Environmentally friendly alternative polyurethane adhesive

Abstract

A two-component liquid curable polyurethane adhesive system is disclosed that includes an isocyanate-reactive part A and an isocyanate-functional part B. One or both parts include a substantial amount of sustainable materials. The mixed adhesive composition of the present invention can effectively bond to a separation membrane of a filtration device. The present invention also relates to a method of bonding filter assembly components using the two-component curable polyurethane adhesive composition, and to a filter assembly bonded together using the adhesive composition.

Description

[Technical Field]

[0001] This disclosure relates, in general, to a two-component liquid-curable polyurethane adhesive system comprising an isocyanate-reactive part A and an isocyanate-functional part B. The isocyanate-functional part B comprises one or more isocyanate-functional materials. The isocyanate-reactive part A comprises an isocyanate-reactive mixture. One or both parts contain a substantial amount of sustainable material. These two parts are mixed immediately before use to form a polyurethane adhesive composition, which react together ("cured") to form an irreversible solid polymer. The mixed adhesive composition of the present invention can effectively penetrate and adhere to the separation membrane of a filtration device. The present invention also relates to a method of bonding components of a filter assembly using this two-component liquid-curable polyurethane adhesive composition, and to a filter assembly bonded to each other using this adhesive composition. [Background technology]

[0002] Polyurethane adhesive is used to bond the components of the membrane filter, such as the membrane sheets themselves, the membrane sheets to the permeable tubes, and the wound filter assembly to the end caps.

[0003] Two-component adhesives are known to be used to bond membrane filter components. A two-component (2K) composition comprises two or more parts, typically an isocyanate-reactive part A and an isocyanate-functionalized part B. Each part is prepared separately from the others, stored in a warehouse, and shipped. The parts are mixed immediately before use. Since the curing reaction begins upon mixing, commercial storage after mixing is not possible.

[0004] However, many conventional adhesives do not function satisfactorily for membrane filter bonding applications. Some mixed adhesives have low viscosity and spread or flow unacceptably on the membrane surface. Some mixed adhesives have high viscosity and are difficult to dispense and work with in this application. Some mixed adhesives do not penetrate the membrane material, resulting in weak adhesion and the possibility of lifting from the membrane surface during use (blistering). "Blistering" is generally understood to mean damage to the membrane bond due to water penetration between the bonded layers. Some cured adhesives dissolve or decompose unacceptably when exposed to the very high or low pH environments common in membrane filter applications. Naturally, cured adhesives must have sufficient strength to maintain bonded components under high pressure in a liquid environment. For food filtration applications, it is highly desirable to use adhesives and materials that are suitable for contact with food. Adhesives must have a sufficiently long open time to allow assembly of components, but a sufficiently short curing time to give the assembled membrane filter sufficient strength to quickly move to the next manufacturing process.

[0005] In each application method, the newly mixed adhesive must be within a specified viscosity range for proper use. Below this range, the applied mixture will spread and flow; above this range, the mixed adhesive will not be applied uniformly or may not be applied at all. The viscosity of the newly mixed adhesive is the sum of the viscosities of each component. Conventionally, two-component curable polyurethane systems have used silica or amine as a rheology modifier in the isocyanate-reactive component to increase the viscosity of the isocyanate-reactive component, thereby increasing the viscosity of the mixed adhesive or thickening the mixture.

[0006] Polyurethane adhesives used to bond components of membrane filters were previously limited to those containing materials derived entirely or substantially from petrochemicals or other non-renewable resources. There is growing interest in using materials made from renewable or sustainable resources as a substitute for conventional non-renewable materials. It is even more desirable to use materials made from renewable or sustainable resources that are not part of the food chain. Naturally, sustainable adhesives must also meet all other stringent requirements for membrane bonding applications. [Overview of the Initiative]

[0007] One aspect of the present disclosure provides a two-component liquid-curable polyurethane adhesive system comprising an isocyanate-functional part B and an isocyanate-reactive part A. The isocyanate-functional part B comprises an isocyanate-functional material or mixture. The isocyanate-reactive part A comprises an isocyanate-reactive mixture. One or both parts contain a substantial amount of sustainable material.

[0008] Another aspect of the present disclosure provides an isocyanate-reactive part A comprising, in any case, 80% sustainable material, preferably 90% sustainable material, and more preferably about 100% sustainable material, based on the weight of the isocyanate-reactive part.

[0009] Another aspect of this disclosure provides sustainable reactive rheological modifiers, preferably isocyanate-reactive part A from non-food sources.

[0010] Another aspect of this disclosure provides a method for bonding filter assembly components using a mixed two-component curable polyurethane system containing substantially sustainable materials.

[0011] Another aspect of the present disclosure provides a filter assembly bonded to one another using a mixed two-component curable polyurethane system substantially containing sustainable materials.

[0012] While embodiments are described herein in order to produce a clear and concise specification, it is intended and understood that embodiments can be combined and separated in various ways without departing from the present invention. For example, it will be understood that all preferred features described herein are applicable to all embodiments of the present invention described herein. [Brief explanation of the drawing]

[0013] [Figure 1] Figure 1 shows a schematic cross-sectional view of a typical filter film. [Figure 2] Figure 2 shows a schematic diagram of a spiral-wound film element in use. [Figure 3] Figure 3 shows the construction process of the membrane leaf element. [Figure 4] Figure 4 shows another step in the construction of the spiral-wound film element. [Figure 5] Figure 5 shows a series of photographs illustrating the film penetration of various mixed adhesives. [Modes for carrying out the invention]

[0014] Detailed description of the invention Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. The following definitions apply as used herein for each of the various embodiments.

[0015] The singular forms "a," "an," and "the" include multiple references unless the context clearly indicates otherwise.

[0016] In relation to numerical values, where "approximately" or "about" is used herein, the value is ±10%, preferably ±5%, and more preferably ±1% or less.

[0017] As used herein, "at least one" means one or more, i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to components, this expression refers to the type of component and not to the absolute number of molecules. Therefore, "at least one polymer" means that, for example, at least one type of polymer can be used, that is, one type of polymer or a mixture of several different polymers.

[0018] As used herein, the terms "comprising", "comprises" and "comprised of" are synonymous with "including", "includes", "containing" or "contains", and are inclusive or open-ended; they do not exclude additional, unlisted members, elements or method steps.

[0019] When amounts, concentrations, dimensions and other parameters are expressed in the form of ranges, preferred ranges, upper limit values, lower limit values, or preferred upper and lower limit values, it should be understood that any range obtained by combining any upper limit or preferred value with any lower limit or preferred value is also specifically disclosed, regardless of whether the resulting range is explicitly mentioned in the context.

[0020] In this specification, the terms "Preferred" and "preferably" are frequently used herein to refer to embodiments of the present disclosure that can provide particular advantages under certain circumstances. However, recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude those other embodiments from the scope of the present disclosure.

[0021] The term "amine" means a molecule comprising at least one -NHR group, wherein R may be a covalent bond, H, hydrocarbyl, or polyether. In some embodiments, an amine may comprise a plurality of -NHR groups (this may also be referred to as a polyamine).

[0022] As used in this context, the term "free of" means that the amount of the corresponding substance in the reaction mixture is less than 0.05% by weight, preferably less than 0.01% by weight, more preferably less than 0.001% by weight, based on the total weight of the reaction mixture.

[0023] The term "hydrocarbyl" means a group comprising carbon and hydrogen atoms. Hydrocarbyl may be a linear, branched, or cyclic group. Hydrocarbyl may be alkyl, alkenyl, alkynyl or aryl. In some embodiments, hydrocarbyl is substituted.

[0024] Isocyanate or NCO content refers to the NCO content measured in accordance with EN ISO 11909.

[0025] Unless otherwise specified, the term "molecular weight" means number average molecular weight. The number average molecular weight Mn and the weight average molecular weight Mw are determined according to the present invention by gel permeation chromatography (also known as GPC or SEC) at 23°C using polystyrene standards. This method is known to those skilled in the art. Polydispersity is obtained from the average molecular weights Mw and Mn, and is calculated as PD = Mw / Mn.

