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WO2020069475A1 - Pré-polymères à base de polypropylène glycol pour le composant isocyanate d'un adhésif polyuréthane à deux composants pour la liaison de membranes - Google Patents

Pré-polymères à base de polypropylène glycol pour le composant isocyanate d'un adhésif polyuréthane à deux composants pour la liaison de membranes Download PDF

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Publication number
WO2020069475A1
WO2020069475A1 PCT/US2019/053702 US2019053702W WO2020069475A1 WO 2020069475 A1 WO2020069475 A1 WO 2020069475A1 US 2019053702 W US2019053702 W US 2019053702W WO 2020069475 A1 WO2020069475 A1 WO 2020069475A1
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WIPO (PCT)
Prior art keywords
component
membrane
separation apparatus
weight percent
polyurethane adhesive
Prior art date
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Ceased
Application number
PCT/US2019/053702
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English (en)
Inventor
Zachary BRYAN
Chih-Min Cheng
James M. Murray
Shuhua Jin
Li KANG
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Henkel IP and Holding GmbH
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Henkel IP and Holding GmbH
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Publication of WO2020069475A1 publication Critical patent/WO2020069475A1/fr
Priority to US17/199,765 priority Critical patent/US20210197126A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/10—Spiral-wound membrane modules
    • B01D63/103—Details relating to membrane envelopes
    • B01D63/1031—Glue line or sealing patterns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/10—Spiral-wound membrane modules
    • B01D63/107—Specific properties of the central tube or the permeate channel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/003—Membrane bonding or sealing
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/04—Specific sealing means
    • B01D2313/042—Adhesives or glues

