WO2013146266A1 - Compositions générant une résine de polyuréthane utilisables à des fins de scellement d'un module membranaire - Google Patents

Compositions générant une résine de polyuréthane utilisables à des fins de scellement d'un module membranaire Download PDF

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Publication number
WO2013146266A1
WO2013146266A1 PCT/JP2013/056996 JP2013056996W WO2013146266A1 WO 2013146266 A1 WO2013146266 A1 WO 2013146266A1 JP 2013056996 W JP2013056996 W JP 2013056996W WO 2013146266 A1 WO2013146266 A1 WO 2013146266A1
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carbon atoms
group
acid
diazabicyclo
general formula
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PCT/JP2013/056996
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English (en)
Japanese (ja)
Inventor
ゆう子 住友
島田　哲也
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三洋化成工業株式会社
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Priority to CN201380009231.2A priority Critical patent/CN104114262B/zh
Priority to JP2014507647A priority patent/JP5802330B2/ja
Publication of WO2013146266A1 publication Critical patent/WO2013146266A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B01D63/021—Manufacturing thereof
    • B01D63/022—Encapsulating hollow fibres
    • B01D63/023—Encapsulating materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/003—Membrane bonding or sealing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
    • C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • 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
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • 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
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1021—Polyurethanes or derivatives thereof

Definitions

  • the present invention relates to a polyurethane resin-forming composition for a sealing material of a membrane module, and particularly relates to a polyurethane resin-forming composition for a sealing material of a membrane module suitable as a sealing material for a blood treatment device or a water purifier.
  • Examples of the polyurethane resin-forming composition for a sealing material of a membrane module include those using a mixture of castor oil-based polyol and N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine as a polyol component. It is known (see, for example, Patent Document 1).
  • a bundle of bundles of many hollow fibers is filled into a cylindrical container, and then a polyurethane resin-forming composition is injected, and the polyurethane resin solution simultaneously bonds the hollow fibers and between the cylindrical containers.
  • a manufacturing method is used in which after the polyurethane resin-forming composition is solidified, a portion where the hollow fibers are bound is cut perpendicularly to the direction in which the hollow fibers are arranged.
  • a step occurs on the end of the hollow fiber and the bottom surface of the polyurethane resin existing between the hollow fibers when the end portion after cutting is viewed. If such unevenness is large, contaminants adhere to the edge, or blood remains in the unevenness when used for blood treatment, so it is desirable that the unevenness of the cut surface is small and smoothness is excellent. Has been.
  • the present invention has been made in view of the above problems, and the object of the present invention is excellent in curability and castability, has low turbidity, and has a smooth cut surface when used as a sealing material for a membrane module.
  • An object of the present invention is to provide a polyurethane resin-forming composition for a sealing material of a membrane module, which is capable of forming a polyurethane resin that is excellent in properties and has little eluate.
  • the present invention is a polyurethane resin-forming composition
  • a bicyclic amidine salt (C) represented by the general formula (1) Containing a bicyclic amidine salt (C) represented by the general formula (1), a polyurethane resin-forming composition for a sealing material of a membrane module; a main agent comprising an organic polyisocyanate component (A); A polyurethane resin-forming composition for a sealing material of a membrane module comprising a curing agent comprising a polyol component (B) and a bicyclic amidine salt (C) represented by the general formula (1); A membrane module using the seal material; a hollow fiber blood treatment device or a water purifier using the membrane module.
  • R 1 is a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a group represented by the general formula (2), or a general formula (3) in a group represented by,
  • X - is a saturated aliphatic carboxylic acid having 1 to 18 carbon atoms, unsaturated aliphatic carboxylic acids having 3-18 carbon atoms, aromatic carboxylic acids having 7 to 9 carbon atoms, 6 carbon atoms
  • An anion obtained by removing protons from
  • R 2 and R 4 each independently represent a hydrogen atom or an alkyl group having a carbon number of 1 to 3
  • R 3 represents a hydrogen atom, an alkyl group or a phenyl group having 1 to 16 carbon atoms
  • R 2 R 3 may be bonded to each other to form a ring having 5 to 8 carbon atoms
  • R 5 and R 6 each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms.