[0026] The term "oligomer" refers to a certain small number of repeating monomer units, such as 2 to 5,000 units, advantageously 10 to 1,000 units, that are polymerized to form a molecule. Oligomers are a subset of the term polymer.

[0027] The term "polyether" refers to a polymer containing a plurality of ether groups in the main polymer chain, wherein each ether group contains an oxygen atom bonded to the top of two hydrocarbyl groups. The repeating units of the polyether chain may be the same or different. Exemplary polyethers include homopolymers such as polyoxymethylene, polyethylene oxide, polypropylene oxide, polybutylene oxide, and polytetrahydrofuran, copolymers such as poly(ethylene oxide-copropylene oxide), and EO-tipped polypropylene oxide.

[0028] The term "polyester" refers to a polymer containing a plurality of ester bonds. The polyester may be either linear or branched.

[0029] The term "polymer" refers to any polymerization product having a chain length and molecular weight greater than those of an oligomer. The polymer may have a degree of polymerization of from about 20 to about 25000. As used herein, the term "polymer" includes both oligomers and polymers.

[0030] The term "polyol" refers to a molecule containing two or more -OH groups.

[0031] Room temperature refers to a temperature of about 25°C.

[0032] The term "substituted" refers to the presence of one or more substituents at any possible position on a molecule. Useful substituents are groups that do not significantly diminish the disclosed reaction scheme. 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(X 1 and X 2Each of these elements independently contains H, alkyl, alkenyl, alkynyl, or aryl, where i is an integer from 0 to 3.

[0033] "Sustainable" refers to materials made from renewable or sustainable resources, such as plant-derived resources. A material is substantially sustainable if, by weight, it contains at least 50% sustainable material, preferably at least 75% sustainable material, more preferably at least 90% sustainable material, and most preferably about 100% sustainable material. Preferably, the sustainable material is derived in part or entirely from non-food sources.

[0034] When expressing quantities, concentrations, dimensions, and other parameters in the form of ranges, preferred ranges, upper limits, lower limits, or preferred upper and lower limits, it should be understood that any range obtained by combining any upper or preferred value with any lower or preferred value is also specifically disclosed, regardless of whether the resulting range is explicitly mentioned in the context.

[0035] In this specification, the terms "preferred" and "preferably" are frequently used to refer to embodiments of the disclosure that may provide particular benefits under specific circumstances. However, the description of one or more preferred or preferred embodiments is not intended to imply that other embodiments are not useful or to exclude these other embodiments from the scope of this disclosure.

[0036] This invention relates to two-component or two-part curable polymer systems. In many embodiments, one-component or one-part curable polymer systems would not be equivalent or useful.

[0037] The first or A part of a two-part curable adhesive composition comprises one or more materials capable of reacting with an isocyanate substructure to form a cured polymer material. This component is referred to herein as the "isocyanate-reactive A part."

[0038] The second or B part of the two-part curable adhesive composition comprises one or more isocyanate-functionalized materials having a reactive isocyanate substructure.

[0039] Isocyanate Reactivity Part A Part A contains one or more isocyanate-reactive components. An isocyanate-reactive component is a compound containing one or more, preferably two or more, functional substructures that react with an isocyanate substructure. Examples of isocyanate-reactive substructures include hydroxyl substructures, amine substructures, olefin substructures, thiol substructures, or combinations thereof.

[0040] One useful isocyanate-reactive compound is polyols. Polyols are compounds that contain more than one OH group in their molecule. Polyols can also have other functional groups besides OH on their molecule.

[0041] Suitable polyol components include aliphatic alcohols having 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 their higher homologs or isomers, which can be obtained by experts extending the hydrocarbon chain one CH2 at a time or by introducing branching into the carbon chain. Higher alcohols, such as glycerol, trimethylolpropane, pentaerythritol, and oligomeric ethers of the aforementioned substances, which may be individual ethers or ethers in the form of mixtures of two or more of the aforementioned alcohols, are also preferred.

[0042] Some suitable polyols include reaction products of low molecular weight polyhydric alcohols with alkylene oxides, so-called polyether polyols. The alkylene oxide preferably contains 2 to 4 carbon atoms. Examples of such reaction products include those resulting from the reaction of ethylene glycol, propylene glycol, isomer butanediol, hexanediol, or 4,4'-dihydroxydiphenylpropane with ethylene oxide, propylene oxide, or butylene oxide, or mixtures of two or more thereof. Reaction products of polyhydric alcohols such as glycerol, trimethylolethane or trimethylolpropane, pentaerythritol or sugar alcohols, or mixtures of two or more thereof, with the aforementioned alkylene oxides are also suitable for forming polyether polyols. Therefore, depending on the desired molecular weight, products obtained by adding only a few moles of ethylene oxide and / or propylene oxide per mole, or more than 100 moles of ethylene oxide and / or propylene oxide, to a low molecular weight polyhydric alcohol may be used. Other polyether polyols can be obtained, for example, by the condensation of glycerol or pentaerythritol with the elimination of water. Suitable polyols include those obtained by the polymerization of tetrahydrofuran.

[0043] The polyether is reacted by known methods, which involve reacting a starting compound having reactive hydrogen atoms with an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, or epichlorohydrin, or a mixture of two or more thereof.

[0044] Suitable starting compounds include, 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-hydroxymethylcyclohexane, 2-methylpropane-1,3-diol, glycerol, trimethylolpropane, hexane-1,2,6-triol, butane-1,2,4-triol, trimethylolethane, pentaerythritol, mannitol, and sorbitol. These include methyl glycosides, sugars, phenols, isononylphenol, resorcinol, hydroquinone, 1,2,2- or 1,1,2-tris-(hydroxyphenyl)-ethane, ammonia, methylamine, ethylenediamine, tetra- or hexamethylenediamine, triethanolamine, aniline, phenylenediamine, 2,4- and 2,6-diaminotoluene, and polyphenyl polymethylene polyamines that can be obtained by aniline / formaldehyde condensation, or mixtures of two or more of these.

[0045] Some suitable polyols include diol EO / PO (ethylene oxide / propylene oxide) block copolymers, EO-tipped polypropylene glycols, or alkoxylated bisphenol A.

[0046] Some suitable polyols include polyether polyols modified with vinyl polymers. These polyols can be obtained, for example, by polymerizing styrene or acrylonitrile or mixtures thereof in the presence of a polyether polyol.

[0047] Some suitable polyols include polyester polyols. For example, polyester polyols can be obtained by reacting caprolactone with a low molecular weight alcohol, more specifically ethylene glycol, diethylene glycol, neopentyl glycol, hexanediol, butanediol, propylene glycol, glycerol, or trimethylolpropane. Other polyhydric alcohols suitable for the production of polyester polyols are 1,4-hydroxymethylcyclohexane, 2-methylpropane-1,3-diol, butane-1,2,4-triol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, and polybutylene glycol.

[0048] Some suitable polyols include polyester polyols obtained by polycondensation. Therefore, polyester polyols may be formed by condensing divalent and / or trivalent alcohols with less than an equivalent amount of dicarboxylic acid and / or tricarboxylic acid or their reactive derivatives. Suitable dicarboxylic acids include, for example, adipic acid or succinic acid and their higher homologs containing up to 16 carbon atoms, unsaturated dicarboxylic acids such as maleic acid or fumaric acid, cyclohexanedicarboxylic acid (CHDA), and aromatic dicarboxylic acids, more specifically phthalic acid isomers such as phthalic acid, isophthalic acid or terephthalic acid. For example, citric acid and trimellitic acid are also suitable tricarboxylic acids. The above acids may be used individually or as a mixture of two or more. A polyester polyol of at least one of the above dicarboxylic acids and glycerol containing a residual OH group is preferred. Suitable alcohols include, but are not limited to, propylene glycol, butanediol, pentanediol, hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripylene glycol, cyclohexanedimethanol (CHDM), 2-methyl-1,3-propanediol (MPDiol), or neopentyl glycol, or their isomers or derivatives, or mixtures of two or more thereof. High molecular weight polyester polyols may also be used in a second synthesis step, for example, as reaction products of a polyhydric, preferably dihydric, alcohol (optionally together with a small amount of trihydric alcohol) and a polybasic, preferably dibasic, carboxylic acid. Instead of free polycarboxylic acid, the corresponding polycarboxylic acid anhydride or the corresponding polycarboxylic acid ester may be used (if possible) with an alcohol preferably containing 1 to 3 carbon atoms. The polycarboxylic acid may be aliphatic, alicyclic, aromatic, heterocyclic, or a combination of both. These may optionally be substituted with, for example, alkyl groups, alkenyl groups, ether groups, or halogens.Suitable polycarboxylic acids include, 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, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, fumaric acid, dimeric or trimeric fatty acids, or mixtures of two or more thereof. The reaction mixture may optionally contain small amounts of monofunctional fatty acids.

