JP2017533088A - Method for producing hollow fiber membrane module using curable composition, and module produced therefrom - Google Patents

Abstract

A method of making a hollow fiber filtration module comprising potting the ends of a plurality of hollow fiber membranes using a multi-pack solventless curing composition. The curable composition includes a Michael donor, a Michael acceptor, and a Michael reaction catalyst.

Description

(Cross-reference of related applications)
This application claims the benefit of US Provisional Application No. 62 / 058,464 (filed Oct. 1, 2014), which is incorporated herein.

(Field of Invention)
The present invention relates to a multipack solvent-free curable composition obtainable by a Michael reaction of a Michael donor and a Michael acceptor in the presence of a suitable catalyst, the field of filtration technology, particularly in applications to hollow fiber filtration. It relates to the use and method for making it.

  The hollow fiber membrane module is a filtration device that can be used in microfiltration and ultrafiltration. In one exemplary structure, the module is introduced into a cylindrical container (housing), and at least one or both ends of the membrane within the housing or a predetermined fixed container (eg, cartridge head) is a potting composition. A plurality of porous hollow fiber membranes that are potted with a cured resin material known as:

  Two-part curable compositions based on polyurethane and epoxy chemicals are used as potting compositions for making hollow fiber membrane modules.

International Publication No. 2011/143530 International Publication No. 2001/043855 European Patent Application No. 0920904 US Pat. No. 6,024,410

  The present invention has low toxicity (i.e., is free of isocyanate) and has suitable characteristics (e.g., no bubbles, low heat generation) when cured, thereby making hollow fiber membranes particularly useful in filtration applications. It relates to a multipack solvent-free ambient temperature curable composition that is suitable for use as a potting composition for potting modules.

  In one aspect, the present invention relates to a method of making a hollow fiber membrane module. The method comprises preparing a mixture of multi-pack solventless curable compositions by combining a multi-functional Michael donor, a multi-functional Michael acceptor, and a Michael reaction catalyst; and a mixture of the curable composition; Introducing into at least one end of a plurality of hollow fiber membranes; solidifying and curing the curable composition to pot the ends of the plurality of hollow fiber membranes.

  In one embodiment, the curable composition further comprises up to 10% by weight filler.

  In some embodiments, the curable composition has an initial viscosity of 200 centipoise (cP) to 10,000 cP at 25 ° C. and a Shore A hardness of 50 or more after curing for 7 days at 25 ° C. and 50% relative humidity. Indicates.

  In one embodiment, the catalyst has a conjugate acid with a pKa greater than 11.

  In another aspect, the present invention relates to a hollow fiber membrane module. The module includes a plurality of hollow fiber membranes having at least one end potted with a potting composition. The potting composition includes a reaction product of a multi-functional Michael donor, a multi-functional Michael acceptor, and a Michael reaction catalyst.

  A conventional polyurethane-based potting composition for potting a hollow fiber membrane requires that the hollow fiber be dried to remove residual moisture before potting, and the residual moisture once removes the composition from the end of the membrane. When applied to the part, it causes foaming (or foam formation) in the composition before curing. Foam formation can reduce filterability and lead to module failure. It is expensive to first dry the fibers before potting, and sometimes even certain fibers that require large amounts of glycerin cannot maintain pore openings because glycerin hinders the reaction between isocyanate and polyol. is there. Epoxy-based potting systems have the constraint that they result in a high exothermic (eg, greater than 120 ° C.) cure profile that causes hollow fiber carbonization or filtration module failure.

  Requirements generally imposed in filtration applications, in particular potting hollow fiber membranes, e.g. suitable initial to allow the composition to penetrate the hollow fiber membranes when the composition is applied to at least one end of the membrane In addition to meeting viscosity and gelation time, excellent chemical resistance to strong acidic and basic solutions, proper pot life, high hardness, etc., the multipack solventless curable composition of the present invention is low The non-foaming properties in the presence of exothermic temperature and moisture are also shown. These features are particularly beneficial in the manufacture of hollow fiber membrane modules for water filtration applications.

  Further objects of the present invention will become clear from the further description below.

It is sectional drawing of one embodiment of the hollow fiber membrane module of this invention.

Glossary In the context of the present invention, these terms have the following meanings:
“Michael reaction” refers to an addition reaction of a carbanion or nucleophile with an activated α, β-unsaturated carbonyl compound or group. The “Michael reaction” is a well-known reaction for forming a carbon-carbon bond and includes a 1,4-addition of a stabilized carbanion to an α, β-unsaturated carbonyl compound.

A “Michael donor” refers to a compound having at least one Michael donor functional group, wherein the functional group is a functional group containing at least one Michael active hydrogen atom, and the hydrogen atom comprises two electrons. Withdrawing groups such as C═O and / or C≡N and / or NO ₂ (nitro) and / or SO ₂ R (sulfone, R is alkyl (linear, branched or cyclic), aryl, hetero Aryl, alkaryl, alkheteroaryl, and organic radicals such as derivatives and substituted versions thereof) are hydrogen atoms bonded to carbon atoms located between them.

