WO2017111043A1 - Composition de formation de résine de polyuréthane, matériau d'étanchéité d'une membrane de module utilisant une membrane de séparation en fibres en forme creuse ou en forme de membrane plate utilisant la composition de formation et composition de polyisocyanate contenant un groupe allophanate dérivée de mdi et procédé de production correspondant - Google Patents

Composition de formation de résine de polyuréthane, matériau d'étanchéité d'une membrane de module utilisant une membrane de séparation en fibres en forme creuse ou en forme de membrane plate utilisant la composition de formation et composition de polyisocyanate contenant un groupe allophanate dérivée de mdi et procédé de production correspondant Download PDF

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WO2017111043A1
WO2017111043A1 PCT/JP2016/088416 JP2016088416W WO2017111043A1 WO 2017111043 A1 WO2017111043 A1 WO 2017111043A1 JP 2016088416 W JP2016088416 W JP 2016088416W WO 2017111043 A1 WO2017111043 A1 WO 2017111043A1
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Prior art keywords
group
allophanate
isocyanate
polyurethane resin
forming composition
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PCT/JP2016/088416
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English (en)
Japanese (ja)
Inventor
太田太
池本満成
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東ソー株式会社
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Priority claimed from JP2015252102A external-priority patent/JP6631246B2/ja
Priority claimed from JP2016185222A external-priority patent/JP6753240B2/ja
Application filed by 東ソー株式会社 filed Critical 東ソー株式会社
Priority to EP16878929.5A priority Critical patent/EP3395849A4/fr
Priority to CN201680075280.XA priority patent/CN108431072B/zh
Priority to US16/063,691 priority patent/US11225547B2/en
Publication of WO2017111043A1 publication Critical patent/WO2017111043A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers

Definitions

  • the present invention relates to a polyurethane resin forming composition, a membrane sealing material for a module using a hollow or flat membrane separation membrane using the forming composition, diphenylmethane diisocyanate (hereinafter referred to as MDI) and an alcohol component.
  • MDI diphenylmethane diisocyanate
  • the present invention relates to a polyisocyanate composition containing derivatized allophanate groups and a method for producing the same.
  • Modules using hollow fibers or flat membranes as separation membranes are widely used in industrial fields such as water treatment and medical fields such as blood treatment.
  • the demand for water purifiers, artificial kidneys, artificial lungs and the like is extremely increasing.
  • polyurethane membranes with excellent flexibility, adhesiveness, and chemical resistance at room temperature are used as membrane sealing materials for bonding and fixing the ends of converged modules using hollow or flat membrane-like fiber separation membranes. It is widely known to use.
  • a polyurethane resin for example, as an isocyanate component, a polyurethane resin obtained by curing an isocyanate group-terminated prepolymer obtained from liquefied diphenylmethane diisocyanate and castor oil or castor oil derivative polyol with a polyol has been proposed. (For example, refer to Patent Document 1).
  • the polyurethane resin used in the conventional membrane sealing material for membrane modules has a problem that it is difficult to balance reactivity, low viscosity, and low temperature storage stability, and a solution is desired.
  • polyisocyanate group-terminated prepolymers containing allophanate groups derived from MDI and alcohol components have low viscosity, low precipitation of MDI monomers at low temperatures, and are easy to handle. Is useful and widely applied.
  • Known catalysts for generating allophanate groups from MDI and alcohol components include zinc acetylacetone, metal carboxylates such as zinc, lead, tin, copper, and cobalt, and hydrates thereof. It is a compound and is not preferred for medical and food applications.
  • Catalysts that do not contain metal compounds that form allophanate groups from isocyanate and alcohol components include, for example, N, N, N-trimethyl-N-2-hydroxypropylammonium hydroxide and N, N, N-trimethyl-N-2- Quaternary ammonium salts such as hydroxypropylammonium-2-ethylhexanoate are also known (see, for example, Patent Document 2), but these quaternary ammonium salts are useful for aliphatic and alicyclic isocyanates.
  • aromatic isocyanates such as MDI
  • the reaction is rapid and insoluble crystals tend to precipitate, and the catalyst is easily deactivated, making it difficult to put it to practical use.
  • a catalyst for generating an isocyanurate group from an isocyanate group a tertiary amine containing a phenolic hydroxyl group such as 2,4,6-tris (dimethylaminomethyl) phenol is known (see, for example, Patent Document 3).
  • a tertiary amine containing a phenolic hydroxyl group such as 2,4,6-tris (dimethylaminomethyl) phenol
  • the present invention has been made in view of the background art described above.
  • the first object of the present invention is to form a polyurethane resin-forming composition for fixing a hollow or flat membrane-like fiber separation membrane capable of providing a balance between reactivity and viscosity reduction and imparting low-temperature storage stability. Is to provide.
  • the second object of the present invention is to provide an MDI prepolymer containing no metal compound and having a high allophanate group content and a production method capable of easily controlling the reaction in the production.
  • an isocyanate group-containing compound (a1) represented by the following general formula (1) (hereinafter referred to as (a1) It was found that the above first problem can be solved by using a polyurethane resin-forming composition containing)), which is also referred to as a structure, and a metal catalyst is included when allophanating MDI with a tertiary amine catalyst.
  • the present inventors have found that the second problem can be solved by the manufacturing method and have completed the present invention.
  • R 1 represents a residue other than the active hydrogen group of the active hydrogen group-containing compound (b1), X represents an oxygen or sulfur atom, and R represents an unreacted isocyanate group of the isocyanate group-containing compound (a2).
  • M represents an integer of 1 or 2.
  • n represents an integer of 1 to 30, and when m is 2, n represents an integer of 1 to 15.