[0049] Polyester polyols may optionally contain a small number of terminal carboxyl groups. Polyesters obtained from lactones, such as ε-caprolactone (also known as "polycaprolactone"), or hydroxycarboxylic acids, such as ω-hydroxycaproic acid, may also be used.

[0050] Polyester polyols derived from oil and fat chemicals may also be used. For example, oil and fat chemical polyester polyols can be obtained by completely ring-opening an epoxidized triglyceride of a fatty mixture containing at least partially olefinically unsaturated fatty acids with one or more alcohols having 1 to 12 carbon atoms, and then forming an alkyl ester polyol having 1 to 12 carbon atoms in the alkyl group by partial transesterification of the triglyceride derivative.

[0051] Some suitable polyols include C36 dimer ols and their derivatives. Some suitable polyols include castor oil and its derivatives. Some suitable polyols include aliphatic polyols, such as hydroxylation products of unsaturated or polyunsaturated natural oils, hydrogenation products of unsaturated and polyunsaturated polyhydroxy natural oils, polyhydroxy esters of alkylhydroxy fatty acids, polymerized natural oils, soybean polyols, and alkylhydroxylated amides of fatty acids.

[0052] Some suitable polyols include, for example, hydroxy-functional polybutadiene known by the trade name "Poly-bd®" and commercially available from Cray Valley USA, LLC in Exton, Pennsylvania.

[0053] Some suitable polyols include polyisobutylene polyols. Some suitable polyols include polyacetal polyols. Polyacetal polyols are understood to be compounds obtained by reacting glycols, such as diethylene glycol or hexanediol, or mixtures thereof, with formaldehyde. Polyacetal polyols can also be obtained by polymerizing cyclic acetals. Some suitable polyols include polycarbonate polyols. Polycarbonate polyols can be obtained 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, such as diphenyl carbonate, or phosgene. Some suitable polyols include polyamide polyols.

[0054] Suitable polyols include polyacrylates containing OH groups. These polyacrylates may be obtained, for example, by polymerizing ethylenically unsaturated monomers having OH groups. Such monomers can be obtained, for example, by esterification of an ethylenically unsaturated carboxylic acid with a dihydric alcohol, where the alcohol is usually present in a small excess. Suitable ethylenically unsaturated carboxylic acids for this purpose include, for example, acrylic acid, methacrylic acid, crotonic acid, or maleic acid. Corresponding OH-functionalized esters include, 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.

[0055] The isocyanate-reactive component may be a polyamine. A polyamine is a compound containing multiple -NHR groups (where R may be a covalent bond, H, hydrocarbyl, or heterohydrocarbyl). Polyamines may further have non-amine functional groups on the molecule. The amine substructure may be a primary amine substructure, a secondary amine substructure, or a combination of both. In some embodiments, the compound comprises two or more amine substructures independently selected from primary and secondary amine substructures. In some embodiments, the compound may be represented by the structure HRN-Z-NRH, where Z is a hydrocarbyl group having 1 to 20 carbon atoms, and R may be a covalent bond, H, hydrocarbyl, heterohydrocarbyl, or polyether. In some embodiments, Z is a linear or branched alkane diradical, or a linear or branched polyether diradical. In some embodiments, Z may be a heterohydrocarbyl diradical. In some embodiments, Z may be a polymer skeleton and / or oligomer skeleton. Such polymer / oligomer skeletons may contain ether, ester, urethane, or acrylate bonds. In some embodiments, R is H.

[0056] Some suitable polyamine compounds include aliphatic polyamines, arylaliphatic polyamines, alicyclic polyamines, aromatic polyamines, heterocyclic polyamines, polyalkoxy polyamines, and combinations thereof. The alkoxy group of the polyalkoxy polyamine is oxyethylene, oxypropylene, oxy-1,2-butylene, oxy-1,4-butylene, or copolymers thereof.

[0057] Examples of aliphatic polyamines include, but are not limited to, ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), trimethylhexanediamine (TMDA), hexamethylenediamine (HMDA), N-(2-aminoethyl)-l,3-propanediamine (N3-amine), N,N'-1,2-ethanediylbis-l,3-propanediamine (N4-amine), and dipropylenetriamine. Examples of arylaliphatic polyamines include, but are not limited to, m-xylylenediamine (mXDA) and p-xylylenediamine. Examples of alicyclic polyamines include, but are not limited to, 1,3-bisaminocyclohexylamine (1,3-BAC), isophoronediamine (IPDA), and 4,4'-methylenebiscyclohexaneamine. Examples of aromatic polyamines include, but are not limited to, diethyltoluenediamine (DETDA), m-phenylenediamine, diaminodiphenylmethane (DDM), and diaminodiphenylsulfone (DDS). Examples of 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. Examples of polyalkoxy polyamines in which the alkoxy group is oxyethylene, oxypropylene, oxy-1,2-butylene, oxy-1,4-butylene, or copolymers thereof include, but are not limited to, 4,7-dioxadecane-1,10-diamine, 1-propanamine, and 2,1-ethanediyloxy()bis(diaminopropylated diethylene glycol). A suitable commercially available polyetheramine is one sold by Huntsman under the trade name Jeffamine®. Suitable polyetherdiamines include Jeffamines® of the D, SD, ED, XTJ, and DR series. Suitable polyethertriamines include Jeffamines® of the T and ST series.

[0058] Suitable commercially available polyamines include aspartic acid ester-based amine-functional resins (Bayer); dimer amines such as Priamine® (Croda) or Versalink® (Evonik).

[0059] The isocyanate-reactive part may be a polythiol having two or more -SH substructures. Polythiols may have functional groups other than thiols on the molecule, such as -OH, -NH, -NH2, -COOH, or epoxides. In some embodiments, polythiols can be represented by the structure HS-Z-SH, where Z is a hydrocarbyl group or heterohydrocarbyl group having 1 to 50 carbon atoms. In some embodiments, Z is a linear or branched alkane, or a linear or branched polyether. Some suitable polythiols include, but are not limited to, pentaerythritol tetra-(3-mercaptopropionate) (PETMP), pentaerythritol tetrakis(3-mercaptobutyrate) (PETMB), trimethylolpropane tri-(3-mercaptopropionate) (TMPMP), glycol di-(3-mercaptopropionate) (GDMP), pentaerythritol tetramercaptoacetate (PETMA), trimethylolpropane trimercaptoacetate (TMPMA), glycol dimercaptoacetate (GDMA), ethoxylated trimethylpropane tri(3-mercaptopropionate) 700 (ETTMP 700), and ethoxylated trimethylpropane tri(3-mercaptopropionate) 1300 (ETTMP It contains 1300), propylene glycol 3-mercaptopropionate 800 (PPGMP 800), propylene glycol 3-mercaptopropionate 2200 (PPGMP 2200), pentaerythritol tetrakis (3-mercaptobutanoate) (Showa Denko KarenzMT PE-1), and soybean polythiol (mercapto-modified soybean oil).