  “Michael acceptor” refers to a compound having at least one Michael acceptor functional group having structure (I):

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は、独立して、水素、又はアルキル（直鎖、分岐鎖、又は環状）、アリール、アルカリール、並びにこれらの誘導体及び置換バージョン等の有機ラジカルである）。Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は、独立して、アルコキシ、アリールオキシ、エーテル結合、カルボキシル基、更なるカルボニル基、これらのチオ類似体、窒素含有基、又はこれらの組み合わせを含有していてもよく、していなくてもよい。

(Wherein R ¹ , R ² , R ³ , and R ⁴ are independently hydrogen, alkyl (linear, branched, or cyclic), aryl, alkaryl, and derivatives and substituted versions thereof. Of organic radicals). R ¹ , R ² , R ³ , and R ⁴ independently contain an alkoxy, aryloxy, ether linkage, carboxyl group, further carbonyl group, their thio analogs, nitrogen-containing groups, or combinations thereof You may or may not.

  “Michael acceptor” also refers to a compound having at least one Michael acceptor functional group having the structure (II):

（式中、Ｒ^５は、アルキル（直鎖、分岐鎖、又は環状）、アリール、ヘテロアリール、アルカリール、アルクヘテロアリール、並びにこれらの誘導体及び置換バージョン等の有機ラジカルである）。Ｒ^５は、独立して、エーテル結合、カルボキシル基、更なるカルボニル基、スルホニル基、これらのチオ類似体、窒素含有基、又はこれらの組み合わせを含有していてもよく、していなくてもよい。

(Wherein R ⁵ is an organic radical such as alkyl (linear, branched or cyclic), aryl, heteroaryl, alkaryl, alkheteroaryl, and derivatives and substituted versions thereof). R ⁵ may independently contain an ether bond, a carboxyl group, a further carbonyl group, a sulfonyl group, a thio analog thereof, a nitrogen-containing group, or a combination thereof. .

  The “gel time” refers to the time it takes for the curable composition to enter a gelled state that can no longer be processed.

  “Equivalent” is defined as the molecular weight of a compound divided by the number of reactive groups or functional groups of the compound associated with the Michael reaction.

  “Ambient temperature” refers to a temperature of 25 ° C. + / − 5 ° C.

  “(Meth) acrylate” refers to acrylate or methacrylate; “(meth) acryl” refers to acrylic or methacrylic.

  The present disclosure relates to a multi-pack solventless curable composition as a potting compound and its use for potting at least one end of a plurality of hollow fiber membranes.

Curable composition The curable composition includes a Michael donor, a Michael acceptor, and a Michael reaction catalyst, and is a multipack system. That is, the composition comprises two or more parts as described herein. The components in each part are stored in containers (packs) separated from other containers until the contents of all containers are mixed to form a mixture of curable compositions prior to application. During application and curing, a solid adhesive is formed that bonds the hollow fiber membranes together. The phrase “multipack” is interchangeable with the phrase “multipart” herein.

  The curable composition can be obtained through a Michael reaction between a Michael donor (eg, an acetoacetylated compound) and a Michael acceptor (eg (meth) acrylate) in the presence of a Michael reaction catalyst. Solvent-free composition containing no isocyanate (no NCO) based on acetylated polymer.

  The curable composition is a liquid immediately after mixing all parts of the composition at ambient temperature, eg, 25 ° C. + / − 5 ° C. As used herein, a composition or ingredient is considered liquid if it is liquid at ambient temperature, eg, 25 ° C. + / − 5 ° C.

  The curable composition has an initial viscosity at 25 ° C. of 10,000 centipoise (cP) or less, or 200 cP or more, 400 cP or more, 500 cP or more, 10,000 cP or less, 4,000 cP or less, 2,500 cP or less, or 1,500 cP or less. Is prescribed to indicate The initial viscosity of the curable composition in the present specification refers to a viscosity required within 1 minute (min) to 5 minutes after all parts of the composition are combined.

  In some embodiments, the curable composition has a gel time of 5 minutes (min) or more, 15 minutes or more, 120 minutes or less, 60 minutes or less, or 30 minutes or less after all parts of the composition are combined. Show.

  The curable composition is formulated to be free of foam and exhibits a low exothermic temperature. In some embodiments, the curable composition exhibits a maximum exotherm temperature of 120 ° C. or lower, or 100 ° C. or lower, or 80 ° C. or lower.

  Moreover, a curable composition is prescribed | regulated so that high hardness may be shown. In some embodiments, the curable composition exhibits a Shore A hardness of 50 or greater, or 60 or greater, or 70 or greater after curing for 7 days at 25 ° C. and 50% relative humidity. In some embodiments, the curable composition exhibits a Shore D hardness of 40 or greater, or 50 or greater after curing for 7 days at 25 ° C. and 50% relative humidity.