  • the polyurethane resin-forming composition for a sealing material of a membrane module of the present invention has the following effects. (1) It has excellent reactivity, exhibits good hardness for cutting in a short time, and maintains the hardness for a long time. (2) Low viscosity and excellent castability. (3) The polyurethane resin formed from the composition has low turbidity and excellent transparency. (4) The cut surface of the end portion of the membrane module using the polyurethane resin formed from the composition is excellent in smoothness. (5) The polyurethane resin formed from the composition has few eluates and is excellent in safety.
  • the polyurethane resin-forming composition for a sealing material for a membrane module of the present invention comprises two types of forms, that is, a main agent containing an organic polyisocyanate component (A) and a curing agent containing a polyol component (B).
  • a form (form 2) which consists of the hardening
  • the bicyclic amidine salt (C) represented by the general formula (1) having catalytic activity is used.
  • n is an integer of 2 to 6, and preferably 2 or 4 from the viewpoint of catalytic activity.
  • R 1 in the general formula (1) is a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a group represented by the general formula (2), or a group represented by the general formula (3).
  • R 2 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 3 represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms or a phenyl group.
  • R 2 and R 3 may be bonded to each other to form a ring having 5 to 8 carbon atoms
  • R 5 and R 6 are each independently a linear or branched alkyl group having 1 to 5 carbon atoms. Represents.
  • R 1 is preferably represented by the general formula (2) in which (C) is incorporated into the polyurethane resin due to the presence of a hydroxyl group, from the viewpoint of non-elution of the bicyclic amidine salt (C). More preferred are 2-hydroxyethyl, 2-hydroxypropyl and 2-hydroxy-1-methylethyl groups.
  • X in the general formula (1) - is a saturated aliphatic carboxylic acid having 1 to 18 carbon atoms, unsaturated aliphatic carboxylic acids having 3-18 carbon atoms, aromatic carboxylic acids having 7 to 9 carbon atoms, C 6 -C
  • the bicyclic amidine salt (C) represented by the general formula (1) includes, for example, a bicyclic amidine compound represented by the general formula (4), a saturated aliphatic carboxylic acid having 1 to 18 carbon atoms, At least one selected from the group consisting of an unsaturated aliphatic carboxylic acid having 3 to 18 carbon atoms, an aromatic carboxylic acid having 7 to 9 carbon atoms, an aromatic sulfonic acid having 6 to 8 carbon atoms, and an amino acid having 2 to 11 carbon atoms. It can be obtained by reacting an acid and / or a phenol having 6 to 8 carbon atoms.
  • N and R 1 in the general formula (4) are the same as those in the general formula (1).
  • bicyclic amidine compound represented by the general formula (4) examples include 1,5-diazabicyclo [4.3.0] -5-nonene (hereinafter abbreviated as DBN), 1,5 -Diazabicyclo [4.4.0] -5-decene (hereinafter abbreviated as DBD), 1,8-diazabicyclo [5.4.0] -7-undecene (hereinafter abbreviated as DBU), 7-methyl-1 , 5-diazabicyclo [4.3.0] -5-nonene, 7-ethyl-1,5-diazabicyclo [4.3.0] -5-nonene, 7-propyl-1,5-diazabicyclo [4.3 .0] -5-nonene, 7-butyl-1,5-diazabicyclo [4.3.0] -5-nonene, 7-pentyl-1,5-diazabicyclo [4.3.0] -5-nonene,
  • DBN, DBD, DBU, HE-DBN, HP-DBN, HE-DBU, and HP-DBU are preferable and non-eluting from the viewpoint of curability, castability, and smoothness of the cut surface of the membrane module.
  • HE-DBN, HP-DBN, HE-DBU and HP-DBU having a hydroxyl group, which are incorporated into a polyurethane resin upon curing are more preferable.
  • a bicyclic amidine compound may be used individually by 1 type, or may use 2 or more types together.