  • R 2 is selected from any one of H, an alkyl group, an alkenyl group, a cycloalkyl group, an arylalkyl group and an aryl group, wherein R 3 and R 4 are each independently an OH group, an alkyl group, An alkenyl group, a cycloalkyl group, an arylalkyl group, an aryl group, an oxyalkyl group, an oxyalkenyl group, an oxycycloalkyl group, an oxyarylalkyl group and an oxyaryl group)
  • the present invention includes the following embodiments (1) to (16).
  • a polyurethane resin-forming composition containing an isocyanate component (A) and a polyol component (B), and an isocyanate group-containing compound represented by the following general formula (1) in the isocyanate component (A) An allophanate group-containing polyurethane resin-forming composition containing a1).
  • R 1 represents a residue other than the active hydrogen group of the active hydrogen group-containing compound (b1), X represents an oxygen or sulfur atom, and R represents an unreacted isocyanate group of the isocyanate group-containing compound (a2).
  • M represents an integer of 1 or 2.
  • n represents an integer of 1 to 30, and when m is 2, n represents an integer of 1 to 15.
  • the content of the isocyanate group-containing compound (a1) represented by the general formula (1) in the isocyanate component (A) is 20 to 90 peak area% in gel permeation chromatography measurement.
  • the allophanate group-containing polyurethane resin-forming composition as described in (1) or (2) above.
  • the isocyanate group-containing compound (a1) is an allophanate group-containing polyisocyanate composition which is a reaction product of diphenylmethane diisocyanate and an alcohol, and the molar ratio of allophanate groups to isocyanurate groups is 80:20 to 100: 0, comprising at least one selected from the group consisting of a carboxylic acid amide, a sulfonic acid amide, and an active methylene compound represented by formula (2), and a tertiary amine catalyst as an allophanatization reaction aid, and a metal catalyst
  • the allophanate group-containing polyurethane resin-forming composition according to any one of (1) to (3) above, wherein the allophanate group-containing polyisocyanate composition does not contain any of the above.
  • R 2 is selected from any one of H, an alkyl group, an alkenyl group, a cycloalkyl group, an arylalkyl group and an aryl group, wherein R 3 and R 4 are each independently an OH group, an alkyl group, An alkenyl group, a cycloalkyl group, an arylalkyl group, an aryl group, an oxyalkyl group, an oxyalkenyl group, an oxycycloalkyl group, an oxyarylalkyl group and an oxyaryl group)
  • a method for producing an allophanate group-containing polyurethane resin comprising reacting the isocyanate component (A) according to any one of (1) to (7) and a polyol component (B).
  • a sealing material comprising a cured product of the allophanate group-containing polyurethane resin-forming composition according to any one of (1) to (7) above.
  • An allophanate group-containing polyisocyanate composition which is a reaction product of diphenylmethane diisocyanate and alcohol, wherein the molar ratio of allophanate group to isocyanurate group is 80:20 to 100: 0, and the carboxylic acid amide, sulfone It contains at least one selected from the group consisting of an acid amide and an active methylene compound represented by the general formula (2), and a tertiary amine catalyst as an allophanatization reaction aid, and does not contain a metal catalyst.
  • An allophanate group-containing polyisocyanate composition which is a reaction product of diphenylmethane diisocyanate and alcohol, wherein the molar ratio of allophanate group to isocyanurate group is 80:20 to 100: 0, and the carboxylic acid amide, sulfone It contains at least one selected from the group consisting of an acid amide and an active methylene compound represented by the general formula (2), and a tert
  • R 2 is selected from any one of H, an alkyl group, an alkenyl group, a cycloalkyl group, an arylalkyl group and an aryl group, wherein R 3 and R 4 are each independently an OH group, an alkyl group, An alkenyl group, a cycloalkyl group, an arylalkyl group, an aryl group, an oxyalkyl group, an oxyalkenyl group, an oxycycloalkyl group, an oxyarylalkyl group and an oxyaryl group)
  • R 2 is selected from any one of H, an alkyl group, an alkenyl group, a cycloalkyl group, an arylalkyl group and an aryl group, wherein R 3 and R 4 are each independently an OH group, an alkyl group, An alkenyl group, a cycloalkyl group, an arylalkyl group, an aryl group, an oxyalkyl group, an oxyalkenyl group, an oxycycloalkyl group, an oxyarylalkyl group and an oxyaryl group)
  • the normal temperature in the present invention means ⁇ 5 ° C. to 45 ° C.
  • Embodiment 1 means for solving the first problem is referred to as Embodiment 1
  • Embodiment 2 means for solving the second problem is referred to as Embodiment 2.
  • the use of the polyurethane resin-forming composition of the present invention makes it possible in particular to improve reactivity, viscosity reduction, and low-temperature storage stability.
  • the polyurethane resin-forming composition according to the present invention is liquid at room temperature (for example, 25 ° C.). This excellent effect is very suitable for use as a binding material for medical and industrial fluid separation devices (ie, sealing materials for membrane modules) using the desired hollow fiber separation membrane or flat membrane separation membrane. can do.
  • a polyisocyanate composition containing an allophanate group which does not contain a metal compound and has a small amount of isocyanurate causing turbidity. It can be used suitably. Moreover, when obtaining the polyisocyanate composition containing the said allophanate group, since reaction can be controlled easily, it is very useful industrially.
  • the polyurethane resin-forming composition that solves the first problem of the present invention comprises an isocyanate component (A) and a polyol component (B).
  • an isocyanate component (A) an isocyanate group-containing compound (a2)
  • the isocyanate component (A) is represented by the general formula (1) obtained by reacting the isocyanate group-containing compound (a2) and the active hydrogen group-containing compound (b1) in the presence of the catalyst (C). Containing the isocyanate group-containing compound (a1).