  Also, the curable composition should be resistant to chemicals such as cleaning / disinfecting reagents such as caustic agents, bleaching agents, acidic agents, or peroxide agents during harsh chemical cleaning cycles. To be prescribed. In some embodiments, the curable composition exhibits a weight change of less than 5% after being immersed in an acidic or caustic solution for 28 days according to the chemical resistance test method described herein.

  Furthermore, the curable composition has other advantages. For example, since the curable composition does not contain a solvent, it does not contain any volatile organic compounds (VOC).

  The curable composition has a processable viscosity and pot life, and also quickly cures and develops a high hardness within 24 hours after combining the multiple parts. Finally, the curable composition provides a strong adhesive bond that is resistant to humidity and chemicals.

  In the curable compositions of the present invention, the relative ratio of multi-functional Michael acceptor to multi-functional Michael donor can be characterized by a relative equivalent ratio, which is determined in the curable mixture (eg, structure I And / or the ratio of all functional groups (in structure II) to the number of Michael active hydrogen atoms in the mixture. The Michael donor component and the Michael acceptor component are such that the equivalent ratio of the functional acrylate group of the Michael acceptor to the active hydrogen of the Michael donor is 0.3 or more, 0.5 or more, 1.5 or less, or 1 or less. And blended immediately before application.

Multifunctional Michael Donor of A Part The A part of the curable composition comprises at least one multifunctional Michael donor. In some embodiments, the A moiety comprises more than one multifunctional Michael donor. In some embodiments, the A portion is liquid at ambient temperature.

  Suitable Michael donors include those that are in liquid form at ambient temperature. Suitable Michael donors also include those that are in solid form at ambient temperature. When a solid form of Michael donor is included in part A, it is preferably mixed with the liquid form of the Michael donor so that part A is liquid at ambient temperature.

  A “Michael donor” is a compound having at least one Michael donor functional group. Examples of Michael donor functional groups include malonate, acetoacetate, malonamide, acetoacetamide (Michael active hydrogen bonded to the carbon atom between two carbonyl groups), cyanoacetate, and cyanoacetamide (Michael active hydrogen is bonded to the carbon atom between the carbonyl group and the cyano group). The Michael donor may have one, two, three, or more separate Michael donor functional groups. Each Michael donor functional group may have one or two Michael active hydrogen atoms. Compounds having two or more Michael active hydrogen atoms are known herein as multifunctional Michael donors. The total number of Michael active hydrogen atoms in the donor molecule is known as the Michael donor functionality. A Michael donor is a compound composed of a Michael donor functional group and a skeleton (or core). As used herein, a “Michael donor backbone” (or core) is part of a donor molecule other than a Michael donor functional group.

  Particularly preferred multifunctional Michael donors include acetoacetylated polyols. Polyols that are acetoacetylated have at least one hydroxyl group, preferably two or more hydroxyl groups. The conversion rate of hydroxyl groups to acetoacetic acid groups should be 80 mol% to 100 mol%, more preferably 85 mol% to 100 mol%.

  Methods for making acetoacetylated polyols are well known in the art, such as, for example, Journal of Organic Chemistry 1991, 56, 1713-1718, “Transacetoacetylation with tert-Butyl Acetate Acetate Acetic Acid”, For example, it is described that acetoacetylated polyols can be prepared by transesterification with tert-butyl acetoacetate.

  In some embodiments, the multifunctional Michael donor comprises at least one acetoacetoxy functional group and a polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, polyurethane polyol, urethane polyol, glycol, monohydric alcohol, polyhydric alcohol. An acetoacetylated polyol comprising a Michael donor backbone selected from the group consisting of a monohydric alcohol, a natural oil polyol, and modifications thereof, and combinations thereof.

  Examples of polyhydric alcohols suitable as skeletons for the multifunctional Michael donor (and the following multifunctional Michael acceptor in the B moiety) include, for example, alkanediols, alkylene glycols, glycerol, saccharides, pentaerythritol, Derivative, cyclohexanedimethanol, hexanediol, castor oil, castor wax, trimethylolpropane, ethylene glycol, propylene glycol, pentaerythritol, trimethylolethane, ditrimethylolpropane, dipentaerythritol, glycerin, dipropylene glycol, N, N , N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, neopentyl glycol, propanediol, butanediol, diethylene glycol and the like.

  Examples of more preferable polyols include trimethylolpropane (TMP), isosorbide, glycerol, neopentyl glycol (NPG), butylethylpropanediol (BEPD), tricyclodecane dimethanol, 1,4-cyclohexanedimethanol, hydroquinone bis. (2-hydroxyethyl) ether, castor oil, castor wax, polybutadiene, polyester polyol, and polyether polyol.

