CN104114262B - The sealing material use polyurethane resin formative compositions of membrane module - Google Patents

The sealing material use polyurethane resin formative compositions of membrane module Download PDF

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Publication number
CN104114262B
CN104114262B CN201380009231.2A CN201380009231A CN104114262B CN 104114262 B CN104114262 B CN 104114262B CN 201380009231 A CN201380009231 A CN 201380009231A CN 104114262 B CN104114262 B CN 104114262B
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carbon number
acid
formula
alkene
membrane module
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CN104114262A (en
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住友优子
岛田哲也
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Sanyo Chemical Industries Ltd
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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

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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

It is an object of the invention to provide the sealing material use polyurethane resin formative compositions of membrane module, its curable and note excellent plasticity, and it is low to form turbidity, the polyurethane resin that the flatness of the section when the encapsulant of membrane module is excellent and leachable is few, the sealing material use polyurethane resin formative compositions of the membrane module of the present invention is made up of the host containing organic multiple isocyanate composition (A) and the firming agent containing polyol component (B), it is characterized in that, described host and/or described firming agent contain two ring types amidine salt (C) represented by formula (1)；The sealing material use polyurethane resin formative compositions of the membrane module of the present invention is characterised by, two ring types amidine salt (C) that the host being made up of organic multiple isocyanate composition (A), the firming agent being made up of polyol component (B) and formula (1) represent are constituted.

Description

The sealing material use polyurethane resin formative compositions of membrane module
Technical field
The present invention relates to the sealing material use polyurethane resin formative compositions of membrane module, particularly relate to be suitable for blood The sealing material use polyurethane resin formative compositions of the membrane module of the encapsulant of liquid processor or water purifier.
Background technology
Sealing material use polyurethane resin formative compositions as membrane module, it is known to use such as Oleum Ricini system is polynary Alcohol and N, N, N ', the mixture of N '-four (2-hydroxypropyl) ethylenediamine (see, for example patent documentation as polyol component 1)。
In recent years, in order to improve the productivity ratio of blood processor or water purifier, it is desirable to the sealing material use of rapidly-curable Polyurethane resin formative compositions.But, in order to obtain rapidly-curable, it is necessary to improve N, N, N ', N '-four (2- Hydroxypropyl) content of ethylenediamine, the viscosity of mixed liquor before this exists because injection raises and pot life shortens and leads Cause is difficult to the problems such as injection molding operation.It addition, the outward appearance expectation of sealing material use polyurethane resin formative compositions Low and transparent for turbidity, but if N, N, N ', the content of N '-four (2-hydroxypropyl) ethylenediamine increases, then have resin Turbidity raise and there is the trend of nebulousurine.On the other hand, in order to obtain rapidly-curable there is also use two Laurels The method of the metal series catalysts such as acid dibutyl tin, but when for purposes such as blood processors, metal is the most molten Go out and make safety have problems to blood.
It addition, generally in hollow fiber film assembly, the bundle of a large amount of doughnut boundlings is filled in cylindrical vessel In, be then injected into polyurethane resin formative compositions, utilize polyurethane resin solution to carry out between doughnut simultaneously and Joint between cylindrical vessel.After the solidification of polyurethane resin formative compositions, doughnut is connected bundles of part Cut off in the direction vertical with the arranged direction of doughnut, use this manufacture method to manufacture hollow fiber film assembly. But, in the case of using conventional polyurethane resin formative compositions, when the end after cutting off is observed, The apex height of doughnut and the bottom surface of polyurethane resin existed between doughnut produce jump (concavo-convex).This Concavo-convex big time, polluter can be attached to end or can be in jog remained blood when blood treatment, therefore phase Hope section concavo-convex little, flatness is excellent.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 53-61695 publication
Summary of the invention
The problem that invention is to be solved
The present invention completes in view of the above problems, it is an object of the invention to provide the membrane module of polyurethane resin Sealing material use polyurethane resin formative compositions, its curable and note excellent plasticity, and turbidity can be formed Low, the polyurethane resin that flatness is excellent and leachable is few of section when the encapsulant of membrane module.