  • the isocyanate group-containing compound (a2) in the present invention is not particularly limited, and any compound that contains two or more isocyanate groups in one molecule can be used.
  • Examples of the compound containing two or more isocyanate groups in one molecule include toluene diisocyanate, MDI, paraphenylene diisocyanate, metaphenylene diisocyanate, naphthalene-1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ′′.
  • -Aromatic isocyanates such as triisocyanate, polyphenylene polymethylene polyisocyanate, hexamethylene diisocyanate, 1,10-decane diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and 1, 4-diisocyanate, isophorone diisocyanate, 2,4- and 2,6-hexahydrotoluylene diisocyanate, hexahydro-1,3- and -1,4-phenylene Isocyanurate-modified, biuret-modified, allophanate-modified, uretdione from aliphatic or alicyclic isocyanates such as isocyanate, perhydro-2,4'- and -4,4'-diphenylmethane diisocyanate, or a part of a series of these isocyanates Modification,
  • aromatic isocyanates are preferred from the viewpoints of being able to form a cured resin that is excellent in the working environment at the time of molding and has good physical properties (for example, mechanical strength such as hardness) required for a sealing material.
  • MDI is more preferable.
  • the active hydrogen group-containing compound (b1) a compound containing one or more active hydrogen groups in one molecule can be used. Monovalent or divalent ones are preferred from the standpoints of excellent workability, suitable physical properties required for the obtained membrane sealing material, and excellent membrane sealing material productivity. Trivalent or higher compounds are not preferred because the viscosity of the resulting isocyanate component (A) increases.
  • the active hydrogen group-containing compound (b1) preferably has 1 to 70 carbon atoms, and more preferably 3 to 30 carbon atoms.
  • Examples of the compound (b1) having a monovalent or divalent active hydrogen group include aliphatic, aromatic, and alicyclic alcohols, diols, and thiols.
  • aliphatic alcohol examples include methanol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol, lauryl alcohol, stearyl alcohol and the like.
  • Examples of the aliphatic diol include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butanediol, and 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, methylpropanediol, 3-methyl-1,5-pentanediol and the like.
  • aromatic alcohol examples include benzyl alcohol, phenethyl alcohol, hydroxybenzyl alcohol, hydroxyphenethyl alcohol, methoxyphenylmethanol and the like.
  • aromatic diol examples include 1,4-benzenedimethanol and 2,3-naphthalenediethanol.
  • Examples of the alicyclic alcohol include cyclohexanol, methylcyclohexanol, dimethylcyclohexanol and the like.
  • Examples of the alicyclic diol include 1,2-cyclopentanediol, 1,3-cyclopentanediol, 3-methyl-1,2-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, Examples include 1,4-cyclohexanediol, 4,4′-bicyclohexanol, 1,4-cyclohexanedimethanol and the like.
  • thiols examples include tridecyl mercaptopropionate, methoxybutyl mercaptopropionate, octyl mercaptopropionate, 3-mercaptobutyrate derivatives, 1,4-bis (mercaptomethyl) benzene, and the like.
  • aliphatic alcohols and aliphatic diols are preferable, and 2-propanol, 2-ethylhexanol, and tridecanol are particularly preferable from the viewpoint of obtaining more suitable physical properties required for the obtained membrane sealing material.
  • the monomer isocyanate content present in the isocyanate component (A) was determined from the peak area% (hereinafter also referred to as PA%) obtained by GPC measurement.
  • the monomer isocyanate content is preferably 10.0 to 70.0 PA% in the sample to be measured, more preferably 20.0 to 60.0 PA%, and the viewpoint that the molding processability is excellent in the production of the membrane sealing material Most preferably, it is present in the range of 30.0 to 50.0 PA%.
  • the isocyanate group content of the isocyanate component (A) is preferably 3 to 30% by mass, more preferably 5 to 28% by mass, and 10 to 26% by mass from the viewpoint of excellent molding processability in the production of the membrane sealing material. Most preferably.
  • the content of the (a1) structure in the isocyanate component (A) is determined from PA% obtained by GPC measurement, and is preferably 20 to 90 PA%, more preferably 30 to 80 PA%, and more preferably 50 to 70 PA% in the sample to be measured. Is most preferred.
  • the viscosity of the isocyanate component (A) is preferably 250 to 1500 mPa ⁇ s at 25 ° C. from the viewpoint of obtaining low viscosity and good moldability.
  • the polyol component (B) is not particularly limited, but any compound containing an active hydrogen group can be used.
  • a low molecular polyol, a polyether polyol, a polyester polyol, a polylactone polyol, a castor oil polyol, a polyolefin polyol, a hydroxyl group-containing amine compound, and the like can be given. These can be used alone or in combination of two or more. Among these, castor oil-based polyol is preferable because it is excellent in chemical resistance and elution resistance.
  • Examples of the low molecular polyol include divalent ones such as ethylene glycol, diethylene glycol, propylene glycol, 1,2-, 1,3- or 1,4-butanediol, 1,5-pentanediol, 3-methyl-1 , 5-pentanediol, 1,6-hexaneglycol, 1,8-octanediol, 1,10-decandiol, neopentylglycol, hydrogenated bisphenol A, etc.
  • Examples include methylolpropane, hexanetriol, pentaerythritol, and sorbitol.
  • the molecular weight of the low molecular polyol is preferably 50 to 200.
  • polyether polyols examples include adducts of the above low molecular polyols with alkylene oxides (alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, etc.), and ring-opening polymers of alkylene oxides.
  • alkylene oxides alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, etc.
  • ring-opening polymers of alkylene oxides examples include polypropylene glycol, polyethylene glycol, polytetramethylene ether glycol, and chipped ether that is a copolymer of ethylene oxide and propylene oxide.