Definitions

  • This invention relates to two-component curable polyurethane systems that are used as the adhesive to bond together membrane leaves used for reverse osmosis.
  • the inventive compositions when the two components are combined, result in polyurethane adhesives that are able to effectively penetrate the separation membrane.
  • the invention is also directed to the membrane leaf that is bonded using this two- component curable polyurethane system.
  • One component of such curable systems comprises an isocyanate functional pre-polymer that is the reaction product of a mixture comprising a polyisocyanate and polypropylene glycol.
  • the pre-polymer comprises an average of at least two isocyanate functionalities per molecule.
  • the other component of the two-component system is a composition comprising an isocyanate reactive component.
  • the isocyanate reactive component is a polyol or polyamine that is capable of reacting with the polyisocyanate pre-polymer, thereby forming a polyurethane (if a polyol is reacted) or polyurea (if a polyamine is reacted).
  • Two-component curable polyurethane adhesive systems can be applied using a number of methods. Viscosity of the newly mixed adhesive will be a composite of the viscosity of each component. Each application method will require the newly mixed adhesive to be within a defined viscosity range for successful use; below this range the applied mixture will spread and run and above this range the mixed adhesive may not apply evenly or at all.
  • Two-component curable polyurethane systems have traditionally relied on modification of the polyol component to effectively increase the viscosity or“thicken” mixtures of the two components. There currently are very few options available to effectively thicken the polyisocyanate component.
  • the most common method of increasing viscosity of the polyisocyanate component is to make an isocyanate functional pre-polymer, but pre-polymers, by their nature have a lower weight percent of NCO functionality, which historically results in poorer properties of the cured adhesive, reduced penetration of filtration in membranes and membrane problems such as blistering.
  • the disclosed two-component adhesive materials maintain the ability to penetrate the membrane layer materials, even at lower weight percent of the reactive isocyanate functionality in the pre-polymer.
  • improved penetration of the membrane (greater than 40%) by the adhesive is correlated with lower incidence of blistering. For consumers, less blistering means fewer failures of the membrane, which gives them greater reliability and value.
  • PPG Polypropylene glycol
  • MDI 2,4- and/or 4,4'-diphenylmethane diisocyanate
  • an embodiment of the two-component polyurethane adhesive disclosed herein made with the particular polypropylene glycol-based isocyanate pre- polymers disclosed herein, exhibits good adhesion to, and unexpected good penetration of, these semi-permeable filtration membrane materials.
  • This invention is specifically applicable to 2-component polyurethanes, used on filtration membranes.
  • One embodiment comprises an isocyanate pre-polymer made from reactants comprising an MDI (4,4-MDI, 2,4-MDI, modified MDI, polymeric MDI), and a long-chain PPG (average molecular weight from 700 to 2000 Daltons) which together produce an isocyanate pre-polymer providing control of viscosity of the two-component adhesive comprising the pre-polymer.
  • the two-component adhesive comprising this PPG-based pre-polymer maintains good penetration on commercial filtration media.
  • PPG-based polyisocyanate pre-polymers can enable the two-component polyurethane adhesive to achieve penetration of semi-permeable barrier membranes intended for reverse osmosis or nano-filtration applications even at NCO weight percent as low as 8% or even lower.
  • the PPG-based pre-polymer disclosed herein can optionally comprise other components.
  • Non-limiting examples of these optional components include: PPG having weight average molecular weight below 700 Dalton, dipropylene glycol which is usually a mixture of the three isomers (DPG), ethohexadiol (EH Diol), polytetrahydrofuran (PTMEG), castor oil, and other optional ingredients such as are known in the art, and mixtures thereof.
  • DPG dipropylene glycol which is usually a mixture of the three isomers
  • EH Diol ethohexadiol
  • PTMEG polytetrahydrofuran
  • castor oil and other optional ingredients such as are known in the art, and mixtures thereof.
  • Figure 1 shows a schematic cross section of a typical reverse-osmosis membrane
  • Figure 2 shows a schematic representation of a spiral-wound membrane element in use
  • Figure 3 shows a step in the construction of a membrane leaf element
  • Figure 4 shows another step in the construction of a membrane leaf element as part of a spiral-wound membrane element.
  • Figure 5 is a graph showing consistent penetration with increasing viscosity.
  • Figure 6 is a graph showing PPG molecular weight, viscosity and penetration.
  • Figure 7 is a schematic representation of a portion of a membrane leaf element. DETAILED DESCRIPTION OF THE INVENTION
  • alkane refers to a hydrocarbon chain or group containing only single bonds between the chain carbon atoms.
  • the alkane can be a straight