  • saturated aliphatic carboxylic acids having 1 to 18 carbon atoms include formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, and tridecanoic acid , Carboxylic acids having no hydroxyl group such as tetradecanoic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid and octylic acid, and aliphatics such as glycolic acid, lactic acid, glyceric acid, hydroxybutyric acid, malic acid, tartaric acid and citric acid A hydroxy acid etc. are mentioned.
  • the unsaturated aliphatic carboxylic acid having 3 to 18 carbon atoms does not have a hydroxyl group such as crotonic acid, myristoleic acid, sapienoic acid, oleic acid, linoleic acid, linolenic acid, pinolenic acid, eleostearic acid and stearidonic acid
  • a hydroxyl group such as crotonic acid, myristoleic acid, sapienoic acid, oleic acid, linoleic acid, linolenic acid, pinolenic acid, eleostearic acid and stearidonic acid
  • unsaturated aliphatic carboxylic acids and unsaturated aliphatic hydroxy acids such as shikimic acid and ricinoleic acid.
  • aromatic carboxylic acids having 7 to 9 carbon atoms include aromatic carboxylic acids having no hydroxyl group such as benzoic acid, phthalic acid, hemimellitic acid and trimellitic acid, salicylic acid, cresotic acid, protocatechuic acid, vanillic acid and shilling. Examples thereof include aromatic hydroxy acids such as acids.
  • aromatic sulfonic acid having 6 to 8 carbon atoms examples include benzenesulfonic acid, p-toluenesulfonic acid and p-ethylbenzenesulfonic acid.
  • amino acids having 2 to 11 carbon atoms include glycine, alanine, valine, leucine and isoleucine.
  • phenol having 6 to 8 carbon atoms examples include phenol, cresol, xylenol and ethylphenol.
  • a saturated aliphatic carboxylic acid having 1 to 18 carbon atoms and an unsaturated aliphatic carboxylic acid having 3 to 18 carbon atoms are preferable from the viewpoint of low toxicity.
  • a saturated aliphatic carboxylic acid having 1 to 18 carbon atoms, an unsaturated aliphatic carboxylic acid having 3 to 18 carbon atoms, an aromatic carboxylic acid having 7 to 9 carbon atoms, an aromatic sulfonic acid having 6 to 8 carbon atoms, and 2 carbon atoms ⁇ 11 amino acids and C6-C8 phenols may be used alone or in combination of two or more. Preferred as a combination of two or more of these is castor oil fatty acid.
  • a bicyclic amidine compound represented by the general formula (4) a saturated aliphatic carboxylic acid having 1 to 18 carbon atoms, an unsaturated aliphatic carboxylic acid having 3 to 18 carbon atoms, and a 7 to 9 carbon atoms.
  • the ratio is important and mixing is performed so that the molar ratio of the acid and / or phenol to the bicyclic amidine compound is preferably in the range of 0.8 to 1.2, more preferably 0.9 to 1.1.
  • Adjust the ratio When the molar ratio is less than 0.8, that is, when the ratio of acid or phenol is extremely low, the ratio of the counter anion decreases, so that the bicyclic amidine compound existing in the free state increases.
  • the pot life after mixing polyol and organic polyisocyanate may be shortened.
  • the molar ratio exceeds 1.2 that is, when the ratio of acid or phenol is extremely large, the curing rate becomes slow and the productivity may be lowered.
  • the bicyclic amidine salt (C) can be added to either the main agent containing the organic polyisocyanate component (A) or the curing agent containing the polyol component (B), or both. Moreover, it can use as a 3rd component different from an organic polyisocyanate component (A) and a polyol component (B).
  • the amount of the bicyclic amidine salt (C) used is preferably 0.0001 to 1.0% by weight, more preferably based on the total weight of the organic polyisocyanate component (A) and the polyol component (B) used. Is 0.001 to 0.2% by weight, particularly preferably 0.01 to 0.1% by weight. Bicyclic amidine salt (C) may be used individually by 1 type, or may use 2 or more types together.