Means for solving the above
The present inventor conducts in-depth research to solve the problems referred to above point, and result obtains the present invention.That is, the present invention Relate to: the sealing material use polyurethane resin formative compositions of membrane module, described polyurethane resin formative compositions Being made up of with the firming agent containing polyol component (B) the host containing organic multiple isocyanate composition (A), its feature exists In, described host and/or described firming agent contain two ring types amidine salt (C) represented by formula (1)；The sealing material of membrane module Material polyurethane resin formative compositions, it is by the host being made up of organic multiple isocyanate composition (A), by polynary Firming agent and two ring types amidine salt (C) represented by formula (1) that alcohol composition (B) is constituted are constituted；Use the film of above-mentioned composition The encapsulant of assembly；Use the membrane module of above-mentioned encapsulant；Use at the hollow fiber type blood of above-mentioned membrane module Reason device or water purifier.
[changing 1]
[in formula, n is the integer of 2～6, R1Be hydrogen atom, carbon number be straight chained alkyl or the branched alkane of 1～5 Base, formula (2) group represented or the group represented by formula (3), X-Be select free carbon number be 1～18 The fragrance that unsaturated aliphatic carboxylic acid that representative examples of saturated aliphatic carboxylic, carbon number are 3～18, carbon number are 7～9 Race's carboxylic acid, carbon number are in the aromatic sulphonic acid of 6～8 and the group of aminoacid that carbon number is 2～11 composition What at least one was sour removes the anion of proton and/or from the hydroxyl of the phenol that carbon number is 6～8 from carboxyl or sulfo group Base removes the anion of proton.]
[changing 2]
[in formula, R2And R4Separately represent hydrogen atom or the alkyl that carbon number is 1～3, R3Represent that hydrogen is former Son, carbon number are the alkyl or phenyl of 1～16, R2With R3Can be mutually bonded and form carbon number is 5～8 Ring, R5And R6Separately represent straight chained alkyl or branched alkyl that carbon number is 1～5.]
Invention effect
The sealing material use polyurethane resin formative compositions of the membrane module of the present invention plays following effect.
(1) reactive excellent, show the hardness that can well cut off in the short time, long-time its hardness of maintenance.
(2) viscosity is low and note excellent plasticity.
(3) the low and transparent excellence of the turbidity of the polyurethane resin formed by said composition.
(4) flatness using the section of the membrane module end of the polyurethane resin formed by said composition is excellent.
(5) leachable of the polyurethane resin formed by said composition is few, excellent in safety.
Detailed description of the invention
The sealing material use polyurethane resin formative compositions of the membrane module of the present invention has two kinds of forms, it may be assumed that by containing Have organic multiple isocyanate composition (A) host and containing polyol component (B) firming agent constitute, above-mentioned host and/ Or above-mentioned firming agent contains the form (form 1) of two ring types amidine salt (C) represented by formula (1)；With by by organic many isocyanides The host that acid esters composition (A) is constituted, the firming agent being made up of polyol component (B) and the two ring type amidines represented by formula (1) The form (form 2) that salt (C) is constituted.In arbitrary form of form 1 and form 2, its feature is all, makes apparatus There are two ring types amidine salt (C) represented by formula (1) of catalyst activity.
[changing 3]
The integer that n is 2～6 in formula (1), from the viewpoint of catalysis activity, preferably 2 or 4.
R in formula (1)1Be hydrogen atom, carbon number be 1～5 straight chained alkyl or branched alkyl, by formula (2) The group represented or the group represented by formula (3).
[changing 4]
R in formula (2)～(3)2And R4Separately represent hydrogen atom or the alkyl that carbon number is 1～3, R3 Represent the alkyl or phenyl that hydrogen atom, carbon number are 1～16, R2And R3Can be mutually bonded and form carbon atom Number is the ring of 5～8, R5And R6Separately represent straight chained alkyl or branched alkyl that carbon number is 1～5.
As R1, from the viewpoint of the not stripping property of two ring types amidine salt (C), preferably make owing to there is hydroxyl (C) group represented by formula (2) of polyurethane resin it is incorporated into, it is further preferred that 2-hydroxyethyl, 2-hydroxyl Propyl group and 2-hydroxyl-1-Methylethyl.