[0060] The isocyanate-reactive part may be an amino alcohol. An amino alcohol is a compound having at least one amino substructure and at least one hydroxyl substructure. In some embodiments, the amine group is at the end of the amino alcohol compound molecule. In some embodiments, the amine group is a secondary amino group on the chain of the amino alcohol compound molecule. In some embodiments, the amino alcohol compound includes terminal primary and secondary amines. In some embodiments, the amino alcohol 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 (wherein Z is a hydrocarbyl group and / or heterohydrocarbyl having 1 to 50 carbon atoms). In some embodiments, Z is a linear or branched alkane or a linear or branched polyether. In some embodiments, Z includes an alicyclic substructure or an aryl substructure. Some suitable amino alcohols include, but are not limited to, diethanolamine, dipropanolamine, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, and diisopropanolamine. Amino alcohol compounds include single compounds or mixtures of two or more amino alcohol compounds.

[0061] Any of the above isocyanate-reactive components may be useful. However, in order to maximize the sustainable content of the adhesive composition, at least some, preferably almost all, of the isocyanate-reactive components, excluding additives, are sustainable materials. In some preferred embodiments, almost all or all of the isocyanate-reactive components, excluding additives, are sustainable materials from non-food chain sources. These embodiments would exclude non-sustainable isocyanate-reactive materials from the Part A composition. Several sustainable isocyanate-reactive materials are known. Castor oil and glycerol are useful sustainable isocyanate-reactive materials that can be obtained from non-food chain sources. U.S. Patents 6,891,053, 8,757,294, and 8,575,378 disclose methods for producing polyols based on modified plants. U.S. Patent 10,294,328 discloses a method for producing transesterified polyols from natural oils and polylactic acid. Other commercially available sustainable isocyanate-reactive components include hydroxylated vegetable oils (also known as bio-polyols), such as hydroxylated soybean oil, almond oil, canola oil, coconut oil, cod liver oil, corn oil, cottonseed oil, flaxseed oil, linseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, sunflower oil, walnut oil, and castor oil.

[0062] Part A allows the use of two or more isocyanate-reactive components in combination. Alternatively, Part A can be formulated to exclude certain isocyanate-reactive materials that are not essential to the adhesive composition.

[0063] Part A preferably has a viscosity of about 100,000 cps or less at 25°C (more preferably about 80,000 cps or less, and most preferably about 75,000 cps or less).

[0064] Isocyanate Sensitivity Part B Part B comprises one or more polyisocyanates. Suitable polyisocyanates include monomeric polyisocyanates; modified monomeric polyisocyanates; polymeric polyisocyanates such as polymer MDI; and isocyanate-functionalized prepolymers.

[0065] Part B preferably has a weight-average isocyanate functional value of about 2.0 to about 3.3. The weight-average functional value (fNCO) of the polyisocyanate mixture of Part B is calculated as follows: fNCO = (wt.% polyisocyanate 1 * f polyisocyanate 1) + (wt.% polyisocyanate i * f polyisocyanate i) + ... In other words, the weight-average functional value is the sum of the results obtained by multiplying the functional value of each given polyisocyanate by its weight % based on the total weight of Part B.

[0066] Part B preferably has a viscosity of about 30,000 cps or less at 25°C (more preferably about 25,000 cps or less, most preferably about 20,000 cps or less). If Part B contains a polyurethane prepolymer, these prepolymers may have a molecular weight (Mn) of 500 to 27,000, or 700 to 15,000, or 700 to 8,000 g / mol.

[0067] Useful monomeric polyisocyanates include 4,4'-diphenylmethane diisocyanate (4,4'MDI) and its 2,4-diphenylmethane diisocyanate (2,4'-MDI), and 2,2'-diphenylmethane diisocyanate (2,2'-MDI) isomers; hexane-1,6-diisocyanate (HDI); hydrogenated MDI (H12MDI); toluene diisocyanate (TDI) and its isomers. Monomeric polyisocyanates in monomeric form can be used as a single isomer or any combination of isomers. For example, three isomers can be used for diphenylmethane diisocyanate (MDI). A mixture of two or more of these isomers can be used in some or all of the polyisocyanates, or one or more of these isomers can be excluded.

[0068] Modified monomer polyisocyanates include polyisocyanates in which 1% or more of the isocyanate groups are modified into carbodiimide, allophanate, biuret, or polymer forms. For example, modified versions of diphenylmethane diisocyanate (MDI) include, for example, carbodiimide-modified diphenylmethane diisocyanate (carbodiimide-modified MDI), allophanate-modified diphenylmethane diisocyanate (allophanate-modified MDI), biuret-modified diphenylmethane diisocyanate (biuret-modified MDI), polymer MDI, and combinations thereof.

[0069] Polyurethane prepolymers comprise a reaction product of a polyol or polyamine with an excess of one or more polyisocyanates. The reaction product is a polyurethane or polyurea having a reactive isocyanate substructure on its molecule. Any of the above polyols or polyamines are useful. However, to maximize the sustainable content of the adhesive composition, it is preferable that some or all of the polyols and / or polyamines used to form the polyurethane prepolymer are sustainable materials.

[0070] A combination of two or more polyisocyanates can be used in Part B. Alternatively, Part B can be formulated to exclude certain polyisocyanates that are not essential to the adhesive composition.

[0071] MDI, modified MDI, polymer MDI, and polyurethane prepolymers prepared using MDI are preferred for use in Part B.

[0072] Reactive rheological modifiers The adhesive composition contains a sustainable reactive rheology modifier. Useful sustainable reactive rheology modifiers include waxes derived from sustainable sources such as sunflower wax, soybean wax, carnauba wax, laurel wax, candelilla wax, rice bean wax, berry wax, natural beeswax, synthetic beeswax, and myrica fruit wax. Unless otherwise specified, beeswax includes natural and synthetic beeswax. In some embodiments, the composition is essentially free of or does not contain a castor oil or castor oil derivative-based reactive rheology modifier. Preferably, the sustainable reactive rheology modifier is from a non-food source. Useful sustainable reactive rheology modifiers from non-food sources include natural or synthetic beeswax, more preferably natural beeswax. Natural beeswax is a by-product of honey extraction from beehives. The beeswax is washed to remove impurities and molded into a shape suitable for subsequent use. Natural beeswax is a sustainable material and is commercially available, for example, from Koster Keunen in Connecticut, USA.

[0073] Natural beeswax is a complex substance secreted in liquid form from specialized wax glands in the abdomen of young worker bees. When exposed to air, it hardens into a scaly structure (which the bees use to build their honeycomb with their jaws). Natural beeswax is chemically different from, but chemically related to, commercially available synthetic homopolymer and copolymer waxes.

[0074] When secreted by bees, pure beeswax is nearly white; after contact with honey and pollen, it turns a variety of strong yellowish colors, and after about four years it turns brown. Beeswax is resistant to the action of bee acids and gastric juices and does not dissolve in water or cold alcohol; it partially dissolves in boiling alcohol and completely dissolves in chloroform, carbon disulfide, and hot turpentine essence. When the wax is treated with boiling alcohol, the dissolving portion is formed by free cerotic acid or cerotic acid mixed with a small amount of melissic acid, while the undissolving portion is formed by ether-melissylpalmitic acid mixed with a small amount of palmitic acid and an ether compound of stearic acid. The density of beeswax at 15°C is approximately 0.960 kg / m³ 3 ~0.970 kg / m 3 It melts at 63.5°C to 64.5°C.

[0075] Natural beeswax is a complex mixture of hydrocarbons, free fatty acids, esters and diesters of fatty acids and fatty alcohols, and exogenous substances (more than 300 components).