  • the organic polyisocyanate component (A) in the present invention is not particularly limited, and is an organic polyisocyanate (a1) having two or more isocyanate groups in one molecule, or an isocyanate group-terminated urethane obtained by a reaction between the organic polyisocyanate and a polyol. It consists of either the prepolymer (a2) or a combination of both.
  • An organic polyisocyanate component (A) may be used individually by 1 type, or may use 2 or more types together.
  • Examples of the organic polyisocyanate (a1) include aliphatic polyisocyanates having 2 to 18 carbon atoms (excluding carbon atoms in the isocyanate group, the same shall apply hereinafter), alicyclic polyisocyanates having 4 to 15 carbon atoms, and 6 carbon atoms. ⁇ 20 aromatic polyisocyanates, aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms, and some isocyanate groups of these polyisocyanates are modified with isocyanurate, biuret, allophanate, uretdione, uretonimine, carbodiimide, oxazolidone, amide or imide And a mixture thereof.
  • Examples of the aliphatic polyisocyanate include diisocyanate [ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, bis (2 -Isocyanatoethyl) fumarate and bis (2-isocyanatoethyl) carbonate, etc.], and triisocyanate [1,6,11-undecane triisocyanate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate, etc.] Can be mentioned.
  • alicyclic polyisocyanate examples include diisocyanates [isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, etc.]. Can be mentioned.
  • aromatic polyisocyanate for example, diisocyanate [2,4- or 2,6-toluene diisocyanate, 4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate is referred to as MDI).
  • MDI diphenylmethane diisocyanate
  • Abbreviation and naphthalene diisocyanate or those having three or more isocyanate groups [polymethylene polyphenyl polyisocyanate having three or more benzene rings].
  • araliphatic polyisocyanate examples include diisocyanates [xylylene diisocyanate, ⁇ , ⁇ , ⁇ , ' ⁇ '-tetramethylxylylene diisocyanate, diisocyanate ethylbenzene, and the like].
  • organic polyisocyanates (a1) aromatic polyisocyanates and modified products thereof are preferable from the viewpoint of reactivity, and 4,4′-, 2,4′- or 2,2′-MDI are more preferable. And a modified product thereof.
  • Examples of the polyol used in the isocyanate group-terminated urethane prepolymer (a2) in the present invention include a low molecular polyol having a number average molecular weight (hereinafter abbreviated as Mn) or a chemical formula weight of less than 300 and a polymer polyol having an Mn of 300 or more. .
  • Mn number average molecular weight
  • Mn in the present invention is measured by gel permeation chromatography using THF as a solvent and polyoxypropylene glycol as a standard substance.
  • the sample concentration may be 0.25% by weight
  • the column stationary phase may be TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (both manufactured by Tosoh Corporation), and the column temperature may be 40 ° C.
  • Examples of the low molecular polyol having Mn or a chemical formula of less than 300 include polyols having 2 to 24 carbon atoms such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin.
  • a low molecular polyol may be used individually by 1 type, or may use 2 or more types together.
  • the hydroxyl value of the low molecular polyol having Mn or a chemical formula of less than 300 is preferably 380 to 2000 mgKOH / g, more preferably 400 to 1500 mgKOH / g, from the viewpoint of the mechanical properties of the resulting polyurethane resin.
  • the number of functional groups of the low molecular polyol having Mn or a chemical formula amount less than 300 is preferably 2 to 8, more preferably 2 to 4, from the viewpoint of mechanical properties of the resulting polyurethane resin.
  • Examples of the polymer polyol having Mn of 300 or more include polyether polyol and polyester polyol.
  • polyether polyols having Mn of 300 or more examples include AO adducts starting from one or a mixture of two or more low-molecular polyols having a chemical formula weight of less than 300, specifically polyethylene glycol. , Polypropylene glycol (hereinafter abbreviated as PPG), polytetramethylene glycol, and the like.
  • PPG Polypropylene glycol
  • Ptetramethylene glycol polytetramethylene glycol
  • Polyester polyols having an Mn of 300 or more include castor oil fatty acid ester polyols (for example, castor oil, partially dehydrated castor oil, and ester exchange reaction between the low molecular weight polyol or polyether polyol and castor oil, or an ester of castor oil fatty acid.