X-in formula (1) be select free carbon number be 1～18 representative examples of saturated aliphatic carboxylic, carbon number be 3～ The fragrance that aromatic carboxylic acid that the unsaturated aliphatic carboxylic acid of 18, carbon number are 7～9, carbon number are 6～8 At least one acid in the group of race's sulfonic acid and aminoacid that carbon number is 2～11 composition remove matter from carboxyl or sulfo group The anion of son and/or remove the anion of proton from the hydroxyl of the phenol that carbon number is 6～8.
Two ring types amidine salt (C) represented by formula (1) such as can be by making the two ring type amidine chemical combination represented by formula (4) Thing and the unsaturated aliphatic that the representative examples of saturated aliphatic carboxylic selecting free carbon number to be 1～18, carbon number are 3～18 Carboxylic acid, carbon number be 7～9 aromatic carboxylic acid, carbon number be 6～8 aromatic sulphonic acid and carbon number be The phenol that at least one is sour and/or carbon number is 6～8 in the group of the aminoacid composition of 2～11 reacts and obtains.
[changing 5]
N and R in formula (4)1Identical with formula (1).
As the concrete example of the above-mentioned two ring type amidine compounds represented by formula (4), can enumerate such as 1,5-diaza is double Ring [4.3.0] nonyl-5-alkene (hereafter abbreviated as DBN), 1,5-diazabicyclo [4.4.0]-decyl-5-alkene (hereafter abbreviated as DBD), 1,8-diazabicyclo [5.4.0]-ten one-7-alkene (hereafter abbreviated as DBU), 7-methyl isophthalic acid, 5-diazabicyclo [4.3.0]-nonyl-5-alkene, 7-ethyl-1,5-diazabicyclo [4.3.0]-nonyl-5-alkene, 7-propyl group-1,5-diazabicyclo [4.3.0]- Nonyl-5-alkene, 7-butyl-1,5-diazabicyclo [4.3.0]-nonyl-5-alkene, 7-amyl group-1,5-diazabicyclo [4.3.0]-nonyl-5- Alkene, 7-isopropyl-1,5-diazabicyclo [4.3.0]-nonyl-5-alkene, 7-isobutyl group-1,5-diazabicyclo [4.3.0]-nonyl-5- Alkene, 7-dimethylamino-1,5-diazabicyclo [4.3.0]-nonyl-5-alkene, 7-dibutylamino-1,5-diazabicyclo [4.3.0]-nonyl -5-alkene, 7-methyl isophthalic acid, 5-diazabicyclo [4.4.0]-decyl-5-alkene, 7-ethyl-1,5-diazabicyclo [4.4.0]-decyl-5-alkene, 7-propyl group-1,5-diazabicyclo [4.4.0]-decyl-5-alkene, 7-butyl-1,5-diazabicyclo [4.4.0]-decyl-5-alkene, 7-amyl group -1,5-diazabicyclo [4.4.0]-decyl-5-alkene, 7-isopropyl-1,5-diazabicyclo [4.4.0]-decyl-5-alkene, 7-isobutyl group -1,5-diazabicyclo [4.4.0]-decyl-5-alkene, 7-dimethylamino-1,5-diazabicyclo [4.4.0]-decyl-5-alkene, 7-dibutyl amine Base-1,5-diazabicyclo [4.4.0]-decyl-5-alkene, 6-methyl isophthalic acid, 8-diazabicyclo [5.4.0]-ten one-7-alkene, 6-ethyl -1,8-diazabicyclo [5.4.0]-ten one-7-alkene, 6-propyl group-1,8-diazabicyclo [5.4.0]-ten one-7-alkene, 6-butyl -1,8-diazabicyclo [5.4.0]-ten one-7-alkene, 6-amyl group-1,8-diazabicyclo [5.4.0]-ten one-7-alkene, 6-isopropyl -1,8-diazabicyclo [5.4.0]-ten one-7-alkene, 6-isobutyl group-1,8-diazabicyclo [5.4.0]-ten one-7-alkene, 6-diformazan Amino-1,8-diazabicyclo [5.4.0]-ten one-7-alkene, 6-dibutylamino-1,8-diazabicyclo [5.4.0]-ten one-7- Alkene, 7-methylol-1,5-diazabicyclo [4.3.0]-nonyl-5-alkene, 7-(2-hydroxyethyl)-1,5-diazabicyclo [4.3.0]- Nonyl-5-alkene (hereafter abbreviated as HE-DBN), 