[0076] Natural beeswax may contain: 12%–16% hydrocarbons with a main chain length of C27–C33, mainly heptacosane, nonacosane, hentricontane, pentacosane, and tricosane; 12%–14% free fatty acids with a chain length of C24–C32; about 1% free fatty alcohols with a chain length of C28–C35; 35%–45% linear wax monoesters and hydroxy monoesters with a chain length of generally C40–C48, basically derived from palmitic acid, 15-hydroxypalmitic acid, and oleic acid; 15%–27% complex wax esters in which 15-hydroxypalmitic acid or diol is bonded to other fatty acid molecules; and exogenous substances, mainly propolis, pollen, fragments of floral components, and residues of contaminants. Naturally, the composition of beeswax varies depending on the bee family and species, as well as the geographical region. For example, see Beeswax: A minireview of its antimicrobial activity and its application in medicine; Asian Pacific Journal of Tropical Medicine; Volume 9, Issue 9, September 2016, Pages 839-843.

[0077] Natural beeswax is a complex combination of long-chain organic substances containing unsaturated (C=C bonds) and hydroxyl (CHOH) and hydroxyl (OH) functional groups within its molecule. Analysis revealed that one sample of sustainable beeswax had an unsaturated content of 0.7%, a hydroxyl content of 1.0%, and a hydroxyl content of 0.5%.

[0078] Synthetic beeswax is an artificial beeswax created to replicate the main components of natural beeswax. Synthetic beeswax is commercially available, for example, from Koster Keunen in Connecticut, USA.

[0079] Because beeswax reacts with the isocyanate substructure of Part B, it must be a component of Part A only. One problem is that beeswax is incompatible with most other isocyanate-reactive materials in Part A. This incompatibility causes the beeswax to separate as a solid from the Part A composition, rendering the Part A composition unusable. Surprisingly, the applicants discovered that shear mixing of beeswax and glycerol produces a stable dispersion that can be added to other isocyanate-reactive materials to form Part A.

[0080] additives The two-component polyurethane adhesive composition may optionally contain one or more additives.

[0081] A two-component curable composition may optionally contain other additives, such as catalysts, fillers, additional thixotrope or rheology modifiers, antioxidants, reaction modifiers, thermoplastic polymers, adhesion promoters, colorants, solvents, tackifiers, plasticizers, flame retardants, diluents, reactive diluents, moisture scavengers, and any combination thereof, to provide desired functional properties, provided that these additives do not significantly interfere with the desired properties of the curable composition or the curing reaction product of the curable composition.

[0082] Curable adhesive compositions may optionally contain catalysts or curing-inducing components to adjust the rate of the initiated reaction. Several suitable catalysts are those conventionally used in polyurethane reactions and curing, including organometallic catalysts, organotin catalysts, and amine catalysts. Exemplary catalysts include (1,4-diazabicyclo[2.2.2]octane)DABCO®T-12 or DABCO® crystals, available from Evonik; DMDEE (2,2'-dimorpholinyl diethyl ether); and DBU (1,8-diazabicyclo[5.4.0]unde-7-ene). When used, curable compositions may contain about 0.01% to about 5% by weight of the catalyst.

[0083] The curable composition may optionally contain fillers. Useful fillers include, for example, lithopone, zirconium silicate, hydroxides (such as hydroxides of calcium, aluminum, magnesium, and iron), diatomaceous earth, carbonates (such as sodium, potassium, calcium, and magnesium carbonates), oxides (such as oxides of zinc, magnesium, chromium, cerium, zirconium, and aluminum), calcium clay, nanosilica, fumed silica, silica surface-treated with silane or silazane (such as AEROSIL® products available from Evonik Industries), silica surface-treated with acrylate or methacrylate (such as AEROSIL® R7200 or R711 available from Evonik Industries), precipitated silica, untreated silica, graphite, synthetic fibers, organic clay (such as Cloisite® nanoclay sold by Southern Clay Products), expanded graphite (such as xGnP® graphene nanoplatelets sold by XG Sciences), and combinations thereof. When used, the curable composition may contain fillers in amounts up to about 90% by weight of the composition, more typically 1% to 30% by weight of the composition.

[0084] The curable composition may optionally contain thixotropic or rheological modifiers. Thixotropic agents can modify the rheological properties of the uncured composition. Some useful thixotropic agents include sustainable organic materials (e.g., castor oil derivatives (Rheocin available from BYK; Thixcin available from Elementis and Albothix available from Albertingk Boley)); and silica (untreated or fused or fumed silica treated to alter the surface chemical properties). Virtually any reinforced fused, precipitated, fumed, or surface-treated silica may be used. Examples of treated fumed silica include polydimethylsiloxane-treated silica, hexamethyldisilazane-treated silica, and other silazane or silane-treated silica. Such treated silicas are commercially available, for example, under the trade names CAB-O-SIL® ND-TS from Cabot Corporation and AEROSIL® (AEROSIL® R805, etc.) from Evonik Industries. Furthermore, silica surface-treated with acrylates or methacrylates such as AEROSIL® R7200 or R711, available from Evonik Industries, is also useful. Examples of untreated silica include commercially available amorphous silicas such as AEROSIL® 300, AEROSIL® 200, and AEROSIL® 130. Commercially available hydrated silicas include NIPSIL® E150 and NIPSIL® E200A from Nippon Silica Industry Co., Ltd. When used, the curable composition may contain thixotrope at a concentration of about 0% to about 50% by weight, preferably about 0% to about 20% by weight, of the composition. In certain embodiments, the filler and the rheology modifier may be the same.

[0085] The curable composition may optionally contain a reaction modifier. A reaction modifier is a material that increases or decreases the reaction rate of the curable composition. For example, 8-hydroxyquinoline (8-HQ) and its derivatives (such as 5-hydroxymethyl-8-hydroxyquinoline) can be used to adjust the curing rate. When used, the curable composition may contain about 0.001 to about 15 weight percent of the reaction modifier.

[0086] The curable composition may optionally contain a thermoplastic polymer. The thermoplastic polymer may be a functional thermoplastic resin or a non-functional thermoplastic resin. Non-limiting examples of suitable thermoplastic polymers include acrylic polymers, functional (e.g., including reactive substructures such as -OH and / or -COOH) acrylic polymers, non-functional acrylic polymers, acrylic block copolymers, acrylic polymers having tertiary alkylamide functionality, polysiloxane polymers, polystyrene copolymers, divinylbenzene copolymers, polyetheramides, polyvinyl acetals, polyvinyl butyral, polyvinyl chloride, methylene polyvinyl ethers, cellulose acetate, styrene acrylonitrile, amorphous polyolefins, olefin block copolymers [OBC], polyolefin plastomers, thermoplastic urethanes, polyacrylonitrile, ethylene acrylate copolymers, ethylene acrylate terpolymers, ethylene butadiene copolymers and / or block copolymers, styrene butadiene block copolymers, and mixtures of any of the above. When used, the curable composition may contain about 1% to about 20% by weight of the thermoplastic polymer relative to the weight of the curable composition.

[0087] The curable composition may optionally contain one or more compatible adhesion promoters known in the art. If used, the curable composition may contain adhesion promoters in an amount of about 0% to about 20% by weight, and preferably about 0.1% to about 15% by weight, of the curable composition.

[0088] Curable compositions may optionally contain one or more colorants. In some applications, colored compositions may be beneficial to allow inspection of the coated composition. Colorants, such as pigments or dyes, can be used to provide a desired color beneficial to the intended application. Exemplary colorants include titanium dioxide, CI Pigment Blue 28, CI Pigment Yellow 53, and phthalocyanine blue BN. In some applications, fluorescent dyes may be added to allow the coated composition to be examined under ultraviolet light. When used, curable compositions may contain colorants in an amount of about 0.002% by weight or more of the total composition. The maximum amount should be determined considering cost, radiation absorption, and interference with the curing of the composition.

[0089] Additives may be included in Part A, Part B, or both, provided that they do not react adversely with the other components of that part.

[0090] In one embodiment, part A of a two-component curable composition has the following composition. All percentages are weight percentages relative to the weight of part A. Typically, part A is liquid to fluid semi-solid at room temperature, with a viscosity of about 5,000 to about 100,000 cP at either 2 rpm or 20 rpm.

[0091] [Table 1]

[0092] The isocyanate-reactive component is optional and represents the content of non-sustainable isocyanate-reactive components. Preferably, it does not contain non-sustainable isocyanate-reactive components so that all non-additive components in Part A are sustainably supplied.