  • castor oil fatty acid ester polyols for example, castor oil, partially dehydrated castor oil, and ester exchange reaction between the low molecular weight polyol or polyether polyol and castor oil, or an ester of castor oil fatty acid.
  • Castor oil fatty acid ester obtained by the conversion reaction); poly (n 2 to 3 or more) carboxylic acid [aliphatic saturated or unsaturated polycarboxylic acid (having 2 to 40 carbon atoms, such as oxalic acid, adipic acid, azelaic acid) , Dodecanoic acid, maleic acid, fumaric acid, itaconic acid and dimerized linoleic acid), aromatic ring-containing polycarboxylic acid (8 to 15 carbon atoms such as phthalic acid, isophthalic acid, terephthalic acid and 2,6-naphthalenedicarboxylic acid) And alicyclic polycarboxylic acids (7 to 15 carbon atoms, such as 1,3-penta Dicarboxylic acid and 1,4-hexanedicarboxylic acid) and the like] and a polyol (the aforementioned low molecular polyol and / or polyether polyol); a linear or branched polyester polyol;
  • polyether polyols and castor oil fatty acid ester polyols are preferable from the viewpoint of the low viscosity of (a2), and polyether polyols are more preferable from the viewpoint of transparency, and further from the viewpoint of mechanical properties.
  • Preferred are castor oil, partially dehydrated castor oil and castor oil fatty acid PPG ester.
  • a high molecular polyol may be used individually by 1 type, or may use 2 or more types together.
  • Mn of the polymer polyol having Mn of 300 or more is preferably 300 to 5,000, more preferably 500 to 3,000, from the viewpoint of mechanical properties of the obtained polyurethane resin.
  • the hydroxyl value of the polymer polyol having Mn of 300 or more is preferably 20 to 350 mgKOH / g, more preferably 40 to 300 mgKOH / g, from the viewpoint of mechanical properties of the obtained polyurethane resin.
  • the number of functional groups of the polymer polyol having Mn of 300 or more is preferably 2 to 8, more preferably 2 to 4, from the viewpoint of mechanical properties of the obtained polyurethane resin.
  • NCO / OH equivalent ratio
  • the mixture of organic polyisocyanate (a1) and isocyanate group terminal urethane prepolymer (a2) is obtained.
  • the organic polyisocyanate component (A) only the organic polyisocyanate (a1) or only the isocyanate group-terminated urethane prepolymer (a2) can be used. From the viewpoint of low viscosity and the hardness of the polyurethane resin, (a1) and (a2 ) Is preferably used in combination.
  • the content of (a2) in the organic polyisocyanate component (A) when used in combination is preferably 20% by weight or more and less than 100% by weight, more preferably 30 to 90% by weight.
  • the reaction temperature in the prepolymerization reaction is usually 30 to 140 ° C., and preferably 50 to 120 ° C. from the viewpoint of reactivity and prevention of side reactions.
  • the reaction is usually carried out in the absence of a solvent, but if necessary, a solvent having no reactivity with an isocyanate group [for example, aromatic hydrocarbons (toluene, xylene, etc.), ketones (methyl ethyl ketone, methyl isobutyl ketone, etc.) and these 2 These solvents may be removed later by distillation.
  • polyol component (B) in the present invention examples include polyols used in the isocyanate group-terminated urethane prepolymer, amine polyols, and mixtures of two or more thereof.
  • polyether polyol and castor oil fatty acid ester polyol are preferable from the viewpoint of low viscosity, and polyether polyol is more preferable from the viewpoint of transparency.
  • polyether polyol, castor oil fatty acid ester polyol and amine polyol are preferred, and castor oil, partially dehydrated castor oil, castor oil fatty acid PPG ester and amine polyol are more preferred.
  • the NCO / OH equivalent ratio when the polyurethane resin is formed from the organic polyisocyanate component (A), polyol component (B) and bicyclic amidine salt (C) constituting the composition of the present invention is preferably 0.5 / 1 to 2.0 / 1, more preferably 0.7 / 1 to 1.5 / 1, and particularly preferably 0.8 / 1 to 1.2 / 1.