7-(2-hydroxypropyl)-1,5-diazabicyclo [4.3.0]-nonyl-5-alkene are (hereafter In be abbreviated as HP-DBN), 7-(2-hydroxybutyl)-1,5-diazabicyclo [4.3.0]-nonyl-5-alkene, 7-(2-hydroxyl penta Base)-1,5-diazabicyclo [4.3.0]-nonyl-5-alkene, 7-methylol-1,5-diazabicyclo [4.4.0]-decyl-5-alkene, 7-(2-hydroxyl Base ethyl)-1,5-diazabicyclo [4.4.0]-decyl-5-alkene, 7-(2-hydroxypropyl)-1,5-diazabicyclo [4.4.0]-decyl-5- Alkene, 7-(2-hydroxybutyl)-1,5-diazabicyclo [4.4.0]-decyl-5-alkene, 7-(2-Hydroxy pentyl)-1,5-diazabicyclo [4.4.0]-decyl-5-alkene, 6-methylol-1,8-diazabicyclo [5.4.0]-ten one-7-alkene, 6-(2-hydroxyethyl)-1,8-phenodiazine Miscellaneous dicyclo [5.4.0]-ten one-7-alkene (hereafter abbreviated as HE-DBU), 6-(2-hydroxypropyl)-1,8-diazabicyclo [5.4.0]-ten one-7-alkene (hereafter abbreviated as HP-DBU), 6-(2-hydroxybutyl)-1,8-diazabicyclo [5.4.0]-ten one -7-alkene and 6-(2-Hydroxy pentyl)-1,8-diazabicyclo [5.4.0]-ten one-7-alkene etc..
Among these, from the viewpoint of the flatness of the section of curable, injection property and membrane module, preferably DBN, DBD, DBU, HE-DBN, HP-DBN, HE-DBU and HP-DBU, never enter from the viewpoint of stripping property One step preferably can be incorporated into HE-DBN, HP-DBN, HE-DBU with hydroxyl of polyurethane resin when solidification And HP-DBU.
Two ring type amidine compounds both can be used alone one, it is also possible to share two or more.
As the representative examples of saturated aliphatic carboxylic that carbon number is 1～18, can enumerate formic acid, acetic acid, propanoic acid, butanoic acid, Valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, undecanoic acid, lauric acid/dodecanoic acid, tridecanoic acid, tetradecylic acid, pentadecanoic acid, Palmic acid, heptadecanoic acid, stearic acid and octanoic acid etc. do not have the carboxylic acid of hydroxyl；And glycolic, lactic acid, glyceric acid, hydroxyl The aliphatic hydroxyl acid such as base butanoic acid, malic acid, tartaric acid, citric acid；Etc..
As the unsaturated aliphatic carboxylic acid that carbon number is 3～18, can enumerate butenoic acid, Semen Myristicae oleic acid, ten Six carbon enoic acids (Sapienic acid), oleic acid, linoleic acid, linolenic acid, Pinolenic acid (Pinolenic acid), eleostearic acid (Eleostearic acid) and parinaric acid (Stearidonic acid) etc. do not have the unsaturated aliphatic carboxylic acid of hydroxyl； And the unsaturated aliphatic hydroxy acid such as shikimic acid and castor oil acid；Etc..
As the aromatic carboxylic acid that carbon number is 7～9, benzoic acid, phthalic acid, benzene-1,2,3-tricarboxylic acid can be enumerated With the aromatic carboxylic acid that trimellitic acid etc. does not has hydroxyl；And it is salicylic acid, cresotic acid (Cresotinic acid), former The aromatic hydroxyl acid such as catechuic acid, vanillic acid and syringic acid；Etc..
As the aromatic sulphonic acid that carbon number is 6～8, benzenesulfonic acid, p-methyl benzenesulfonic acid and to ethyl can be enumerated Benzenesulfonic acid etc..
As the aminoacid that carbon number is 2～11, can enumerate glycine, alanine, valine, leucine and Isoleucine etc..
As the phenol that carbon number is 6～8, phenol, cresol, xylenols and ethyl-phenol etc. can be enumerated.