  • 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.
  • the alkane can be substituted.
  • Exemplary 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
  • 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.
  • R can be a covalent bond, H, hydrocarbyl or polyether.
  • an amine can comprise a plurality of -NHR groups (which may be referred to as a polyamine).
  • 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(0)-0-R’ where R and R’ are
  • 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.
  • 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;
  • 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.
  • Molecular weight refers to weight average molecular weight unless otherwise specified.
  • the number average molecular weight M n is determined according to the present invention by gel permeation chromatography (GPC, also known as SEC) at 23°C using a styrene standard. This method is known to one skilled in the art.
  • Polydispersity indicates the width of the molecular weight distribution and thus of the different degrees of polymerization of the individual chains in polydisperse polymers.
  • polydispersity value For many polymers and polycondensates, a polydispersity value of about 2 applies. Strict monodispersity would exist at a value of 1. A low polydispersity of, for example, less than 1.5 indicates a comparatively narrow molecular weight distribution.
  • Olemer refers to a defined, small number of repeating monomer units such as 2-5,000 units, and advantageously 10-1 ,000 units which have been
  • 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 polyoxymethylene, polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetrahydrofuran, and copolymers such as poly(ethylene oxide co propylene oxide), and EO tipped
  • 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.
  • Polyol refers to a molecule comprising two or more -OH groups.
  • “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) 3 , COOX 1 , SX 1 , 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.
  • a thiol can comprise a plurality of -SH groups (which may be referred to as a polythiol).
  • This invention relates to two-component or two-part curable polymeric systems.
  • the first component of such systems comprises a PPG-based
  • polyisocyanate pre-polymer component that is made from a polyisocyanate and polypropylene glycol (PPG).
  • PPG polypropylene glycol
  • the second component of the two-part curable polymeric system is a material that is capable of reacting with the PPG-based polyisocyanate pre-polymer material to form a polymeric material.
  • This component is referred to herein as“the isocyanate reactive component”.
  • the isocyanate reactive component of the present invention comprises one or more isocyanate reactive compounds.
  • an isocyanate reactive compound is a compound containing one or more, preferably two or more, 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.
  • One or more of the polyols, amines, thiols and aminoalcohols described below can individually be used or excluded from the isocyanate reactive component as desired.
  • the isocyanate reactive component can comprise or 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,
  • polystyrene resin examples include diol EO/PO (ethylene oxide/propylene oxide) 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:
  • 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 are 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 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 w-hydroxycaproic acid, may also be used.
  • Polyester polyols of oleochemical 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. Some 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 hydroxyl fatty acids, polymerized natural oils, soybean polyols, and alkylhydroxylated amides of fatty acids. Some suitable polyols include the hydroxy functional polybutadienes known, for example, by the commercial name of“Poly-bd ® " available from Cray Valley USA, LLC Exton, PA.
  • polystyrene resins examples include polyisobutylene polyols.
  • suitable 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.
  • suitable polyols include polyamide polyols.
  • polyacrylates containing OH groups 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 comprise or 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 polymeric/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-l, 4-butylene or a co-polymer thereof.
  • aliphatic polyamines include, but are not limited to
  • ethylenediamine EDA
  • diethylenetriamine DETA
  • triethylenetetramine TETA
  • trimethyl hexane diamine TMDA
  • hexamethylenediamine HMDA
  • N3-Amine N,N'-l,2-ethanediylbis-l,3- propanediamine (N4-amine)
  • dipropylenetriamine examples include, but are not limited to m-xylylenediamine (mXDA), and p- xylylenediamine. Examples of
  • 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
  • DDS diaminodiphenylsulfone
  • 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 e.g. Priamine ® (Croda); or diamines such as Versalink ® (Evonik).
  • 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 comprise or 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 heterohydrocarbyl group having 1 to 50 carbon atoms.
  • Z is a straight or branched alkane or a straight or branched polyether.