  • the molecular weight of the polyether polyol is preferably 200 to 7000.
  • the molecular weight is more preferably 500 to 5,000 from the viewpoint of excellent molding processability during the production of the membrane sealing material.
  • Polyester acids include polycarboxylic acids (aliphatic saturated or unsaturated polycarboxylic acids such as azelaic acid, dodecanoic acid, maleic acid, fumaric acid, itaconic acid, ricinoleic acid, dimerized linoleic acid, and aromatic polycarboxylic acids.
  • examples thereof include a polyol obtained by condensation polymerization of phthalic acid, isophthalic acid, terephthalic acid) and a polyol (at least one selected from the group consisting of the above low-molecular polyol and polyether polyol).
  • the molecular weight of the polyester polyol is preferably 200 to 5,000.
  • the molecular weight is more preferably 500 to 3000 from the viewpoint of excellent molding processability during the production of the membrane sealing material.
  • Polylactone-based polyols include polymerization initiators such as glycols and triols, ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, and ⁇ -methyl- ⁇ -valerolactone.
  • Examples include polyols obtained by addition polymerization of at least one selected from the group consisting of organic metal compounds, metal chelate compounds, fatty acid metal acyl compounds and the like in the presence of a catalyst.
  • the molecular weight of the polylactone polyol is preferably 200 to 5,000.
  • the molecular weight is more preferably 500 to 3000 from the viewpoint of excellent molding processability during the production of the membrane sealing material.
  • the castor oil-based polyol a linear or branched polyester obtained by a reaction between a castor oil fatty acid and a polyol (at least one selected from the group consisting of the above low-molecular polyol and polyether polyol), for example, a diglyceride of castor oil fatty acid.
  • a polyol at least one selected from the group consisting of the above low-molecular polyol and polyether polyol
  • a diglyceride of castor oil fatty acid for example, a diglyceride of castor oil fatty acid.
  • the molecular weight of the castor oil-based polyol is preferably 300 to 4000.
  • the molecular weight is more preferably 500 to 3000 from the viewpoint of excellent molding processability during the
  • polystyrene-based polyol examples include polybutadiene-based polyol in which a hydroxyl group is introduced at the end of a copolymer of polybutadiene or butadiene and styrene or acrylonitrile.
  • polyether ester polyols obtained by addition reaction of an alkylene oxide such as ethylene oxide or propylene oxide with a polyester having at least one selected from the group consisting of a carboxyl group and a hydroxyl group at the terminal.
  • hydroxyl group-containing amine compound examples include amino alcohols as oxyalkylated derivatives of amino compounds.
  • amino alcohols include N, N, N ′, N′-tetrakis [2-hydroxypropyl] ethylenediamine, N, N, N ′, N, which are propylene oxide or ethylene oxide adducts of amino compounds such as ethylenediamine.
  • examples include '-tetrakis [2-hydroxyethyl] ethylenediamine, mono-, di- and triethanolamine, N-methyl-N, N'-diethanolamine, and the like. Of these, propylene oxide or ethylene oxide adducts of amino compounds such as ethylenediamine are preferred, and N, N, N ′, N′-tetrakis [2-hydroxypropyl] ethylenediamine is more preferred.
  • Use of N, N, N ′, N′-tetrakis [2-hydroxypropyl] ethylenediamine is effective in improving processability during molding and lowering the eluate.
  • the amount of the hydroxyl group-containing amine compound used is preferably in the range of 1 to 30% by mass, particularly preferably in the range of 5 to 25% by mass with respect to 100% by mass of the polyol component (B). . If the proportion in the polyol (B) is less than 1% by mass, the effect of the hydroxyl group-containing amine compound cannot be obtained, and if it exceeds 30% by mass, the reactivity becomes too high, the workability deteriorates and the filling property is impaired. Moreover, there is a possibility that the problem that the hardness of the obtained sealing material becomes too high may occur.
  • Catalyst (C) for example, any known catalyst that can promote the allophanatization reaction of the isocyanate group-containing compound (a2) and the active hydrogen group-containing compound (b1) is included.
  • the catalyst (C) for example, metal salts, quaternary ammonium salts, and tertiary amines.
  • metal salts such as zinc acetylacetonate (ZnAcAc), stannous octoate, and zinc octoate.
  • Quaternary ammonium salts include tetraalkylammonium such as N, N, N, N, -tetramethylammonium, N, N, N-trimethyl-N-octylammonium, and N- (2-hydroxyethyl) -N, N. , N, -trimethylammonium, N- (2-hydroxypropyl) -N, N, N, -trimethylammonium and other hydroxyalkyltrialkylammonium and chloride, bromide, hydroxide, formate, caproate, hexanoate, 2-ethyl This compound is a combination of counter ions such as hexanoate and monoalkyl carbonate.
  • Tertiary amines include N, N, N-benzyldimethylamine, N, N, N-dibenzylmethylamine, N, N, N-cyclohexyldimethylamine, N-methylmorpholine, N, N, N-tribenzyl Trialkylamines such as ruamine, N, N, N-tripropylamine, N, N, N-tributylamine, N, N, N-tripentylamine or N, N, N-trihexylamine and N, N, Polymethylpolyalkylenepolyamines such as N ′, N′-tetramethylethylenediamine, N, N, N ′, N ′, N ′′ -pentamethyldiethylenetriamine and 2- (N, N-dimethylamino) ethanol, 3- ( N, N-dimethylamino) propanol, 2- (N, N-dimethylamino) -1-methylpropanol, ⁇ 2- (N, N
  • the catalyst (C) is preferably 1 to 100 ppm, more preferably 10 to 50 ppm based on the mass of the isocyanate component (A). If it is less than 1 ppm, the reaction may not proceed. If it exceeds 100 ppm, the reaction may be fast and difficult to control.