  Examples of Michael donors include methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, t-butyl acetoacetate, ethylene glycol bisacetoacetate, 1,2 propanediol bis Acetoacetate, 1,3-propanediol bisacetoacetate, 1,4 butanediol bisacetoacetate, neopentyl glycol bisacetoacetate, isosorbide bisacetoacetate, trimethylolpropane trisacetoacetate, glycerol trisacetoacetate, castor oil trisacetoacetate , Castor wax trisacetoacetate, glucose trisacetoacetate, glucose tetraacetoacetate, sucro Sacetoacetate, sorbitol trisacetoacetate, sorbitol tetraacetoacetate, ethoxylated and propoxylated diols, triols, and acetoacetates of polyols such as ethoxylated neopentyl glycol bisacetoacetate, propoxylated glucose acetoacetate, propoxylated sorbitol Acetoacetate, propoxylated sucrose acetoacetate, polyester acetoacetate in which the polyester is derived from at least one diacid and at least one diol, polyesteramide acetoacetate in which the polyesteramide is derived from at least one diacid and at least one diamine 1,2 ethylene bisacetamide, 1,4 butane bisacetamide, 1,6 hexane bisacetate Acetamide, piperazine bisacetamide, an acetamide of an amine-terminated polypropylene glycol, an acetamide of a polyesteramide acetoacetate in which the polyesteramide is derived from at least one diacid and at least one diamine, a polyacrylate containing a comonomer with an acetoacetoxy functionality (e.g. , Derived from acetoacetoxyethyl methacrylate), and polyacrylates containing acetoacetoxy functional groups and silylated comonomers, such as, but not limited to, vinyltrimethoxysilane.

B Part Multifunctional Michael Receptor The B part of the curable composition comprises at least one multifunctional Michael acceptor. In some embodiments, the B moiety comprises more than one multifunctional Michael acceptor. In some embodiments, the B portion is liquid at ambient temperature.

  A “Michael acceptor” is a compound having at least one acceptor functional group as described above. Compounds having two or more Michael acceptor functional groups are known herein as multi-functional Michael acceptors. The number of functional groups in the acceptor molecule is the functionality of the Michael acceptor. As used herein, the “Michael acceptor backbone” is the portion of the acceptor molecule other than the functional group.

  The multi-functional Michael acceptor may have any of a wide range of skeletons. Examples of multi-functional Michael acceptor backbones include: polyhydric alcohols (eg, those described hereinabove in the A-part Michael donor section); polymers such as polyalkylene oxides, polyurethanes Polyethylene vinyl acetate, polyvinyl alcohol, polybutadiene, hydrogenated polybutadiene, alkyd, alkyd polyester, (meth) acrylic polymer, polyolefin, polyester, halogenated polyolefin, halogenated polyester, or combinations thereof.

  Preferably, the multifunctional Michael acceptor is a multifunctional (meth) acrylate, which includes multifunctional (meth) acrylate monomers, oligomers, polymers, and combinations thereof.

  Examples of polyfunctional (meth) acrylates suitable as multi-functional Michael acceptors include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol Ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, cyclohexane dimethanol diacrylate, alkoxylated hexanediol diacrylate, alkoxylated cyclohexane dimethanol diacrylate, propoxy Neopentyl glycol diacrylate, trimethylolpropane triacrylate, ethoxylated tri Tyrolpropane triacrylate, propoxylated trimethylolpropane triacrylate, acrylated polyester oligomer, bisphenol A diacrylate, ethoxylated bisphenol A diacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, acrylated aliphatic urethane oligomer, acrylic And aromatic urethane oligomers, and combinations thereof.

  Other examples of suitable multifunctional (meth) acrylates include tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane-tetraacrylate, ditrimethylolpropane-tetramethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetra And methacrylate. According to the present invention, the curable composition may further contain a mono α, β-unsaturated compound, such as a monoacrylate.

  Further examples of suitable multifunctional Michael acceptors include multifunctional (meth) acrylates whose backbone is a polymer. The (meth) acrylate group can be attached to the polymer backbone in a wide variety of ways. For example, a (meth) acrylate ester monomer can be bonded to a polymerizable functional group via an ester bond, and the polymerizable functional group can be linked to other groups in a manner that leaves the double bond of the (meth) acrylate group unchanged. Polymerizable with monomers. In another example, the polymer may be made with functional groups (eg, polyester with residual hydroxyl), which reacts with (meth) acrylate esters (eg, by transesterification) and is pendant. A polymer having a (meth) acrylate group can be obtained. In yet another example, a homopolymer or copolymer containing a polyfunctional (meth) acrylate monomer (eg, trimethylolpropane triacrylate) may be made in a manner that does not react all acrylate groups.

  Mixtures or combinations of suitable multifunctional Michael acceptors are also suitable.

  Examples of suitable commercially available multi-functional Michael acceptors include: multifunctional polyester acrylates under the trade names CN292, CN2283, CN2207, and CN2203; polyethylene glycol diacrylates under the trade name SR344; trade names SR349, SR601, and SR602. Ethoxylated bisphenol A diacrylate; Tricyclodecane dimethanol diacrylate with trade name SR833 S; Hexafunctional aromatic urethane acrylate with trade name CN975; Trifunctional urethane acrylate with trade name CN929; and Aliphatic polyester with trade name CN968 Based urethane hexaacrylates, all of which are available from Sartomer USA, LLC (Exton, PA).