  • thiols include but are not limited to pentaerythritol tetra-(3- mercaptopropionate) (PETMP), pentaerythritol tetrakis(3- mercaptobutylate) (PETMB), trimethylolpropane tri-(3-mercaptopropionate) (TMPMP), glycol di-(3- mercaptopropionate) (GDMP), pentaerythritol tetramercaptoacetate (PETMA), trimethylolpropane trimercaptoacetate (TMPMA), glycol dimercaptoacetate (GDMA), ethoxylated trimethylpropane tri(3-mercapto-propionate) 700 (ETTMP 700), ethoxylated trimethylpropane tri(3-mercapto-propionate) 1300 (ETTMP 1300), propylene glycol 3- mercaptopropionate 800 (PPGMP 800), propylene glyco
  • the isocyanate reactive component can comprise or 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. In some embodiments the
  • aminoalcohol compound can be represented by one of the following structures: HO-Z- NH-Z-OH or H2N-Z-NH-Z-OH or H2N-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.
  • aminoalcohol compound encompasses a single compound or a mixture of two or more aminoalcohol compounds.
  • the two-component polyurethane adhesives can optionally contain one or more additives.
  • the additives can be contained in either or both of the PPG-based polyisocyanate pre-polymer component or the polyisocyanate-reactive component.
  • the curable compositions (two component polyurethane adhesives) disclosed herein can include a catalyst or cure-inducing component to modify speed of the initiated reaction.
  • catalysts are those conventionally used in polyurethane reactions and polyurethane curing, including organometallic catalysts, organotin catalysts and amine catalysts.
  • Exemplary catalysts include (1 ,4- diazabicyclo[2.2.2]octane) DABCO ® T-12 or DABCO ® crystalline, available from Evonik; DMDEE (2,2'-dimorpholinildiethylether); DBU (1 ,8-diazabicyclo[5.4.0]undec-7-ene).
  • 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.
  • filler 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.
  • 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
  • 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.
  • 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, castor oil derivatives such as RHEOCIN and THIXIN and silicas, such as fused or fumed 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, hexamethyldisilazane-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 under the tradename AEROSIL ® , such as AEROSIL ® R805.
  • AEROSIL ® such as AEROSIL ® R805.
  • the silicas that have been surface treated with an acrylate or methacrylate such as AEROSIL ® R7200 or R711 available from Evonik Industries.
  • untreated silicas examples include commercially available amorphous silicas such as AEROSIL ® 300, AEROSIL ® 200 and AEROSIL ® 130.
  • commercially available 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 the composition and advantageously in concentrations of about 0% to about 20% by weight of the composition.
  • the filler and the rheology modifier can be the same.
  • the curable composition can optionally include an antioxidant.
  • antioxidants include those available commercially from BASF under the tradename IRGANOX ® . When used, the antioxidant should be present 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, divinylbenzene copolymer, polyetheramide, polyvinyl acetal, polyvinyl butyral, polyvinyl chloride, methylene polyvinyl ether, cellulose acetate, styrene acrylonitrile, amorphous polyolefin, olefin block copolymer [OBC], polyolefin plastomer, thermoplastic urethane, polyacrylonitrile, ethylene acrylate copoly
  • 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.l. Pigment Blue 28, C.l. 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.
  • the polyisocyanate pre-polymers described herein are synthesized by reacting a stoichiometric excess of a polyisocyanate with at least one polyol comprising polypropylene glycol (PPG) wherein the reaction product pre-polymers have an NCO weight % between 8% and 25%.
  • the polyol used to form the PPG-based polyisocyanate pre-polymer comprises at least 20% or more by weight of polyol of polypropylene glycol (PPG).
  • PPG polypropylene glycol
  • the polyol used to form the prepolymer can be a mixture of polypropylene glycols of different molecular weights.
  • polyisocyanate is defined as a compound comprising at least two reactive isocyanate groups.
  • a polyol is understood to mean a compound comprising at least two hydroxyl groups per molecule that can react with the isocyanate groups on the polyisocyanate.“Excess” is understood to mean that there are more equivalents of isocyanate functionality from the polyisocyanate compound than equivalents of hydroxyl functionality from the polyol present during reaction to form the pre-polymer. All of the PPG is reacted and the resulting PPG-based polyisocyanate pre-polymers comprise reactive isocyanate groups.
  • the term“PPG- based polyisocyanate pre-polymer” is applied to any compound made according to the foregoing description, i.e., as long as the compound is made with a stoichiometric excess of isocyanate groups to hydroxyl groups.
  • the weight percent of reactive NCO in the pre-polymer is a function of the weight average molecular weight of the PPG used to make the pre-polymer. If the weight average molecular weight of the PPG is higher, there will be a lower weight percent of reactive NCO in the resulting prepolymer.