  • the terminator (D) is used as a terminator for the allophanatization reaction.
  • the terminator (D) includes any known one that deactivates the catalyst (C).
  • the terminator (D) includes any known one that deactivates the catalyst (C).
  • the terminator (D) is preferably added in an amount equal to or greater than the number of moles of the catalyst (C), and is preferably added in an amount of 1.0 to 1.5 times.
  • the polyisocyanate composition containing an allophanate group that solves the second problem of the present invention is a reaction product of MDI and an alcohol, wherein the molar ratio of allophanate group to isocyanurate group is 80:20 to 100: 0. And an allophanate group-containing polyisocyanate composition characterized by not containing a metal catalyst.
  • the reaction is rapid and difficult to control, and even if the reaction can be stopped at the desired reaction rate, the amount of isocyanurate produced is low. Because there are many, prepolymer tends to become cloudy.
  • E component used in the present invention may be any generally available MDI monomer.
  • the isomer of the MDI monomer is usually 0 to 5% by weight of 2,2'-MDI, 0 to 95% by weight of 2,4'-MDI, and 5 to 100% by weight of 4,4'-MDI.
  • the E component used in the present invention is preferably the above-mentioned MDI monomer.
  • polymethylene polyphenylene polyisocyanate which is polymeric MDI, is also used. Can be used.
  • the content of polymethylene polyphenylene polyisocyanate is preferably 0 to 50% by weight in the isocyanate component used. When it exceeds 50% by weight, the viscosity becomes too high, and insoluble matter is easily generated.
  • the (F) at least one alcohol component (hereinafter also referred to as “F component”) used in the present invention a compound containing a hydroxyl group having 1 to 2 number average functional groups, that is, a monool or a diol can be used.
  • a compound containing a phenolic hydroxyl group is not preferred because the isocyanurate group generation rate is increased and the viscosity is increased.
  • triol or higher polyol is not preferable because of its high viscosity.
  • Preferred monools for the F component used in the present invention include, for example, methanol, ethanol, propanol, 1- and 2-butanol, 1-pentanol, 1-hexanol, 2-methyl-1-pentanol, and 4-methyl.
  • polyalkylene glycol monoalkyl / aryl ethers which are oxyalkylene adducts using compounds containing phenolic hydroxyl groups such as phenol, cresol, xylenol, and nonylphenol as initiators, and mixtures thereof Is mentioned.
  • monocarboxylic acid ester of polyalkylene glycol, a mixture thereof, etc. are mentioned.
  • Preferred diols for the F component used in the present invention include, for example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, Aliphatic glycols such as 1,5-pentanediol, 2,2′-dimethyl-1,3-propanediol, 1,6-hexanediol, 2-methyl-2-butyl-1,3-propanediol, and these glycols And polyalkylene glycols, which are oxyalkylene adducts having an initiator as the initiator, and mixtures thereof.
  • the (G) carboxylic acid amide used in the present invention at least one (hereinafter also referred to as “G component”) carboxylic acid amide selected from the group consisting of a carboxylic acid amide, a sulfonic acid amide, and an active methylene compound represented by the above formula (2)
  • G component carboxylic acid amide selected from the group consisting of a carboxylic acid amide, a sulfonic acid amide, and an active methylene compound represented by the above formula (2)
  • G sulfonic acid amide used in the present invention examples include methylsulfonamide, butylsulfonamide, t-butylsulfonamide, phenylsulfonamide, benzylsulfonamide, o-toluylsulfonamide, p-toluylsulfonamide, 3 -Aminophenylsulfonamide, 4-aminophenylsulfonamide and mixtures thereof.
  • Examples of the active methylene compound of G component used in the present invention include acetylacetone, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, 3,5-heptanedione, 3,5- Examples include heptanedione, 6-methyl-2,4-heptanedione, methyl acetoacetate, ethyl acetoacetate, methyl 3-oxopentanoate, malonic acid, dimethyl malonate, diethyl malonate, and mixtures thereof.
  • H component As the (H) tertiary amine (hereinafter also referred to as “H component”) used in the present invention, for example, trialkylamine, polymethylpolyalkylenepolyamine, tertiary aminoalcohol and the like can be used.
  • trialkylamine examples include N, N, N-benzyldimethylamine, N, N, N-dibenzylmethylamine, N, N, N-cyclohexyldimethylamine, N-methylmorpholine, N, N, N-tone.
  • examples include rebenzylamine, N, N, N-tripropylamine, N, N, N-tributylamine, N, N, N-tripentylamine or N, N, N-trihexylamine.
  • polymethylpolyalkylenepolyamine examples include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ′, N ′′ -pentamethyldiethylenetriamine and the like.
  • tertiary amino alcohols examples include 2- (dimethylamino) ethanol, 3- (dimethylamino) propanol, 2- (dimethylamino) -1-methylpropanol, 2- ⁇ 2- (dimethylamino) ethoxy ⁇ ethanol, 2 - ⁇ 2- (diethylamino) ethoxy ⁇ ethanol, 2-[ ⁇ 2- (dimethylamino) ethyl ⁇ methylamino] ethanol and the like.
  • tertiary amino alcohols are particularly preferred because of volatilization during the reaction and less elution when they become final resins.
  • the combined use of a quaternary ammonium salt is effective when the time until the reaction starts (hereinafter also referred to as “induction period”) becomes long.
  • Quaternary ammonium salts are useful for shortening the production time because the reaction starts within a few minutes after addition.
  • quaternary ammonium salt used in combination with the H component for example, a tetraalkylammonium, a compound in which a hydroxyalkyltrialkylammonium is combined with a counter ion, or the like can be used.