  It is believed that a linear molecular structure is obtained by reaction of a Michael donor with functionality 2 and a Michael acceptor with functionality 2. In order to create a branched and / or cross-linked molecular structure, at least one component having a functionality of 3 or higher is used. Accordingly, it is preferred that the multifunctional Michael donor or the multifunctional Michael acceptor, or both, have a functionality of 3 or greater.

  In the practice of the present invention, the skeleton of the multifunctional Michael acceptor may be the same as or different from the skeleton of the multifunctional Michael donor.

Michael reaction catalyst The curable composition also includes a Michael reaction catalyst. A Michael reaction catalyst is a catalyst that can initiate a Michael reaction. The catalyst may be included in the A portion, or the B portion, or a combination thereof.

  Alternatively, the catalyst may be provided to the curable composition as a separate component such as a C moiety.

  The catalyst is present in the curable composition in an amount of 0.1% or more, 0.5% or more, 10% or less, or 1.5% or less, based on the moles of Michael active hydrogen atoms.

  Useful Michael reaction catalysts include both strong base catalysts where the conjugate acid has a pKa greater than 11 and weak base catalysts where the conjugate acid has a pKa of 4-11. Examples of suitable strong base catalysts include guanidine, amidine, and combinations thereof, such as 1,1,3,3-tetramethylguanidine (TMG), 1,8-diazabicyclo {5.4.0} -7. -Undecene (DBU) and 1,5-diazabicyclo {4,3,0} -5-nonene (DBN). Examples of suitable weak base catalysts include tertiary amines, alkali metal carbonates, alkali metal bicarbonates, alkali metal hydrogen phosphates, phosphines; alkali metal salts of carboxylic acids such as triethylamine, sodium carbonate , Potassium carbonate, sodium bicarbonate, potassium bicarbonate, potassium hydrogen phosphate (monobasic and dibasic), and potassium acetate. Examples of other Michael reaction catalysts include triphenylphosphine, triethylphosphine, and tributylphosphine.

In some embodiments, the Michael reaction catalyst is conjugate acid preferably strong base catalyst having a pK _a of 11, or greater than 12 to 14. Preferably, the base is organic. Examples of such bases include amidine and guanidine. More preferred catalysts include 1,1,3,3-tetramethylguanidine (TMG), 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), and 1,5-diazabicyclo [4, 3,0] -5-nonene (DBN).

Combination of D-Partial Multifunctional Michael Donor and Multifunctional Michael Acceptor In some embodiments, the multifunctional Michael donor and acceptor can be put together in one pack, and the Michael reaction catalyst Can be put in another pack. The two packs are mixed immediately before application.

  Thus, in some embodiments, the adhesive composition includes a D portion and a C portion. The D portion includes a combination of any one of the A portions described herein and any one of the B portions described herein. The C moiety includes any one of the Michael reaction catalysts described herein. D part and C part are mixed immediately before application.

  In some embodiments, the D moiety comprises a bifunctional compound that includes a Michael donor functional group and a Michael acceptor functional group. The bifunctional compound may be a bifunctional monomer, bifunctional oligomer, bifunctional polymer, and combinations thereof.

Other Additives The curable composition may also contain other optional additives in any part of the multi-pack curable composition, these being antioxidants, plasticizers, adhesion promoters, Catalysts, catalyst deactivators, colorants (eg pigments and dyes), surfactants, waxes, antifoaming agents, diluents (including reactive diluents), tackifiers, reinforcing fillers, toughening agents, Includes impact modifiers, stabilizers such as triethyl phosphate, and combinations thereof.

  In some embodiments, the curable composition comprises less than 10 wt%, or less than 5 wt%, or 1 wt% to 3 wt% filler, based on the weight of the curable composition. May be. The filler may be included in any part of the multipack curable composition. Examples of suitable fillers include fumed silica, calcium carbonate, and combinations thereof.

Production and Use Method The curable composition of the present invention is a multi-pack composition. That is, the composition includes two or more parts, and the components in each part are mixed with other containers until the contents of all containers are mixed to form a mixture of curable compositions prior to application. Stored in a separate container (pack). Each individual pack of the multi-pack composition is storage stable. All pack mixing may be performed at ambient or elevated temperatures.

  The curable composition of the present invention is useful for potting a porous hollow fiber membrane for producing a hollow fiber membrane module.

  Hollow fiber membranes typically have two ends.

  In one embodiment, the hollow fiber membrane is potted at one end of the membrane using a potting composition that is the reaction product of any one of the aforementioned multi-pack solventless curable compositions of the present invention. Is done. In particular, the potting composition includes a reaction product of a multi-functional Michael donor, a multi-functional Michael acceptor, and a Michael reaction catalyst.