  • Aromatic polyisocyanates are characterized by the fact that the isocyanate groups are positioned directly on the benzene ring.
  • Suitable aromatic polyisocyanates include diphenyl methane diisocyanate (MDI) including the 2,2’- 2,4’- and 4,4'- isomers, polymeric MDI (pMDI), the isomers of toluene diisocyanate (TDI) and naphthalene-1 , 5- diisocyanate (NDI).
  • MDI diphenyl methane diisocyanate
  • pMDI polymeric MDI
  • TDI toluene diisocyanate
  • NDI 5- diisocyanate
  • polyisocyanates include but are not limited to 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- diisocyanato-2, 4, 4-trimethyl hexane, 1-isocyanatomethyl-3-isocyanato-1 ,5,5-trimethyl cyclohexane (IPDI), chlorinated and brominated diisocyanates, phosphorus-containing diisocyanates, 4,4'-diisocyanatophenyl perfluoroethane, tetramethoxybutane-1 ,4- diisocyanate, butane
  • diisocyanate 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.
  • Aromatic polyisocyanates are preferred and diphenyl methane diisocyanate (MDI) and polymeric MDI (pMDI) are more preferred as part or all of the polyisocyanates used for synthesis of the PPG-based pre-polymers.
  • MDI diphenyl methane diisocyanate
  • pMDI polymeric MDI
  • One or more of the polyisocyanates described above can individually be used or excluded from the isocyanate reactive component as desired.
  • the polypropylene glycols (PPG) used in the preparation of the PPG- based pre-polymers disclosed herein advantageously have a weight average molecular weight between 200 and 2500 Daltons and more typically between 400 and 2000 Daltons.
  • the polypropylene glycols (PPG) used in the preparation of the PPG-based pre-polymers disclosed herein advantageously have a functionality of 2 or more and typically about 2. Linear and branched polypropylene glycols are both suitable.
  • the PPG-based pre-polymers disclosed herein can be prepared using a mixture of different polypropylene glycols.
  • Polypropylene glycol is understood to mean, for example, a polyether polymer comprising the general structure:
  • n can have an average range from 8- 40.
  • the PPG can optionally contain minor amounts (e.g., up to 10 weight) of other epoxides such as ethylene oxide (EO) or butene oxide.
  • EO-tipped PPG or EO/propylene oxide random copolymers can also be used in the practice of this invention or excluded.
  • Dipropylene glycol and butane diol may also be incorporated or excluded.
  • FIGS. 1-4 The following description refers to FIGS. 1-4.
  • a typical thin-film composite membrane 10 intended for reverse osmosis and/or nanofiltration is generally rectangular in shape and is comprised of overlying layers having the general structure shown as a schematic cross-section in FIG. 1.
  • the membrane 10 comprises generally three layers: a thin, dense semi-permeable barrier layer 12 overlying a microporous substrate 14, the microporous substrate 14 overlying a porous support layer 16.
  • the porous support layer 16 is for example, a non-woven polyester, but is not necessarily limited to a non-woven polyester.
  • the porous support layer 16 is generally constructed and arranged to allow fluid to pass through it easily, while providing physical support for the other layers of the composite membrane 10.
  • the semi-permeable barrier layer 12 is commonly, but not necessarily a polyamide film, and the microporous substrate 14 is usually but not always comprised of a polysulfone film.
  • the materials of construction and their thickness, etc. may be varied depending on the exact separation application for which the membrane 10 is intended to be used.
  • the semi-permeable layer 12 is the active surface of the membrane 10 and is usually considered to be effecting the separation, either on its own or in combination with the intermediate microporous substrate 14, depending on the exact nature of the compounds being separated. For instance, if the membrane 10 is intended to be used to purify water, the membrane 10 will allow water to pass through, but not contaminants such as salt ions. [0078] A plurality of these membranes 10 are bonded together into a spiral- wound membrane element, using the two-component polyurethane adhesive that comprises, as the isocyanate component, the PPG-based pre-polymer disclosed herein.
  • FIGS. 2 - 4 show together, a typical spiral-wound membrane element 20 (FIG. 2) and the various components and the construction of the spiral-wound membrane element 20.
  • FIG. 2 shows schematically one embodiment of a spiral-wound membrane element 20 comprised of a center perforated permeate tube 26, around which is wound one or more membrane leaf elements 30 (one shown in FIG.7).
  • a permeate tube 26 is open to allow permeate 22 to flow out and the opposing end is sealed to prevent ingress of a feed stream 18 into the permeate tube 26.
  • the membrane leaf elements 30 are described in more detail below.
  • Each membrane leaf element 30 may be separated by a feed spacer 28, typically a polymeric net structure.
  • a feed stream 18 enters the spiral-wound membrane element 20 flowing through the space between the membrane leaf element provided by the feed spacer 28.
  • the feed stream 18 is comprised of at least two constituents.