  • tetraalkylammonium examples include N, N, N, N, -tetramethylammonium, N, N, N-trimethyl-N-octylammonium and the like.
  • hydroxyalkyltrialkylammonium examples include N- (2-hydroxyethyl) -N, N, N-trimethylammonium, N- (2-hydroxypropyl) -N, N, N, -trimethylammonium and the like.
  • Examples of the counter ion combined with ammonium include chloride, bromide, hydroxide, formate, caproate, hexanoate, 2-ethylhexanoate, monoalkyl carbonate, and the like.
  • tetraalkylammonium is suitable as the counter ion, but as the counter ion to be combined, carboxylate and monoalkyl carbonate are preferable from the viewpoint of compatibility with MDI.
  • reaction is not controlled by the G component without using a tertiary amine and the quaternary ammonium salt alone is not effective because it deactivates during the reaction.
  • the G component used in the present invention can be added at any time from immediately before the urethanization reaction by the E component and the F component to immediately after the start of the allophanatization reaction. If the H component is added, the effect cannot be exerted, so the G component is added immediately before the urethanization reaction and after the completion of the urethanization reaction, immediately before the addition of the H component and until the allophanatization starts. Or it is preferable to add G component and H component simultaneously.
  • the amount of addition of the H component in the present invention is preferably 0.1 to 100 ppm with respect to the total amount of the E component and the F component, and particularly preferably 1 to 50 ppm, depending on its catalytic activity. If it is less than 0.1 ppm, the reaction may not proceed, and if it exceeds 100 ppm, the reaction may be fast and difficult to control.
  • the amount of G component used in the present invention is preferably about 0.1 to 50 times mol of H component, and if it is less than 0.1 times mol, the reaction becomes abrupt and cannot be controlled, and exceeds 50 times mol. If added, the reaction may hardly proceed.
  • the temperature at which the E component and the F component are allophanatized with the G component and the H component the higher the temperature, the more the allophanate group is produced and the lower the viscosity, but side reactions such as uretdioneization and carbodiimidization occur.
  • the reaction temperature is preferably 20 ° C. or more and 200 ° C. or less, and the production ratio of isocyanurate groups is suppressed to 20 mol% or less. In order to make it lower viscosity, 60 degreeC or more and 160 degrees C or less are preferable.
  • an acidic substance is suitable, for example, anhydrous hydrogen chloride, sulfuric acid, phosphoric acid, monoalkyl sulfate, alkyl sulfonic acid, alkyl benzene sulfone. Also included are acids, mono- or dialkyl phosphates, benzoyl chloride and Lewis acids. The amount added is preferably equivalent to or more, and preferably 1.0 to 1.5 times the molar equivalent of the number of moles of the tertiary amine or quaternary ammonium salt of the H component as the catalyst.
  • the catalyst (C) was added to this, heated to 90 ° C., the reaction was followed while sampling the internal solution and measuring the NCO content, and when the NCO content was predicted to reach 21.0%, the terminator (D) was placed. The reaction was stopped by adding a fixed amount to obtain an isocyanate component (A-1).
  • the isocyanate component (A-1) was light yellow and transparent, and its viscosity at 25 ° C. was 550 mPa ⁇ s.
  • a polyol component (B-1) was prepared by mixing 80 parts by mass of the polyol (b13) and 20 parts by mass of the polyol (b15).
  • Measuring device “HLC-8120 (trade name)” (manufactured by Tosoh Corporation) Column: Columns filled with three kinds of TSKgel G3000HXL, TSKgel G2000HXL, and TSKgel G1000HXL (all trade names, manufactured by Tosoh Corporation) as packing materials were connected in series, and measured at a column temperature of 40 ° C.
  • Detector RI (refractive index)
  • meter Eluent Tetrahydrofuran (THF) (Flow rate: 1 ml / min, 40 ° C.)
  • Calibration curve A calibration curve was obtained using the following grade polystyrene (TSK standard POLYSTYRENE).
  • a calibration curve was obtained from a chart obtained by detecting the refractive index difference using polystyrene as a standard substance.
  • the PA% of the peak near the peak top molecular weight (number average molecular weight) 230 indicating the monomer MDI, and (a1) structure
  • the PA% near the peak top molecular weight (number average molecular weight) 3800, 3360, 2600, 2000, 1260, 700 was determined.
  • the isocyanate components (A-1) to (A-4), (A-13) and (A-14) according to Production Examples 1 to 4, 13, and 14 shown in Tables 1 and 2 have a low viscosity. In addition, it has excellent low-temperature storage stability. In contrast, the isocyanate components (A-5) and (A-7) according to Production Example 5 and Production Example 7 have low viscosity but are inferior in low-temperature storage stability. In addition, the isocyanate components (A-9) to (A-12) according to Production Examples 9 to 12 are excellent in low-temperature storage stability but have a high viscosity.
  • the polyurethane resin-forming compositions according to Examples 1 to 6 all have a low initial mixing viscosity and a short pot life, so that the moldability is balanced.
  • the polyurethane resin-forming compositions according to Comparative Example 1 and Comparative Example 2 have a low initial mixing viscosity, but take a long time to form a membrane module because of their long pot life.
  • the polyurethane resin-forming compositions according to Comparative Examples 3 to 6 all have high mixing viscosities, there is a concern that the filling property at the time of membrane module molding is inferior and poor filling occurs.
  • the predetermined amount means each composition amount shown in Table 5.
  • Example 7 A predetermined amount of isoE1 was added to a 1 liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly F1 was added with stirring, and the temperature was raised to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature was stabilized at 110 ° C., a predetermined amount of amide G1 diluted to 1% with polyF1 was added, and then a predetermined amount of catalyst H1 diluted to 1% with polyB1 was immediately added.