  In another embodiment, the hollow fiber membrane is potted at both ends of the membrane using a potting composition that is the reaction product of a multi-functional Michael donor, a multi-functional Michael acceptor, and a Michael reaction catalyst. .

  In some embodiments, the hollow fiber membrane may be potted with a single layer potting composition that is the reaction product of a multi-functional Michael donor, a multi-functional Michael acceptor, and a Michael reaction catalyst. .

  In some embodiments, the hollow fiber membrane is a potting composition in which at least one of the potting compositions is a reaction product of a multi-functional Michael donor, a multi-functional Michael acceptor, and a Michael reaction catalyst. Potting may be done using more than one layer of potting composition.

  As one embodiment, FIG. 1 shows a hollow fiber membrane module 1. The module 1 includes a plurality of porous hollow fiber membranes 3 contained in a cylindrical housing 4. In this embodiment, the hollow fiber membrane 3 is potted inside the housing 4 at both ends of the membrane 3 using the potting composition 2. The potting composition 2 contains the reaction product of any one of the aforementioned multi-pack solventless curable compositions of the present invention.

  The membrane module can be made using any suitable method of potting at least one end of a plurality of hollow fiber membranes.

  In one embodiment, a step of introducing the ends of a plurality of porous hollow fiber membranes into a predetermined container (for example, a housing), a step of preparing a mixture of the curable composition of the present invention, and the curable composition A step of introducing a mixture of materials into the container, a step of allowing the curable composition to flow around and permeate the end portion, a solidifying and curing of the curable composition, and an end portion of the hollow fiber membrane. A hollow fiber membrane module including a step of potting. Preparation of the mixture involves combining all parts of the curable composition just prior to applying the curable composition.

  Useful application temperatures range from 20 ° C to 50 ° C or from 20 ° C to 35 ° C. Low temperatures are preferred during the coating process to extend the pot life of the curable composition.

  The present invention encompasses various hollow fiber membrane filtration modules with methods of making and using them via any of the aforementioned curable compositions of the present invention. The structure of the hollow fiber membrane module is not particularly limited. Examples of various hollow fiber membrane filtration modules in which the curable composition of the present invention is particularly useful include, for example, U.S. Patent Nos. 8,758,621, 8, which are incorporated herein by reference in their entirety. No. 518,256, No. 7,931,463, No. 7,022,231, No. 7,005,100, No. 6,974,554, No. 6,648,945, Nos. 6,290,756 and U.S. Patent Application Publication No. 2006/0150373, and their production methods.

  The present disclosure may be further understood with reference to the following examples. These examples are intended to be representative of specific embodiments of the disclosure and are not intended to limit the scope of the disclosure.

  Unless otherwise specified, all parts, ratios, proportions, and amounts set forth herein and in the examples are by weight.

Test Method Viscosity Brookfield DV-II + Pro Viscometer using Spindle # 27 and 12 gram sample at 2 rpm (rotations per minute) at 25 ° C. ± 5 ° C. or 30 ° C. ± 5 ° C. and 50% relative humidity. (Brookfield Engineering, USA).

Glass transition temperature ( _Tg )
The glass transition temperature (T _g ) of the cured composition is that the sample is conditioned at 140 ° C. for 2 minutes, the sample is quenched to −60 ° C., and then the sample is heated to 140 ° C. at a rate of 20 ° C./min. Measured in accordance with ASTM D-3418-83, entitled “Standard Test Method for Transition Temperatures of Polymers by Differential Scanning Calibration (DSC)”. The reported _Tg is the temperature at which the phase change is initiated.

Shore A Hardness The Shore A hardness of the cured composition is measured at 25 ° C. ± 5 ° C. and 50% relative humidity using a handheld hardness tester (Paul N. Gardner Company, Inc. USA) and Shore A scale. The cured composition is cured at 25 ° C. ± 5 ° C. and 50% relative humidity for 7 days.

Shore D hardness The Shore D hardness of the cured composition is measured at 25 ° C. ± 5 ° C. and 50% relative humidity using a handheld hardness tester (Paul N. Gardner Company, Inc. USA) and Shore D scale. The cured composition is cured at 25 ° C. ± 5 ° C. and 50% relative humidity for 7 days.

Gelation Time The gelation time of the multipack curable composition is measured using a Gardco Standard Gel Timer (from Paul N. Gardner Company, Inc., USA) at 25 ° C. ± 5 ° C. and 50% relative humidity. 110 grams of a mixture of Part A (Michael Donor and Michael Reaction Catalyst) and Part B (Michael Acceptor) were mixed and deposited in an aluminum pan in a timer unit, a wire stirrer was inserted, the display was set to zero, the timer Start up. The gel timer is agitated until gel is formed (the viscosity of the mixture increases until the drag exceeds the motor torque and the motor stops) and the timer and stirrer are stopped. The timer time is recorded as the gel time (minutes).