[0093] Typically, the components of Part A are added together and heated with stirring until the mixture reaches a temperature sufficient to melt the reactive rheological modifier. Once combined, the heat is removed and the mixture is allowed to cool. The mixture will thicken and become cloudy as it cools. Once cooled, the Part A composition is packaged to remove air and moisture.

[0094] In one embodiment, part B of a two-component curable composition has the following composition. All percentages are weight percentages relative to the weight of part B. Typically, part B will have a viscosity of about 8,000 to about 30,000 cPs at 20 rpm. Since part B is usually not thixotropic, the viscosity will usually be the same at 2 rpm.

[0095] [Table 2]

[0096] Part B can be prepared by adding non-isocyanate-containing components to a reactor and heating under vacuum with stirring to remove moisture. If a sustainable isocyanate-reactive component is used in Part B, it can be added together with other non-isocyanate components. Once moisture has been removed, the isocyanate-containing component can be added. Mixing under vacuum is continued until the mixture is homogenized and the desired isocyanate content is reached. The mixed Part B is cooled and packed into a sealed container to prevent moisture ingress.

[0097] In one embodiment, the mixed curable composition has the following properties.

[0098] [Table 3]

[0099] In one embodiment, the curing reaction product of the mixed curable composition has the following characteristics.

[0100] [Table 4]

[0101] In some embodiments, the adhesive composition is preferably a homogeneous solid that does not contain gas, and is preferably non-foaming. In these embodiments, the composition part and the mixed adhesive composition do not contain a foaming agent.

[0102] Use of adhesive compositions manufactured using the disclosed two-part adhesive composition The following explanation will be based on reference to Figures 1 to 4.

[0103] A typical thin-film composite membrane 10 for spirally wound filtration systems, such as reverse osmosis and / or nanofiltration systems, has a general structure shown as a schematic cross-sectional view in Figure 1. In one embodiment, the membrane 10 comprises two or three layers, with a thin, dense, semipermeable barrier layer 12 superimposed on a microporous substrate 14, the microporous substrate 14 optionally superimposed on a porous support layer 16. The porous support layer 16 may be, for example, a polyester nonwoven fabric layer. The porous support layer 16 is typically configured and positioned to allow fluid to pass through easily while providing physical support to the other layers of the composite membrane 10. Similarly, the semipermeable barrier layer 12 is typically polyamide, but not necessarily, and the microporous substrate 14 typically, though not always, contains polysulfone. The constituent materials and their thicknesses, etc., may be modified depending on the specific separation application for which the membrane 10 is intended to be used.

[0104] The semipermeable layer 12 is the active surface of the membrane 10 and is thought to influence the separation, either by itself or in combination with the intermediate microporous substrate 14, depending on the exact properties of the compounds being separated. For example, if the membrane 10 is intended to be used to purify water, the membrane 10 will allow water to pass through but not contaminants or salt ions.

[0105] Multiple of these films 10 are bonded together to form a spiral-wound membrane element using a two-component polyurethane adhesive prepared by mixing the disclosed parts A and B.

[0106] Figures 2-4 show a typical spiral-wound film element 20 (Figure 2) and various components and constructions of the spiral-wound film element 20 together.

[0107] Figure 2 schematically shows one embodiment of a spiral-wound membrane element 20, which includes a central perforated permeable tube 26 around which one or more membrane leaf elements 30 (shown in Figure 4) are wound. These membrane leaf elements 30 are described in more detail below. Each membrane leaf element may be separated by a feed spacer 28, which is typically a polymer net structure. A feed stream 18 flows through the intermembrane space provided by the feed spacer 28 and enters the spiral-wound membrane element 20. The feed stream 18 comprises at least two components. A typical example of the feed stream 18 is brine with an initial concentration of salt, which is then separated by the membrane 10 into a permeate stream 22 of clean water and a concentrate stream 24 containing water with a higher concentration of salt than the feed stream 18. The permeate stream 22 is spirally guided into the permeable tube 26 and discharged from there. The concentrate stream 24 flows between the membrane leaf elements 30 and is discharged.

[0108] Typical constructions of spiral-wound membrane elements 20 are known in the art, and one variation generally involves the following steps: As shown in Figure 3, a sheet of membrane 10 is unfolded and folded in half along line AA such that the semipermeable layer 12 faces the inside of the folded sheet 10 and the support layer 16 (not visible in Figure 3) faces the outside. A layer of feed spacer or feed carrier 28 is placed inside the folded sheet 10. The feed spacer or feed carrier layer 28 is intended to provide space for the feed 18 to flow freely inside the folded membrane sheet 10. Fine details of the material and thickness of the feed carrier 28 depend on the intended application of the spiral-wound membrane element 20, but are typically nonwoven materials that allow for the free flow of the feed flow 18 between adjacent folded portions of the membrane sheet 10. Note that the feed carrier 28 may be slightly smaller than the folded membrane sheet 10, as schematically shown in Figure 3.

[0109] Figure 4 shows one embodiment of a membrane leaf element 30 wound around a permeable tube 26. As is known in the art, one or more of these membrane leaf elements 30 are wound around the permeable tube 26, but only one is shown in Figure 4. The membrane leaf element 30 generally comprises three parts: a porous permeable carrier layer 32, folded membrane sheets 10, and a feed spacer 28 positioned between the folded membrane sheets 10.

[0110] During the construction of the membrane leaf element 30, a porous permeable carrier layer 32 is bonded to the central perforated permeable tube 26. A two-component polyurethane adhesive 36 as described herein may optionally be used for this bonding. The porous permeable carrier 32 is configured and positioned to allow the permeate 22 to flow into the permeable tube 26. The permeable tube 26 has a plurality of perforations 34 that allow the permeate 22 to flow into the permeable tube 26 and thus out of the spiral-wound membrane element 20.

[0111] The two-component polyurethane adhesive 36 described herein may optionally be used to bond a folded membrane sheet 10 and a permeable carrier 32 on three sides, forming an envelope that is open to the permeable tube 26 but closed to the feed source. The method of applying the two-component polyurethane adhesive 36 is not particularly limited, and preferred methods are known to those skilled in the art. For example, the components of the two-component polyurethane adhesive 36 may be dispensed separately from a tube or other container as needed and mixed in a static mixer immediately before use. The mixed adhesive 36 may be applied as a continuous bead along the opening edge of the porous permeable carrier 32, as shown in Figure 4. The size of the bead is not particularly limited, but only the edges of the folded sheet 10 should be bonded to the permeable carrier 32, leaving each inner portion unbonded. A preferred bead width may be, for example, about 0.3 cm to about 2 cm, or about 0.3 cm to about 0.6 cm. The membrane 10 is placed on a permeable carrier 32 and adhesive 36, and the fold of the membrane sheet 10 (line AA in Figure 2) is aligned along the permeable tube 26. Ideally, the adhesive 36 penetrates 90% or more into some or all of the layers of the membrane 10 (porous support layer 16, microporous layer 14, and barrier layer 12 shown in Figure 1) and the permeable carrier 32. However, it has been shown that in some adhesive spiral-wound membrane components, acceptable performance can be obtained even with low penetration of up to 5%.

[0112] This bonding process, which involves bonding the porous permeable carrier layer 32 to the centrally perforated permeable tube 26 and then bonding the folded membrane sheet 10 (having a feed carrier 28 between the folded sheets 10) to the porous permeable carrier layer 32 on three sides to form the membrane leaf element 30, is repeated the required number of times until the desired number of membrane leaf elements are attached to the permeable tube 26. After that, the membrane leaf elements 30 are tightly wrapped around the permeable tube 26 to form the spiral-wound element 20.

[0113] Caps, sometimes called anti-telescopic devices, are molded plastic components that hold the rolled membrane leaves in place, preventing them from moving axially under pressure and ensuring that the load is evenly distributed among all parts of the filter assembly. In some embodiments, the caps can be bonded to the membrane elements using a disclosed two-component polyurethane adhesive. [Examples]

[0114] Preparation of Part A : Add the ingredients of Part A together and heat to 80°C, stirring until all ingredients are dissolved and mixed. Once mixed, remove the heat and allow the mixture to cool while continuing to stir. Once cooled, package the Part A composition to remove air and moisture.