  • the synthesized prepolymer was a light yellow transparent liquid at room temperature, and the amount of isocyanurate groups was small, and the prepolymer which was the object of the present invention was obtained.
  • the properties and the molar ratio of each functional group are shown in Table 5, and the transition of the NCO content during the reaction is shown in FIG. The reaction was stable and control of the reaction was easy.
  • Example 8 A predetermined amount of isoE2 was added to a 1 liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly F1 was added with stirring, and the temperature was raised to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature was stabilized at 110 ° C., a predetermined amount of catalyst H1 diluted to 1% with polyF1 was added. When an increase in the liquid temperature was confirmed about 15 minutes after addition of the catalyst H1, a predetermined amount of amide G1 diluted to 1% with polyF1 was added.
  • the reaction was followed while sampling the internal solution and measuring the NCO content, and when the NCO content was predicted to be 22.8%, a predetermined amount of catalyst poison J was added to stop the reaction.
  • the synthesized prepolymer was a light yellow transparent liquid at room temperature, and the amount of isocyanurate groups was small, so that the prepolymer (P-1) which was the object of the present invention was obtained.
  • the properties and the molar ratio of each functional group are shown in Table 5, and the transition of the NCO content during the reaction is shown in FIG. The reaction was stable and control of the reaction was easy.
  • Example 9 A predetermined amount of isoE1 was added to a 1 liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly F1 was added with stirring, and the temperature was raised to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature stabilized at 110 ° C., a predetermined amount of amide G1 diluted to 1% with polyF1 was added, and then a predetermined amount of catalyst H2 diluted to 1% with polyF1 was immediately added.
  • the synthesized prepolymer was a light yellow transparent liquid at room temperature, and the amount of isocyanurate groups was small, and the prepolymer which was the object of the present invention was obtained.
  • the properties and the molar ratio of each functional group are shown in Table 5, and the transition of the NCO content during the reaction is shown in FIG. The reaction was stable and control of the reaction was easy.
  • Example 10 A predetermined amount of isoE1 was added to a 1-liter four-necked flask, and the temperature was adjusted to 70 ° C. while stirring under a nitrogen stream. Next, a predetermined amount of poly F1 was added while stirring, and then a predetermined amount of catalyst H3 diluted to 1% with poly F1 was immediately added. Next, a predetermined amount of amide G1 diluted to 1% with polyF1 was added, and then a predetermined amount of catalyst H2 diluted to 1% with polyF1 was immediately added, and the temperature was adjusted to 110 ° C.
  • the synthesized prepolymer was a light yellow transparent liquid at room temperature, and the amount of isocyanurate groups was small, and the prepolymer which was the object of the present invention was obtained.
  • the properties and the molar ratio of each functional group are shown in Table 5, and the transition of the NCO content during the reaction is shown in FIG. The reaction was stable and control of the reaction was easy.
  • Example 11 A predetermined amount of isoE2 was added to a 1 liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly F2 was added while stirring, and the temperature was raised to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature was stabilized at 110 ° C., a predetermined amount of catalyst H1 diluted to 1% with polyF2 was added. When an increase in the liquid temperature was confirmed approximately 15 minutes after addition of the catalyst H1, a predetermined amount of amide G2 diluted to 1% with polyF2 was added.
  • the reaction was followed while sampling the internal solution and measuring the NCO content, and when the NCO content was predicted to be 13.8%, a predetermined amount of catalyst poison J was added to stop the reaction.
  • the synthesized prepolymer was a pale yellow transparent liquid at 25 ° C., and the amount of isocyanurate groups was small, so that the prepolymer (P-2) which was the object of the present invention was obtained.
  • the properties and the molar ratio of each functional group are shown in Table 5, and the transition of the NCO content during the reaction is shown in FIG. The reaction was stable and control of the reaction was easy.
  • Example 12 A predetermined amount of isoE2 was added to a 1 liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly F3 was added while stirring, and the temperature was raised to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature was stabilized at 110 ° C., a predetermined amount of methylene E3 diluted to 1% with polyF3 was added, and then a predetermined amount of catalyst H1 diluted to 1% with polyF3 was immediately added.
  • the synthesized prepolymer was a light yellow transparent liquid at room temperature, and the amount of isocyanurate groups was small, so that the prepolymer (P-3) which was the object of the present invention was obtained.
  • Table 5 shows the properties and the molar ratio of each functional group, and FIG. 2 shows the transition of the NCO content during the reaction. The reaction was stable and control of the reaction was easy.
  • Example 13 A predetermined amount of isoE2 was added to a 1 liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly F3 was added while stirring, and the temperature was raised to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature was stabilized at 110 ° C., a predetermined amount of methylene G4 diluted to 1% with polyF3 was added, and then a predetermined amount of catalyst D1 diluted to 1% with polyF3 was immediately added.
  • the synthesized prepolymer was a light yellow transparent liquid at room temperature, and the amount of isocyanurate groups was small, and the prepolymer which was the object of the present invention was obtained.
  • Table 5 shows the properties and the molar ratio of each functional group, and FIG. 2 shows the transition of the NCO content during the reaction. The reaction was stable and control of the reaction was easy.
  • Comparative Example 7 A predetermined amount of isoE2 was added to a 1 liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly F1 was added with stirring, and the temperature was raised to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature was stabilized at 110 ° C., a predetermined amount of catalyst H1 diluted to 1% with polyF1 was added. About 15 minutes after addition of the catalyst H1, the rise in the liquid temperature was confirmed, and the reaction was followed. However, the reaction temperature could not be controlled due to rapid exotherm, and the prepolymer which is the object of the present invention was not obtained because of gelation. It was. Therefore, it could not be used as a prepolymer that solves the first problem.