Chemical resistance test method Chemical resistance is determined as follows:
Test samples are prepared by making 10 gram packs of curable two-part (Michael donor and Michael acceptor) compositions. The composition pack is cured at 25 ° C. ± 5 ° C. and 50% relative humidity for 7 days. Weigh the cured sample and record the initial weight. The cured sample is immersed in acidic or basic conditions for 28 days. In acidic conditions, three cured pack samples are immersed in a pH 1 solution (0.1 M HCl) for 28 days at 25 ° C. ± 5 ° C. and 50% relative humidity. In basic conditions, three cured pack samples are immersed in a pH 12 solution (NaOH _aq ) at 40 ° C. ± 5 ° C. and 50% relative humidity. After 7, 14, 21, and 28 days, the pack is removed from the test solution, rinsed with deionized water at ambient temperature, dried for 1 hour, recorded, and re-immersed in an appropriate new solution. Chemical resistance is reported as percent weight change (weight loss or weight increase) of the cured pack sample.

Exotherm The exotherm of the multi-pack curable composition is that standard mixture after mixing 100 grams of A part (Michael donor and Michael reaction catalyst) and B part (Michael acceptor) in a plastic beaker. It is determined by measuring the temperature and time of the mixture using a digital thermometer. The exotherm is recorded as the maximum (max) temperature (° C.) that the mixture reaches when it cures.

Bubble Formation Test Method Bubble formation of the multi-pack solventless adhesive composition is accomplished by mixing 100 g of a mixture of part A (donor and catalyst) and part B (acceptor) and mixing the mixture at 25 ° C. ± 5 ° C. and relative Determined by curing for 7 days at 50% humidity. After curing, the composition is visually inspected for bubble formation. If there are no bubbles in the cured composition, it is acceptable. If there are bubbles in the cured composition, it is rejected.

Michael Donor The following Michael donor was used to make the cured compositions tested in the examples:
Donor 1 (D-1) (acetoacetoxytrimethylolpropane (AATMP)
Donor 1 was prepared by adding trimethylolpropane and tert-butyl acetoacetate (TBAA) to a reaction kettle equipped with a stirrer and a distillation column connected to a vacuum line. The amount of polyol and TBAA was used such that the desired degree of conversion of the polyol was 100 mole% using a 1/3 molar excess of TBAA. The reaction was carried out at 120 ° C. for 2 hours and the tert-butanol byproduct was recovered by distillation. The reaction was continued at this temperature until no more tert-butanol was recovered. The reaction was allowed to cool to ambient temperature, a vacuum was applied, and the reaction was heated to 120 ° C. over 1 hour to recover any residual tert-butanol and tert-butyl acetoacetate. The reaction was heated until no more tert-butanol and tert-butyl acetoacetate were recovered at 125 ° C. for 3-4 hours or longer. The acetoacetylated polyol was cooled and stored for use.

Donor 2 (D-2) (Voranol 230-660 triacetoacetate)
Donor 2 was prepared according to the procedure of D-1, except that Voranol 230-660 (polyether polyol, commercially available from Dow Chemical) was used instead of trimethylolpropane.

Donor 3 (D-3) (mixture of 75% by weight D-1 and 25% by weight Voranol 220-056N diacetate)
Donor 3 was prepared by mixing 75 wt% D-1 and 25 wt% Voranol 220-056N diacetoacetate. Voranol 220-056N diacetate was prepared according to the procedure of D-1, except that Voranol 220-056N (polyether polyol, commercially available from Dow Chemical) was used instead of trimethylolpropane.

Donor 4 (D-4)
Donor 4 (D) according to the procedure of D-1, except that K-FLEX® UD-320-100 (polyurethanediol, commercially available from King Industries, Norwalk, CT) was used instead of trimethylolpropane. -4) was prepared.

Michael Receptor The following Michael acceptor was used to make the curable compositions tested in the examples:
Receptor 1 (A-1): Multifunctional polyester acrylate oligomer (CN292, available from Sartomer USA, LLC).
Receptor 2 (A-2): ethoxylated (10) bisphenol A diacrylate (SR602, available from Sartomer USA, LLC).
Receptor 3 (A-3): multifunctional polyester acrylate oligomer (CN2283, available from Sartomer USA, LLC).
Receptor 4 (A-4): Ethoxylated (4) Bisphenol A diacrylate (SR 601 available from Sartomer USA, LLC).
Receptor 5 (A-5): urethane hexaacrylate oligomer based on 90% SR 602 and 10% aliphatic polyester (CN968, available from Sartomer USA, LLC).
Receptor 6 (A-6): 90% SR 602 and 10% hexafunctional aromatic urethane hexaacrylate oligomer (CN975, available from Sartomer USA, LLC).
Receptor 7 (A-7): 20% CN 292, 60% SR833 S (tricyclodecane dimethanol diacrylate, available from Sartomer USA, LLC) and 20% CN 929 (trifunctional urethane acrylate, Sartomer USA, Available from LLC).
Receptor 8 (A-8): 20% CN 292, 75% SR833 S, and 5% CN 929.
Receptor 9 (A-9): 25% CN 292, 50% SR833 S, and 25% CN 929.