[0115] Part B Henkel's LOCTITE UK178B was used as the Part B isocyanate functional composition for all samples. Mondur CD was added to the Part B samples to maintain the index of all samples between 1.1 and 1.2.

[0116] Preparation of a 2-part polyurethane adhesive composition : Parts A and B were mixed in a 1:1 volume ratio until homogeneous. The mixed composition had an index (NCO:NCO reactivity) of approximately 1.1:1 to 1.2:1.

[0117] viscosity: The samples from Part A and Part B were at room temperature (23-25°C) before testing. For the mixed composition, the separate portions of Part A and Part B were homogenously mixed in a static mixer. Tests were performed at 25°C using a Brookfield viscometer with a #6 spindle. The 2 rpm test was performed within 1 minute after mixing. The 20 rpm test was performed within 2 minutes after mixing. Viscosity results are shown in cPs units.

[0118] Thixotropy index: The thixotropy of a material is calculated by dividing the viscosity of a sample taken at 2 rpm by the viscosity of a sample taken at 20 rpm. The thixotropy index can be calculated not only for mixed samples but also for each individual component.

[0119] Opening hours: Open time is the time it takes for the mixed sample to reach twice its viscosity at 20 rpm (2X).

[0120] Gel time: The gelation time is the time it takes for the mixed sample to reach a viscosity three times (3X) that of 20 rpm.

[0121] Shore hardness: The sample was prepared by dispensing a 1:1 Part A:Part B mixture into a 100g plastic beaker using a static mixer. After curing the material for 24 hours, the cured 100g pack was removed from the beaker. The pack measured approximately 2 inches in diameter and 3 inches in thickness. Sample measurements were performed according to ASTM D2240.

[0122] Measurement of film permeability using adhesives A square membrane (approximately 7.5 cm x 7.5 cm) was placed on a porous support layer 16. Approximately 5 grams of mixed adhesive were placed on the membrane. A second porous support layer 16 for the membrane was placed on top of the mixed adhesive. A non-stick plastic square (polyethylene, approximately 12 cm x 12 cm) was placed on top of the assembled membrane. A weight of approximately 450 grams was then placed on the entire non-stick plastic square. After leaving the weight for 20 minutes, it was removed. The assembly was allowed to cure for at least 8 hours, and the permeability was visually evaluated and reported as the membrane permeability. Unless otherwise specified, FILMTEC® BW30 membrane was used for the permeability test.

[0123] The permeability was qualitatively evaluated by visually analyzing the ratio of dark to light areas on the reverse side (i.e., the barrier layer side 12 opposite the support layer 16). No visual change corresponds to 100% light area and 0% permeability. Complete permeability corresponds to 100% dark area and 100% permeability. To ensure consistency, samples were evaluated by multiple people side-by-side.

[0124] Example 1: The following Part A compositions were prepared or provided. All amounts are in weight % of the part. In Comparative Example A, Henkel's LOCTITE UK178A was used as the isocyanate-reactive composition for Part A.

[0125] [Table 5]

[0126] Sample 1 had a part A containing beeswax but no glycerol. The composition of part A of Sample 1 showed instability, with the beeswax separating as a solid phase from the other components in just 5-10 minutes. When glycerol was added to the part A composition while heating and mixing, as in Examples 2, 3, and 4, the composition stabilized, and after 30 minutes, the beeswax in the composition was maintained with little to no separation.

[0127] The addition of glycerol was also surprisingly effective in reducing the viscosity of the Part A composition. Surprisingly, this viscosity-reducing effect was limited. Samples 2 and 3 show how the viscosity decreased compared to Sample 1, which did not contain glycerol. Sample 4 shows that adding more than approximately 3% glycerol to the Part A composition actually increased the viscosity of Part A compared to Sample 1, which did not contain glycerol. This increase in viscosity with increasing glycerol content is surprising, given that the viscosity of glycerol is only about 1412 cPs.

[0128] Henkel's LOCTITE UK178B was used as the isocyanate functionalized composition for Part B of all samples. Mondur CD was added to the Part B samples to maintain the index of all samples between 1.1 and 1.2. Each of the Part A compositions was mixed with the Part B composition of LOCTITE UK178B in a 1:1 volume ratio. All amounts are in weight percent of the part. The results of the physical property tests of the cured compositions for the mixed adhesive compositions are shown below.

[0129] [Table 6]

[0130] Example 2: The pre-formed composition of Part A was mixed with LOCTITE UK178B as described above and used to form hardness test specimens. All amounts are in weight percent of the part. The samples were checked with a probe and their tackiness was subjectively evaluated. Once the samples lost their tackiness, the Shore A hardness was checked. The test results are shown below.

[0131] [Table 7]

[0132] Example 3: The pre-formed composition of Part A was mixed with LOCTITE UK178B as described above, and the membrane permeability was tested. The results are shown in the table and Figures 5 and 6 below.

[0133] [Table 8]

[0134] Example 4: The following compositions were formed into 1 mm cast films and cured. The cured films were cut into 1-inch circles, weighed, and then placed in glass bottles containing deionized (DI) water at different pH levels (1.5, neutral (7-8), 12.5). The pH 1.5 solution was prepared by adding hydrochloric acid to deionized water. The pH 12.5 solution was prepared by adding NaOH to deionized water. The samples were kept in the solutions at 80°C for 2 weeks or at 50°C for 4 weeks, with weight checks performed weekly (the samples were removed from the bottles, dried, weighed, and then returned to the bottles for preparation). The results of the chemical resistance tests of the cured compositions shown below are expressed as a percentage of the weight loss (-) or weight increase (+) from the unconditioned sample.

[0135] [Table 9]

[0136] Within each temperature range, a weight loss or increase of less than 2% is considered acceptable, and a weight loss or increase of less than 1% is preferred. A weight loss or increase of 5% or more is considered unacceptable in many applications.

[0137] Comparative samples B and C were obtained by replacing glycerol with triethanolamine and polyvinyl chloride, respectively. Both comparative samples B and C showed high solubility of the cured material in the test medium and therefore low chemical resistance.

[0138] Example 5: Samples 2, E, and F were prepared as described above and mixed with LOCTITE UK178B as described above. Samples 5 and D were prepared by heating the components of Part A to 55°C and applying a very high shear force from a 2400 rpm mixer. Samples 5 and D were mixed with LOCTITE UK178B as described above. All amounts are in weight % of their respective parts. The properties of the samples were checked. The test results are shown below.

[0139] [Table 10]

[0140] The preparation methods for samples 5 and D resulted in a significantly higher viscosity of part A compared to the other samples. Comparative sample E contained particles of beeswax reacted with isocyanate from LOCTITE UK178B; however, after mixing parts A and B and waiting 24 hours, the mineral oil had not reacted, and the sample remained fluid at room temperature. In comparative sample F, the beeswax and isocyanate from LOCTITE UK178B reacted to form a slightly gelled or solid upper layer on top of a fluid lower layer. The upper layer was not solid enough to obtain a Shore A hardness reading. Neither sample E nor sample F had an acceptable open time or gelling time. Samples 2 and 5 demonstrate that beeswax in this composition is a sustainable alternative to leosine. These samples demonstrate that beeswax is an effective reactive thickener when combined with castor oil.

[0141] Samples 2 and 5 showed shorter and more desirable open times and gelation times compared to sample D, which was prepared using commercially available RheoBYK thixotrope. Beeswax is an astonishingly excellent thixotrope and a sustainable resource.

[0142] In some embodiments, the present invention as described herein may be interpreted as excluding elements or process steps that do not substantially affect the basic and novel characteristics of the composition or process. Furthermore, in some embodiments, the present invention may be interpreted as excluding elements or process steps not specified herein.