  • Comparative Example 8 A predetermined amount of isoE1 was added to a 1 liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly F1 was added with stirring, and the temperature was raised to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature was stabilized at 110 ° C., a predetermined amount of catalyst H1 diluted to 1% with polyF1 was added. About 10 minutes after addition of catalyst H1, the rise in the liquid temperature could be confirmed, and the reaction was followed. However, the reaction temperature could not be controlled due to rapid exotherm, so when the internal temperature reached 124 ° C, catalyst poison J was removed.
  • the reaction was stopped by adding a predetermined amount.
  • the synthesized prepolymer was a pale yellow transparent liquid at room temperature, but the amount of isocyanurate groups was large and the prepolymer which was the object of the present invention was not obtained. From the viewpoint that the reaction cannot be controlled, it has been difficult to use it as a prepolymer that solves the first problem.

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

Abstract

L'invention concerne une composition de formation de résine de polyuréthane qui présente un bon équilibre entre la réactivité et une faible viscosité, qui peut conférer une stabilité au stockage à basse température et qui fixe une membrane de séparation en forme creuse ou en forme de membrane plate et un prépolymère de MDI ne contenant pas de composé métallique et présentant une teneur élevée en groupes allophanate et un procédé de production dans lequel une réaction peut être facilement régulée dans la production correspondante. La solution porte sur l'utilisation d'une composition de formation de résine de polyuréthane contenant un composé contenant un groupe isocyanate spécifique dans un constituant isocyanate et la réaction d'un MDI en présence d'au moins l'un choisi dans le groupe constitué par un amide d'acide carboxylique, un amide d'acide sulfonique et un composé actif de méthylène, sans contenir de catalyseur métallique, lorsque le MDI est allophanatisé avec un catalyseur de type amine tertiaire.
PCT/JP2016/088416 2015-12-24 2016-12-22 Composition de formation de résine de polyuréthane, matériau d'étanchéité d'une membrane de module utilisant une membrane de séparation en fibres en forme creuse ou en forme de membrane plate utilisant la composition de formation et composition de polyisocyanate contenant un groupe allophanate dérivée de mdi et procédé de production correspondant WO2017111043A1 (fr)

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EP16878929.5A EP3395849A4 (fr) 2015-12-24 2016-12-22 Composition de formation de résine de polyuréthane, matériau d'étanchéité d'une membrane de module utilisant une membrane de séparation en fibres en forme creuse ou en forme de membrane plate utilisant la composition de formation et composition de polyisocyanate contenant un groupe allophanate dérivée de mdi et procédé de production correspondant
CN201680075280.XA CN108431072B (zh) 2015-12-24 2016-12-22 聚氨酯树脂形成性组合物、使用其的膜密封材料以及多异氰酸酯组合物及其制造方法
US16/063,691 US11225547B2 (en) 2015-12-24 2016-12-22 Polyurethane resin-forming composition, module membrane seal material using a hollow-shaped or flat membrane-shaped fiber separation membrane using said forming composition, and allophanate group-containing polyisocyanate composition derived from MDI and production method therefor

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JP2015-252102 2015-12-24
JP2015252102A JP6631246B2 (ja) 2015-12-24 2015-12-24 膜シール材用ポリウレタン樹脂形成性組成物、及び該形成性組成物を用いた中空状或いは平膜状繊維分離膜を用いたモジュール用膜シール材
JP2016058205 2016-03-23
JP2016-058205 2016-03-23
JP2016-185222 2016-09-23
JP2016185222A JP6753240B2 (ja) 2016-03-23 2016-09-23 Ｍｄｉから誘導されるアロファネート基含有ポリイソシアネート組成物及びその製造方法

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JP2019056097A (ja) * 2017-09-19 2019-04-11 東ソー株式会社 ポリウレタン樹脂形成性組成物、ならびに、該形成性組成物を用いたシール材及び膜モジュール
US11136481B2 (en) 2017-07-25 2021-10-05 Tosoh Corporation Polyurethane resin-formable composition for membrane seal material, and membrane seal material and membrane module using said composition

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JPH07224140A (ja) * 1994-02-03 1995-08-22 Bayer Ag ５℃より高温で液体であるポリイソシアネート混合物
JPH09125001A (ja) * 1995-09-18 1997-05-13 Bayer Ag ジフェニルメタンジイソシアネートに基づき、アロファネート基とブロックされたイソシアネート基を含有するポリイソシアネート
JP2004263108A (ja) * 2003-03-03 2004-09-24 Nippon Polyurethane Ind Co Ltd ウレタンエラストマー形成性組成物およびシール材

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JPH07224140A (ja) * 1994-02-03 1995-08-22 Bayer Ag ５℃より高温で液体であるポリイソシアネート混合物
JPH09125001A (ja) * 1995-09-18 1997-05-13 Bayer Ag ジフェニルメタンジイソシアネートに基づき、アロファネート基とブロックされたイソシアネート基を含有するポリイソシアネート
JP2004263108A (ja) * 2003-03-03 2004-09-24 Nippon Polyurethane Ind Co Ltd ウレタンエラストマー形成性組成物およびシール材

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11136481B2 (en) 2017-07-25 2021-10-05 Tosoh Corporation Polyurethane resin-formable composition for membrane seal material, and membrane seal material and membrane module using said composition
JP2019056097A (ja) * 2017-09-19 2019-04-11 東ソー株式会社 ポリウレタン樹脂形成性組成物、ならびに、該形成性組成物を用いたシール材及び膜モジュール
JP7326700B2 (ja) 2017-09-19 2023-08-16 東ソー株式会社 ポリウレタン樹脂形成性組成物、ならびに、該形成性組成物を用いたシール材及び膜モジュール

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