  • a typical illustrative example of the feed stream 18 would be salt water having an initial concentration of salt. Water with none or a lower concentration of salt goes through the membranes 10 to form a permeate stream 22 of clean water.
  • the permeate stream 22 is directed through a porous permeate carrier layer 32 into the permeate tube 26 and discharged therefrom.
  • the concentrate stream 24 flows through a feed spacer 28 between the membrane leaf elements 30 and is discharged separately from the permeate stream 22.
  • each membrane leaf element 30 is comprised of two membranes, each 10, separated by a porous permeate carrier layer 32.
  • the membranes 10 are arranged so that each barrier layer 12 faces outwardly and each support layer 16 is adjacent to the carrier layer 32.
  • the two-component polyurethane adhesive 36 having the PPG-based polyisocyanate pre-polymer described herein is applied to a portion of the porous permeate carrier layer 32 and/or one or both of the adjacent porous support layers 16. Adhesive 36 is applied only adjacent one or more edges of the membrane material and is not applied over the entire surface.
  • the method of applying the two-component polyurethane adhesive 36 is not particularly limited and suitable methods are known to the skilled person.
  • the components of two-component polyurethane adhesive 36 can be mixed just before use and applied as a continuous bead along the open edges of the porous permeate carrier 32, as seen in FIG. 4.
  • the bead size is not particularly limited but it should bond only the edges of folded sheet 10 to the permeate carrier 32, leaving the interior portion of each unbonded.
  • Suitable bead widths can be for instance about 0.3 cm to about 2 cm or about .3 cm to about 0.6 cm.
  • the layers 10, 32, 10 are superimposed. It is desirable for the adhesive 36 to penetrate through the permeate carrier layer 32 and into or through each of the membranes 10.
  • the adhesive seals the membrane edges 10 to prevent the feed stream from entering into the membrane 10 and carrier layer 32 and also prevent permeate 22 from exiting the membranes except through the permeate tube 26.
  • the adhesive 36 must penetrate 40% or more into all three layers (porous support layer 16, microporous layer 14 and the barrier layer 12 shown in FIG. 1) of the membrane 10 and permeate carrier 32 to be acceptable. Penetration of 50%, 60%, 70%, 80% or more is preferable. This bonding process, i.e.
  • the membrane leaf element 30 layers are separated by a layer of feed spacer or feed carrier 28.
  • a layer of membrane 10 is laid out such that the semi-permeable layer 12 is facing toward the inside of the sheet 10 and the support layer 16 (not visible in FIG. 3) is on the outside.
  • a layer of feed spacer or feed carrier 28 is placed over a portion of the surface of permeable layer 12.
  • the combined layers are folded along line A-A to form a composite structure with the feed spacer 28 disposed between two membrane layers 10.
  • the feed spacer or feed carrier layer 28 is intended to provide space so that the feed 18 can flow freely inside the folded membrane sheet 10.
  • the feed carrier 28 depends on the intended application of the spiral-wound membrane element 20, but usually it is a non-woven material that allows free flow of the feed stream 18 between the adjacent folded portions of membrane sheet 10. Note that the feed carrier 28 may be slightly smaller than the folded membrane sheet 10, as shown schematically in FIG. 3.
  • FIG. 4 shows one embodiment in which a single leaf element 30 is wound around the permeate tube 26.
  • the permeate tube 26 has a plurality of perforations 34.
  • the porous permeate carrier layer 32 of the membrane leaf element 30 is wrapped around and bonded to the center perforated permeate tube 26 with adjacent layers of the leaf element separated by a feed carrier 28.
  • the two-component polyurethane adhesive 36 having the PPG-based polyisocyanate pre-polymer described herein can optionally be used to bond the carrier layer 32 to the permeate tube 26.
  • the porous permeate carrier 32 provides a flow channel to allow permeate 22 to flow through membrane 10, through the permeate carrier 32 and into the permeate tube 26.
  • PPG Polypropylene glycol
  • MDI methylene diphenylene diisocyanate; can be 1 ,4- or 2,4-MDI
  • DPG Dipropylene glycol; molecular weight: 134.2; mixture of the three isomers; chain extender, functionality 2.0 (Univar)
  • Castor Oil usually used as the polyol component of the two-component adhesive]; molecular weight 923.7 Daltons, average functionality 2.7 (Vertellus) 2-EH diol: Ethohexadiol; molecular weight: 146 Daltons, functionality 2.0 chain extender (Dixie Chemical)
  • PolyTHF/ PTMEG Polytetrahydrofuran; molecular weight 997.4 Daltons;
  • BASF alternative type of polyol
  • RHEOCIN ® A micronized hydrogenated castor oil; rheology modifier (BYK) Reverse Osmosis Membrane: Dow membrane BW30: (Dow)
  • ARCOL ® PPG 425 polypropylene glycol; molecular weight 426.6 Daltons, functionality 2.0 (Covestro)
  • ARCOL ® PPG 725 polypropylene glycol; molecular weight 763.2 Daltons, functionality 2.0 (Covestro)
  • ARCOL ® PPG 1000 polypropylene glycol; molecular weight 1010.8 Daltons, functionality 2.0 (Covestro)
  • ARCOL ® PPG 2000 polypropylene glycol; molecular weight 2003.6 Daltons, functionality 2.0 (Covestro)