Michael Reaction Catalyst The following Michael reaction catalyst was used to make the cured compositions tested in the examples:
1,8-diazabicyclo [5.4.0] -7-undecene (available from DBU, Air Products).

Examples 1-15 and Comparative Examples 1-2
Each cured composition of Examples 1-15 and Comparative Examples 1-2 was prepared by combining the A and B parts according to Table 1 at ambient temperature prior to testing, and then the various tests described herein. Tested according to the method. The results are shown in Tables 1 and 2 below.

^＊２部分ポリウレタン接着剤、Ｈ．Ｂ．Ｆｕｌｌｅｒ（Ｓｔ．Ｐａｕｌ，ＭＮ）から市販。
^＊＊２部分エポキシ接着剤、Ｈ．Ｂ．Ｆｕｌｌｅｒから市販。
^＊＊＊適用せず。

^* Two-part polyurethane adhesive, H.P. B. Commercially available from Fuller (St. Paul, MN).
^** 2-part epoxy adhesive, H.P. B. Commercially available from Fuller.
^*** Not applicable.

^＊合格：重量の増加又は減少が５％未満。
^＊＊ＮＴ：試験せず。

^* Pass: Increase or decrease in weight is less than 5%.
^** NT: Not tested.

  The above specification, examples and data provide a complete description of the disclosure. Since many embodiments can be made without departing from the spirit and scope of the disclosure, the invention resides in the claims hereinafter appended.

Claims (20)

A method for producing a hollow fiber membrane module,
Preparing a mixture of multi-pack solventless curable compositions by combining a multi-functional Michael donor, a multi-functional Michael acceptor, and a Michael reaction catalyst;
Introducing the mixture of curable compositions into at least one end of a plurality of hollow fiber membranes;
Solidifying and curing the curable composition, thereby potting the ends of the plurality of hollow fiber membranes.   The method of claim 1, wherein the curable composition further comprises 0 wt% or more and less than 10 wt% filler, based on the weight of the curable composition.   The method of claim 1, wherein the curable composition exhibits an initial viscosity of 200 centipoise (cP) to 10,000 cP at 25 ° C. The multifunctional Michael donor is
At least one acetoacetoxy functional group;
Selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, urethane polyols, polybutadiene polyols, glycols, monohydric alcohols, polyhydric alcohols, natural oil polyols, and modifications thereof, and combinations thereof. The method of claim 1, comprising an acetoacetylated polyol having a backbone.   The method of claim 1, wherein the multifunctional Michael acceptor is selected from the group consisting of multifunctional (meth) acrylate monomers, oligomers, and polymers, and combinations thereof.   6. The multi-functional Michael acceptor comprising multi-functional polyester acrylate, ethoxylated bisphenol A diacrylate, urethane acrylate oligomer, polyethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, and combinations thereof. The method described.   The method of claim 6, wherein the curable composition exhibits non-foaming properties in the presence of moisture upon curing.   The method of claim 6, wherein the urethane acrylate oligomer comprises a hexafunctional aromatic urethane acrylate oligomer, an aliphatic polyester-based urethane hexaacrylate oligomer, and combinations thereof.   The process of claim 1, wherein the catalyst is a strong base catalyst having a conjugate acid with a pKa greater than 11.   The method of claim 1, wherein the catalyst comprises amidine and guanidine.   The catalyst is 1,1,3,3-tetramethylguanidine (TMG), 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), and 1,5-diazabicyclo [4,3, 10. The method of claim 9, comprising 0] -5-nonene (DBN).   The method of claim 1, wherein the cured composition exhibits a maximum exotherm temperature of 120 ° C. or less.   The process of claim 1 wherein the equivalent ratio of Michael acceptor functional acrylate to Michael donor active hydrogen is 0.3: 1 to 1.5: 1.   The process of claim 1, wherein the catalyst is present in an amount of 0.1% to 10%, based on moles of Michael active hydrogen atoms.   The method of claim 1, wherein the curable composition exhibits a gel time of 3 minutes to 120 minutes.   The method of claim 1, wherein the curable composition exhibits a Shore A hardness of 50 or greater after curing for 7 days at 25 ° C. and 50% relative humidity.   The method of claim 1, wherein the curable composition exhibits a Shore D hardness of 40 or greater after curing for 7 days at 25 ° C. and 50% relative humidity. A hollow fiber membrane module,
A plurality of hollow fiber membranes having at least one end potted with a potting composition;
The potting composition is
Multifunctional Michael donor,
A hollow fiber membrane module comprising a multi-functional Michael acceptor and a reaction product of a Michael reaction catalyst.   The hollow fiber membrane module according to claim 18, wherein the potting composition exhibits a Shore A hardness of 50 or more after curing for 7 days at 25 ° C. and 50% relative humidity.   The hollow fiber membrane module according to claim 18, wherein the potting composition exhibits non-foaming properties in the presence of moisture.

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