  • the polyurethane resin-forming composition for the sealing material of the membrane module of the present invention comprises an organic polyisocyanate component (A), a polyol component (B) and a bicyclic amidine salt (C), or a bicyclic amidine salt ( C) can be produced by mixing two components, which are previously mixed with the organic polyisocyanate component (A) and / or the polyol component (B), with a predetermined amount at the time of use and then mixing with a static mixer or mechanical mixer. Usually, the reaction starts almost simultaneously with the mixing and cures to become the polyurethane resin for the sealing material of the membrane module of the present invention.
  • the time until the fluidity is lost after mixing and reacting is usually 3 to 60 minutes, and curing requires 12 to 240 hours at room temperature (20 to 30 ° C.), and the hardness of the polyurethane resin changes. The point at which is no longer recognized is considered to be complete curing.
  • the polyurethane resin it is preferably cured until the hardness (Shore D: instantaneous value) is in the range of 20 to 100.
  • the curing time can be shortened by increasing the curing temperature (for example, 40 to 60 ° C.).
  • the hardness in this invention is measured according to JISK7312, and an instantaneous value is a value immediately after pressing the needle
  • the temperature of the mixture (A), (B) and (C) is adjusted to 25 ° C., and after mixing, the viscosity of the mixed solution 30 seconds later is preferably from the viewpoint of curability and castability. 50 to 10,000 mPa ⁇ s, more preferably 100 to 5,000 mPa ⁇ s, and particularly preferably 200 to 2,000 mPa ⁇ s.
  • the preferable range of the viscosity of the liquid mixture of (A) and (B) when (C) is previously mixed with (A) and / or (B) is the same as described above.
  • the hardness (Shore D: instantaneous value) of the cured polyurethane resin obtained by reacting (A) and (B) in the presence of (C) was bound by the mechanical strength to be provided as the sealing material and the polyurethane resin. From the viewpoint of the cutting property of the hollow fiber, it is preferably 20 to 100, more preferably 30 to 80.
  • the polyurethane resin-forming composition of the present invention is suitably used as a sealing material for a membrane module, and in particular, a hollow fiber type blood treatment device or a hollow fiber type membrane module for a water purifier used for an artificial organ (artificial kidney or the like). It is useful as a sealing material.
  • the polyol component (B) in which a predetermined amount of the bicyclic amidine salt (C) is mixed in advance and the organic polyisocyanate component (A) are individually degassed under reduced pressure (0.1 mmHg ⁇ 2 hours).
  • a predetermined amount of these two liquids are weighed, mixed with stirring, and then poured into a container in which hollow fibers are set by centrifugal molding, and the hollow fibers are fixed to the container.
  • the centrifugal molding method for example, a method described in JP-B-57-58963 can be used.
  • the hollow fiber material Generally, cellulose, acrylic, polyvinyl alcohol, polyamide, polysulfone, etc. are used as the hollow fiber material.
  • the container is made of polycarbonate, ABS or polystyrene.
  • the two-component liquid mixture loses its fluidity 3 to 60 minutes after the injection, and the membrane module can be removed from the molding machine.
  • the hollow fiber membrane bound with polyurethane resin is cut with a rotary cutter or the like to obtain an opening at the end of the hollow fiber membrane.
  • an autoclave it sterilizes by steam heating at 120 degreeC for 1 hour, and commercializes. Sterilization can also be carried out by methods other than steam heating, for example, gamma irradiation.
  • Production Example 1 [Production of polyether polyol] After charging 150 parts of propylene glycol and 0.09 part of tris (pentafluorophenyl) borane into a stainless steel autoclave equipped with a stirrer, temperature controller, heat exchanger as a condensation facility, raw material supply line and exhaust line 2,290 parts of PO was continuously added to the liquid phase over 12 hours while controlling the reaction temperature to be maintained at 70 to 80 ° C. After aging at 70 ° C. for 4 hours, 200 parts of water was added and heated at 130 to 140 ° C. for 1 hour.