  • ARCOL ® Poly-G 30-168 Polyether Triol; molecular weight 1002.0 comprises all secondary OH groups; glycerol propoxylated, functionality 3.0 (Covestro)
  • TMP Trimethylolpropane; crosslinker; molecular weight 135.3, functionality 3.0 (Nexeo)
  • MONDUR ® MB high-purity grade difunctional isocyanate; diphenylmethane 4,4'- diisocyanate; 33.6% NCO; molecular weight 250.0, functionality 2.0 (Covestro)
  • MONDUR ® CD modified 4,4’-MDI; modified with carbodiimide; 29.5% NCO; molecular weight 314.6, functionality 2.2 (Covestro)
  • MONDUR ® MLQ mixture of 4,4-methylene diphenylene diisocyanate (MDI) and 2,4-MDI; 33.6% NCO; molecular weight 250.0, functionality 2.0 (Covestro)
  • MONDUR ® MR Light poly MDI (mixture of polymerized 4,4- and 2,4 pMDI ); 33.5% NCO; molecular weight 372.4, functionality 2.8 (Covestro)
  • the polyisocyanate was first melted at 50°C prior to use, if it is not liquid.
  • the polyisocyanate was charged into a reactor heated to about 70°C.
  • the PPG was charged into the reactor next.
  • Selection of the weight average molecular weight (typically, 700 - 2000 Dalton) of the PPG is based on the target weight percent NCO of pre-polymer.
  • One or more optional components were also charged to the reactor if they were being used. These can include, but are not limited to, EH-Diol, DPG, PPG, PTMEG, and mixtures thereof. Catalysts can optionally also be used.
  • a polyol formulation used as the isocyanate reactive component to mix with the PPG-based polyisocyanate pre-polymers was prepared as follows. A mixture of 96.5 weight % Castor Oil and 3.5 % RHEOCIN ® was prepared by mixing these materials together at about 50°C for one hour at high shear in a temperature-controlled double planetary reactor under vacuum. The mixture was then cooled to room
  • the various PPG-based polyisocyanate pre-polymers described below were evaluated by mixing them with the isocyanate reactive component described above.
  • the PPG-based polyisocyanate pre-polymer and the isocyanate reactive component were weighed out to provide a mixed adhesive with a 1.1-1.2 index (i.e., with a slight stoichiometric excess of isocyanate moieties from the PPG-based polyisocyanate pre-polymer) and mixed in a speed mixer at 2000 RPM for 30 seconds.
  • Penetration was qualitatively estimated by visual analysis of the ratio of dark area to light area on the back side (i.e. on the barrier layer side 12 opposite the support layer 16). No visual change would be 100% light area and would correspond to 0% penetration. Complete penetration would be 100% dark area and would correspond to 100% penetration. The samples were evaluated side-by-side by more than one person to ensure consistency.
  • Samples were conditioned at 25°C in an oven for at least 18 hours before testing. They were quickly removed and tested using Brookfield RV Spindle 6 at 20 RPM. If the viscosity was over 50,000 mPa-sec, it was tested at 2 RPM using spindle 6. In one case it was over 1 M mPa-sec, so this was tested with Spindle 7 at 2 RPM.
  • Example 1 Effect of type of isocyanate and molecular weight of PPG in the pre- polvmer on membrane penetration
  • the pre-polymers shown in Table 3 were made and evaluated.
  • the molecular weight of the PPG used to make the pre-polymers was kept constant at 1000 Daltons and the likewise only one type of polyisocyanate was used to prepare the pre-polymers. Therefore, the effect of weight percent NCO on membrane penetration is demonstrated.
  • the pre-polymer formulations are shown as weight percent. The viscosities are reported for the pre-polymer and the percent of membrane penetration is for the final adhesive.
  • Example 4 The effect on membrane penetration of blends of various molecular weight of PPG in the pre-polymer
  • sample 12 45% penetration; 21 ,750 mPa-sec viscosity
  • sample 11 90% penetration; 30,850 mPa-sec viscosity
  • the pre-polymer formulations are shown as weight percent.
  • Example 6 The effect of using castor oil to make the pre-polymers compared to using PPO
  • Sample 21 with 34.3 % PPG-1000 had good membrane penetration of 85%, but the 10% PPG- 1000 in sample 22 was not enough to mitigate the detrimental effect of the castor oil in the pre-polymer, as shown by the membrane penetration of only 25%.
  • These results demonstrate that including PPG in the pre-polymer can result in pre-polymers having a much lower NCO% than castor oil.
  • Pre-polymers made with PPG effectively penetrated the membrane even with % NCO lower than 8%, but castor oil used alone had 0% penetration at 10 % NCO.
  • a blend of an adequate amount of PPG with castor oil in pre-polymer improved the membrane penetration by 15% compared to castor oil alone.
  • the results show that this blending effect is not linear.
  • Sample G, made with all castor oil (46.5%) had 70% penetration, while sample 22 made with 36.5% castor oil and 10% PPG having molecular weight of approximately 1000 only had membrane penetration of 25%.
  • the invention herein can be construed as excluding any element or process step that does not materially affect the basic and novel characteristics of the composition or process. Additionally, in some embodiments, the invention can be construed as excluding any element or process step not specified herein.