[0143] While the present invention is illustrated and described herein with reference to specific embodiments, it is not intended to be limited to the details shown. Rather, various modifications to the details may be made without departing from the invention, within the scope and region equivalent to the claims.

[0144] While embodiments are described herein in a manner that allows for a clear and concise description, it is intended and will be understood that embodiments may be combined and separated in various ways without departing from the present invention. For example, it will be understood that all preferred features described herein are applicable to all embodiments of the present invention described herein. 。 Examples of reference formats are provided below. 1. A two-part curable polyurethane adhesive composition, Isocyanate reactive components; Part A including sustainable reactive rheological modifiers, glycerol, and optionally additives; and Part B includes polyisocyanates and optionally additives; Includes, A two-part curable polyurethane adhesive composition wherein the polyurethane adhesive composition contains at least 60% by weight of sustainable material by the weight of the composition. 2. The two-part curable polyurethane adhesive composition according to claim 1, wherein part B comprises an isocyanate-functional polyurethane prepolymer which is a reaction product of MDI or modified MDI with an isocyanate-reactive component. 3. The two-part curable polyurethane adhesive composition according to item 1 or 2, wherein the isocyanate-reactive component of part A is 95-100% sustainable. 4. The two-part curable polyurethane adhesive composition according to any one of claims 1 to 3, wherein the isocyanate-reactive component of Part A comprises a sustainable vegetable oil having 2 to 4 hydroxyl groups. 5. A two-part curable polyurethane adhesive composition according to any one of claims 1 to 3, wherein the reactive rheology modifier comprises natural beeswax. 6. A separation device, A membrane capable of separating the first component from a feed fluid mixture containing the first component and the second component; The film comprises a mixed two-component polyurethane adhesive arranged in one or more separate regions on the film, wherein the two-component polyurethane adhesive is Isocyanate reactive components; Part A including sustainable reactive rheological modifiers, glycerol, and optionally additives; and Part B comprises polyisocyanate and optionally additives, The polyurethane adhesive composition comprises at least 60% by weight of sustainable material, and the mixed two-component polyurethane adhesive has a penetration rate into the film layer before curing, in a separation device. 7. The separation apparatus according to item 6, wherein the penetration rate of the polyurethane adhesive into the film layer is at least 5%. 8. The separation apparatus according to claim 6 or 7, wherein the penetration rate of the polyurethane adhesive into the film layer is at least 50%. 9. The separation apparatus according to claim 6 or 7, wherein the penetration rate of the polyurethane adhesive into the film layer is at least 80%. 10. The separation apparatus according to claim 6 or 7, wherein the separation apparatus further comprises a feed carrier material. 11. The separation apparatus according to claim 6 or 7, further comprising a porous permeable carrier layer bonded with the two-component polyurethane adhesive. 12. The separation apparatus according to item 6 or 7, wherein part A has a viscosity of less than 100,000 cPs at 25°C. 13. The separation apparatus according to item 6 or 7, wherein the viscosity of part A at 25°C is less than 30,000 cPs, as measured with a Brookfield viscometer at 20 RPM and spindle 6. 14. The separation apparatus according to item 6 or 7, wherein component A and component B are present in a stoichiometric ratio of 0.95:1 to 1.40:1 based on the number of moles of isocyanate groups in part B and the number of moles of isocyanate-reactive groups in part A. 15. The separation apparatus according to item 6 or 7, wherein part A comprises 50% to 95% by weight of castor oil as an isocyanate reactive component and 0.5% to 20% by weight of beeswax as a sustainable reactive rheology modifier. 16. The separation apparatus according to claim 6 or 7, wherein the polyisocyanate comprises methylenediphenyl diisocyanate. 17. Use of a two-component polyurethane adhesive for bonding components of a spiral-wound film element, wherein the two-component polyurethane adhesive is Isocyanate reactive components; Part A including sustainable reactive rheological modifiers, glycerol and optionally additives; and Part B comprises polyisocyanate and optionally additives; The polyurethane adhesive composition contains 60 to 100% by weight of sustainable materials; A step of applying the mixed polyurethane adhesive to at least one spiral-wound element or end cap to form an adhesive area; and The process of curing the polyurethane adhesive. Use including. 18. The use according to item 17, wherein the two-component polyurethane adhesive has a penetration rate into the film of at least 5%.

Claims

1. A two-part curable polyurethane adhesive composition, (i) 50% to 95% by weight of vegetable oil having 2 to 4 hydroxyl groups, (ii) 0.5% to 20% by weight of beeswax, (iii) glycerol, and optionally additives; and Part B, containing polyisocyanates and optionally additives. Includes, A two-part curable polyurethane adhesive composition comprising, in total, at least 60% by weight of materials made from plant-derived resources and beeswax, relative to the weight of the composition.

2. The two-part curable polyurethane adhesive composition according to claim 1, wherein part B comprises an isocyanate-functional polyurethane prepolymer which is a reaction product of MDI or modified MDI and an isocyanate-reactive component.

3. The two-part curable polyurethane adhesive composition according to claim 1 or 2, wherein the beeswax comprises natural beeswax.

4. A separation device, A membrane capable of separating the first component from a feed fluid mixture containing the first component and the second component; The film comprises a mixed two-component polyurethane adhesive arranged in one or more separate regions on the film, wherein the two-component polyurethane adhesive is (i) 50% to 95% by weight of vegetable oil having 2 to 4 hydroxyl groups, (ii) 0.5% to 20% by weight of beeswax, (iii) glycerol, and optionally additives; and Part B comprises polyisocyanate and optionally additives, The polyurethane adhesive composition contains at least 60% by weight of materials made from plant-derived resources and beeswax in total, relative to the weight of the composition, and the mixed two-component polyurethane adhesive has a penetration rate into the film layer before curing, in a separation device.

5. The separation apparatus according to claim 4, wherein the penetration rate of the polyurethane adhesive into the film layer is at least 5%.

6. The separation apparatus according to claim 4 or claim 5, wherein the penetration rate of the polyurethane adhesive into the film layer is at least 50%.

7. The separation apparatus according to claim 4 or claim 5, wherein the penetration rate of the polyurethane adhesive into the film layer is at least 80%.

8. The separation apparatus according to claim 4 or claim 5, wherein the separation apparatus further includes a feed carrier material.

9. The separation apparatus according to claim 4 or claim 5, wherein the separation apparatus further comprises a porous permeable carrier layer bonded with the two-component polyurethane adhesive.

10. The separation apparatus according to claim 4 or 5, wherein part A has a viscosity of less than 100,000 cPs at 25°C.

11. The separation apparatus according to claim 4 or 5, wherein the viscosity of part A at 25°C is less than 30,000 cPs, as measured with a Brookfield viscometer at 20 RPM and spindle 6.

12. The separation apparatus according to claim 4 or claim 5, wherein part A and part B are present in a stoichiometric ratio of 0.95:1 to 1.40:1 based on the number of moles of isocyanate groups in part B and the number of moles of isocyanate-reactive groups in part A.

13. The separation apparatus according to claim 4 or 5, wherein the vegetable oil having 2 to 4 hydroxyl groups is castor oil.

14. The separation apparatus according to claim 4 or 5, wherein the polyisocyanate comprises methylenediphenyl diisocyanate.

15. The use of a two-component polyurethane adhesive for bonding components of a spiral-wound film element, wherein the two-component polyurethane adhesive is (i) 50% to 95% by weight of vegetable oil having 2 to 4 hydroxyl groups, (ii) 0.5% to 20% by weight of beeswax, (iii) glycerol and optionally additives, Part A; and Part B comprises polyisocyanate and optionally additives; The polyurethane adhesive composition contains a total of 60 to 100% by weight of materials made from plant-derived resources and beeswax, relative to the weight of the composition; A step of applying the mixed polyurethane adhesive to at least one spiral-wound element or end cap to form an adhesive area; and The process of curing the polyurethane adhesive. Use including.

16. The use according to claim 15, wherein the two-component polyurethane adhesive has a penetration rate into the film of at least 5%.

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