  • Production Example 5 [Production of polyol component (B-2)] A polyol component (B-2) was obtained in the same manner as in Production Example 3, except that 55 parts of “HS 2G-120” and 20 parts of “ELA-DR” were changed to 75 parts of the polyether polyol of Production Example 1. (B-2) had a hydroxyl value of 274 mgKOH / g and a viscosity of 430 mPa ⁇ s / 25 ° C.
  • Examples 1 to 12 and Comparative Examples 1 to 4 The isocyanate component (A-1) obtained in Production Example 2 was used as the main agent in Examples 1 to 10 and Comparative Examples 1 to 4, and the isocyanate component (A-2) obtained in Production Example 3 was used as the main agent in Examples 11 to 12. It was.
  • a reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube first, according to the formulation of Table 1, bicyclic amidine salt (C) or “dibutyltin dilaurate” or “TEDA- L33 ”was added, the polyol component (B) was added, and the mixture was stirred and mixed at 40 to 50 ° C. for 1 hour to obtain the curing agents of Examples 1 to 12 and Comparative Examples 1 to 3.
  • the curing agent of Comparative Example 4 was only polyol (B-1).
  • the number of parts shown in Table 1 (the number of parts described in the total value column for the curing agent) and the curing agent are stirred and mixed for 30 seconds with an agitator equipped with a rotary propeller blade
  • the following methods are used to determine the viscosity before casting of the mixed solution, pot life, hardness of cured resin, tin elution amount, potassium permanganate consumption, resin appearance, resin turbidity, and smoothness of the cut surface in the membrane module.
  • Table 2 shows the results of measurement or evaluation.
  • Viscosity before casting of liquid mixture Viscosity (mPa ⁇ s) 30 seconds after mixing was measured with a rotary viscometer (B-type viscometer).
  • the polyurethane resin-forming composition for sealing material of the membrane module of the present invention has excellent reactivity, expresses good hardness in cutting in a short time, maintains the hardness for a long time, has low viscosity and excellent castability
  • the polyurethane resin formed from the composition has low turbidity and excellent transparency, excellent smoothness of the cut surface when used as a sealing material for a membrane module, and there is little eluate and excellent safety. It is extremely useful for a wide range of applications for membrane modules (such as blood treatment devices and water purifiers), especially for hollow fiber blood treatment devices for artificial organs.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • External Artificial Organs (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'objet de la présente invention concerne des compositions générant une résine de polyuréthane utilisables à des fins de scellement d'un module membranaire et présentant une remarquable capacité de durcissement et une exceptionnelle coulabilité, ainsi qu'une faible turbidité, et se révélant, par ailleurs, capables d'assurer une planéité parfaite d'une partie coupée en cas d'utilisation en tant que matériau de scellement pour module membranaire, ainsi que de générer une résine de polyuréthane moins susceptible d'éluer. La présente invention concerne deux compositions générant une résine de polyuréthane utilisables à des fins de scellement d'un module membranaire, à savoir une composition générant une résine de polyuréthane comprenant un matériau principal contenant (A) un composant de type polyisocyanate organique et un agent de durcissement contenant (B) un composant de type polyol, ladite composition étant caractérisée en ce que le matériau principal et/ou l'agent de durcissement contiennent (C) un sel d'amidinium bicyclique de formule générale (1) ; et une composition générant une résine de polyuréthane caractérisée en ce qu'elle comprend un matériau principal contenant (A) un composant de type polyisocyanate organique et un agent de durcissement contenant (B) un composant de type polyol, et (C) un sel d'amidinium bicyclique de formule générale (1).
