene. After cooling to 0°C, 3-amino-1 ,2-propan-diol (18.3g, 200mmol) in toluene (100ml_) was added dropwise over a period of 30 min. The resulting viscous solution was warmed to room temperature (RT) and stirred for 2 hours. Toluene was evaporated to give the intermediate amic acid as a very viscous liquid.
  • the flask was heated to about 150°C and when the material starts to flow the materials is transferred to a 500m L 4 necked flask equipped with a mechanical stirrer and a nitrogen bubbler.
  • the mixture was heated to about 170°C. When the mixture becomes sufficiently flowable, mechanical stirring was started and nitrogen was bubbled through the mixture. The mixture slowly reaches a temperature of about 70°C after most of water generated by the imidization was flushed out by nitrogen bubbling.
  • the mixture was further heated for another 1 hour to remove last traces of water. This gave the imide diol as a light brown viscous liquid.
  • Example 9 Synthesis of the one-part moisture curable hot melt adhesive.
  • Viscosity at 121°C very high viscosity liquid, exceeding the measuring range with a SC4-27 spindle on a Brookfield DV-I or DV-II viscometer.
  • Example 10 Synthesis of one-part moisture curable hotmelt adhesive comprising polyurethane polyisobutylene hybrid polymer.
  • Example 8 To a clean reactor, charge in 30 grams Dynacoll 7360, 30 grams of Dynacoll 7250, and 20 grams of PIBSA based diol A form Example 8. Warm up to about 115°C to melt the ingredient. With stirring pull vacuum to dry the ingredients for 2 hours. Then charge in 20 grams of molten DI. Seal the reactor and react for 1 hour. Then pull vacuum for 1 hour. Viscosity at 121°C: 8200 cps
  • Comparative Example C Synthesis of one part moisture curable hotmelt adhesive comprising conventional polyurethane.
  • Example 11 One-pot synthesis of one-part moisture curable liquid adhesive comprising polyurethane polyisobutylene hybrid polymer.
  • Part B is Desmodur N-3900. Curable Adhesive:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des compositions, des oligomères et des polymères durcissables hybrides polyuréthane-polyisobutylène ayant des propriétés améliorées de barrière contre l'humidité. L'invention concerne également un procédé de préparation des oligomères et polymères hybrides polyuréthane-polyisobutylène.
PCT/US2014/046074 2014-07-10 2014-07-10 Adhésif polyuréthane ayant des propriétés de barrière améliorées WO2016007157A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210017432A1 (en) * 2018-03-16 2021-01-21 3M Innovative Properties Company Compositions, method of bonding, and bonded assembly

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02202908A (ja) * 1989-02-02 1990-08-13 Nippon Zeon Co Ltd ウレタン組成物
US6545101B2 (en) * 1997-06-25 2003-04-08 Exxonmobil Chemical Patents Inc. Star-branched polymer with dendrimer core

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02202908A (ja) * 1989-02-02 1990-08-13 Nippon Zeon Co Ltd ウレタン組成物
US6545101B2 (en) * 1997-06-25 2003-04-08 Exxonmobil Chemical Patents Inc. Star-branched polymer with dendrimer core

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210017432A1 (en) * 2018-03-16 2021-01-21 3M Innovative Properties Company Compositions, method of bonding, and bonded assembly

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