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

Abstract

L'invention concerne un adhésif de polyuréthane à deux composants à pénétration élevée pour un appareil de séparation, tel que des membranes de filtration par osmose inverse composites à couches minces. Le côté polyuréthane de l'adhésif à deux composants est un pré-polymère obtenu avec certains polypropylène glycols. De manière surprenante, des prépolymères de haute viscosité ayant un faible pourcentage en poids de fonctionnalité isocyanate ont présenté une excellente pénétration vis-à-vis de ces membranes. L'invention concerne également un procédé d'utilisation de ces adhésifs de polyuréthane à deux composants pour lier ces membranes.
PCT/US2019/053702 2018-09-28 2019-09-28 Pré-polymères à base de polypropylène glycol pour le composant isocyanate d'un adhésif polyuréthane à deux composants pour la liaison de membranes Ceased WO2020069475A1 (fr)

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US17/199,765 US20210197126A1 (en) 2018-09-28 2021-03-12 Hydrogenated natural oils to thicken the polyol component of a two-component polyurethane adhesive for bonding membranes

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US201862738079P 2018-09-28 2018-09-28
US62/738,079 2018-09-28

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PCT/US2019/053704 Continuation-In-Part WO2020069477A1 (fr) 2018-09-28 2019-09-28 Huiles naturelles hydrogénées pour épaissir le composant polyol d'un adhésif polyuréthane à deux constituants pour coller des membranes

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021262631A1 (fr) * 2020-06-23 2021-12-30 Henkel IP & Holding GmbH Adhésif thermofusible pour liaison de membrane enroulée en spirale
WO2022240551A1 (fr) * 2021-05-10 2022-11-17 Henkel IP & Holding GmbH Adhésif en polyuréthane de remplacement vert

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090026130A1 (en) * 2006-03-09 2009-01-29 Shinichi Chikura Spiral membrane element and process for producing the same
US20100096308A1 (en) * 2008-10-17 2010-04-22 General Electric Company Separator assembly
JP2011121029A (ja) * 2009-12-14 2011-06-23 Nippon Polyurethane Ind Co Ltd 膜シール材用ポリウレタン樹脂形成性組成物、及び該形成性組成物を用いた中空或いは平膜状繊維分離膜を用いたモジュール用膜シール材
US20130175214A1 (en) * 2010-09-07 2013-07-11 Toray Industries Inc. Separation membrane, separation membrane element, and method for producing separation membrane
US20150122407A1 (en) * 2013-11-04 2015-05-07 Bostik Sa Polyurethane-based two-component adhesive composition
US20150259583A1 (en) * 2014-03-12 2015-09-17 Cytec Industries Inc. Polyurethane adhesives for reverse osmosis modules
US20160298009A1 (en) * 2015-04-09 2016-10-13 Cytec Industries Inc. Polyurethane adhesives for reverse osmosis modules

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090026130A1 (en) * 2006-03-09 2009-01-29 Shinichi Chikura Spiral membrane element and process for producing the same
US20100096308A1 (en) * 2008-10-17 2010-04-22 General Electric Company Separator assembly
JP2011121029A (ja) * 2009-12-14 2011-06-23 Nippon Polyurethane Ind Co Ltd 膜シール材用ポリウレタン樹脂形成性組成物、及び該形成性組成物を用いた中空或いは平膜状繊維分離膜を用いたモジュール用膜シール材
US20130175214A1 (en) * 2010-09-07 2013-07-11 Toray Industries Inc. Separation membrane, separation membrane element, and method for producing separation membrane
US20150122407A1 (en) * 2013-11-04 2015-05-07 Bostik Sa Polyurethane-based two-component adhesive composition
US20150259583A1 (en) * 2014-03-12 2015-09-17 Cytec Industries Inc. Polyurethane adhesives for reverse osmosis modules
US20160298009A1 (en) * 2015-04-09 2016-10-13 Cytec Industries Inc. Polyurethane adhesives for reverse osmosis modules

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021262631A1 (fr) * 2020-06-23 2021-12-30 Henkel IP & Holding GmbH Adhésif thermofusible pour liaison de membrane enroulée en spirale
JP2023532445A (ja) * 2020-06-23 2023-07-28 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン スパイラル型膜接合用のホットメルト接着剤
WO2022240551A1 (fr) * 2021-05-10 2022-11-17 Henkel IP & Holding GmbH Adhésif en polyuréthane de remplacement vert

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