PCT/JP2013/056996 2012-03-29 2013-03-13 Compositions générant une résine de polyuréthane utilisables à des fins de scellement d'un module membranaire WO2013146266A1 (fr)

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CN201380009231.2A CN104114262B (zh) 2012-03-29 2013-03-13 膜组件的密封材料用聚氨酯树脂形成性组合物
JP2014507647A JP5802330B2 (ja) 2012-03-29 2013-03-13 膜モジュールのシール材用ポリウレタン樹脂形成性組成物

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
JP2018172598A (ja) * 2017-03-31 2018-11-08 東ソー株式会社 Ｍｄｉから誘導されるアロファネート変性体を含むポリイソシアネート組成物及びその製造方法
JP2019006856A (ja) * 2017-06-21 2019-01-17 東ソー株式会社 膜シール材用ポリウレタン樹脂形成性組成物、これを用いたシール材、及び中空糸膜モジュール
JP2020147684A (ja) * 2019-03-14 2020-09-17 東ソー株式会社 膜シール材用ポリウレタン樹脂形成性組成物、ならびに、これを用いた膜シール材及び膜モジュール
WO2024075775A1 (fr) * 2022-10-07 2024-04-11 東ソー株式会社 Composition de formation de résine de polyuréthane, et matériau d'étanchéité de film et module de film obtenus chacun à l'aide de ladite composition de formation de résine de polyuréthane

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JPS5893716A (ja) * 1981-11-27 1983-06-03 アクゾ・エヌ・ヴエ− 埋封材料
JPS6420287A (en) * 1987-03-25 1989-01-24 Tremco Inc Catalyst rapid curable polyurethane sealant composition
JP2002187927A (ja) * 2000-10-13 2002-07-05 Tosoh Corp 二成分系ポリウレタンシーラント製造用の触媒
JP2007332257A (ja) * 2006-06-14 2007-12-27 Cemedine Co Ltd 湿気硬化型ポリウレタン組成物
WO2009104700A1 (fr) * 2008-02-22 2009-08-27 旭硝子株式会社 Composition durcissable

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ES2257369T3 (es) * 2000-10-13 2006-08-01 Tosoh Corporation Catalizador para la preparacion de una composicion sellante de dos componentes a base de poliuretano.

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Publication number Priority date Publication date Assignee Title
JPS5893716A (ja) * 1981-11-27 1983-06-03 アクゾ・エヌ・ヴエ− 埋封材料
JPS6420287A (en) * 1987-03-25 1989-01-24 Tremco Inc Catalyst rapid curable polyurethane sealant composition
JP2002187927A (ja) * 2000-10-13 2002-07-05 Tosoh Corp 二成分系ポリウレタンシーラント製造用の触媒
JP2007332257A (ja) * 2006-06-14 2007-12-27 Cemedine Co Ltd 湿気硬化型ポリウレタン組成物
WO2009104700A1 (fr) * 2008-02-22 2009-08-27 旭硝子株式会社 Composition durcissable

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018172598A (ja) * 2017-03-31 2018-11-08 東ソー株式会社 Ｍｄｉから誘導されるアロファネート変性体を含むポリイソシアネート組成物及びその製造方法
JP2019006856A (ja) * 2017-06-21 2019-01-17 東ソー株式会社 膜シール材用ポリウレタン樹脂形成性組成物、これを用いたシール材、及び中空糸膜モジュール
JP7135279B2 (ja) 2017-06-21 2022-09-13 東ソー株式会社 膜シール材用ポリウレタン樹脂形成性組成物、これを用いたシール材、及び中空糸膜モジュール
JP2020147684A (ja) * 2019-03-14 2020-09-17 東ソー株式会社 膜シール材用ポリウレタン樹脂形成性組成物、ならびに、これを用いた膜シール材及び膜モジュール
JP7334431B2 (ja) 2019-03-14 2023-08-29 東ソー株式会社 膜シール材用ポリウレタン樹脂形成性組成物、ならびに、これを用いた膜シール材及び膜モジュール
WO2024075775A1 (fr) * 2022-10-07 2024-04-11 東ソー株式会社 Composition de formation de résine de polyuréthane, et matériau d'étanchéité de film et module de film obtenus chacun à l'aide de ladite composition de formation de résine de polyuréthane

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CN104114262A (zh) 2014-10-22
CN104114262B (zh) 2016-08-31
JP5802330B2 (ja) 2015-10-28

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