Among these carboxylic acids, from the viewpoint of hypotoxicity, preferably carbon number is the representative examples of saturated aliphatic of 1～18 Carboxylic acid and the unsaturated aliphatic carboxylic acid that carbon number is 3～18, never from the viewpoint of stripping property, preferably by The representative examples of saturated aliphatic hydroxyl carboxylic that carbon number is 1～18 of polyurethane resin can be incorporated in having hydroxyl or amino Acid, carbon number be 3～18 unsaturated aliphatic hydroxy carboxylic acid, carbon number be 7～9 aromatic hydroxyl carboxylic Acid and carbon number are the aminoacid of 2～11.
Unsaturated aliphatic carboxylic acid that representative examples of saturated aliphatic carboxylic that carbon number is 1～18, carbon number are 3～18, Aromatic sulphonic acid, carbon number that aromatic carboxylic acid that carbon number is 7～9, carbon number are 6～8 are 2～11 Aminoacid and the phenol that carbon number is 6～8 both can use independent a kind, it is also possible to share two or more.As Share in them two or more and preferably Castor Oil Fatty Acid.
In the present invention, formula (4) the two ring type amidine compounds represented and select free carbon number be 1～18 saturated The aromatic series carboxylic that unsaturated aliphatic carboxylic acid that aliphatic carboxylic acid, carbon number are 3～18, carbon number are 7～9 Acid, carbon number be 6～8 aromatic sulphonic acid, carbon number be 2～11 aminoacid and carbon number be 6～8 Phenol composition group at least one acid and/or the mixed proportion of phenol be important, relative according to above-mentioned acid and/or phenol Molar ratio in two ring type amidine compounds preferably reaches 0.8～1.2, further preferably reach the scope of 0.9～1.1 Mode regulates mixed proportion.When molar ratio is less than 0.8, acid or the ratio of phenol extremely low time, due to balance anion Ratio reduce, increase, thus by alcohol and organic multiple isocyanate with the two ring type amidine compounds that free state exists Mixed working life, (pot-life) likely shortened.When molar ratio is more than 1.2, acid or the ratio of phenol very big time, Curing rate is slack-off, and productivity ratio is likely to decrease.
Two ring types amidine salt (C) can be added on the host containing organic multiple isocyanate composition (A) or become containing polyhydric alcohol Divide in any one in the firming agent of (B) or be added in both.Furthermore it is possible to as being different from organic polyisocyanic acid Ester composition (A) and the 3rd composition of polyol component (B) and use.
On the basis of the gross weight of the organic multiple isocyanate composition (A) used and polyol component (B), two ring type amidines The usage amount of salt (C) is preferably 0.0001～1.0 weight %, more preferably 0.001～0.2 weight %, the most excellent Elect 0.01～0.1 weight % as.Two ring types amidine salt (C) both can use independent a kind, it is also possible to share two or more.
Organic multiple isocyanate composition (A) in the present invention is not particularly limited, can by 1 molecule has 2 with The organic multiple isocyanate (a1) of upper NCO or the reaction by this organic multiple isocyanate with polyhydric alcohol obtain NCO end polyurethane prepolymer (a2) in any one constitute, or constituted by share both.Organic Polyisocyanate component (A) both can use independent a kind, it is also possible to share two or more.
As organic multiple isocyanate (a1), such as carbon number can be enumerated and (do not include that the carbon in NCO is former Son, lower with) aliphatic polyisocyante of 2～18；Carbon number is the ester ring type polyisocyanates of 4～15；Carbon is former Subnumber is the aromatic polyisocyanate of 6～20；Carbon number is the aromatic-aliphatic polyisocyanates of 8～15；Right A part for the NCO of these polyisocyanates carries out isocyanurate-modified, biuret modified, allophanic acid Ester modified, urea diketone modification, uretonimine-modified, carbodiimide modified, oxazolidone are modified, amide modifications or acyl Imine modified compound；And the mixture of above-mentioned substance.
As aliphatic polyisocyante, can enumerate such as, diisocyanate [ethylidene diisocyanate, four sub- Methyl diisocyanate, hexamethylene diisocyanate, ten dimethylene diisocyanates, 2,2,4-trimethyl six are sub- Methyl diisocyanate, 2,6-bis-isocyanate group methyl caproate, fumaric acid two (2-isocyanatoethyl) ester and carbonic acid Two (2-isocyanatoethyl) ester etc.] and triisocyanate ester [1,6,11-hendecane triisocyanate and 2-Carbimide. Base ethyl 2,6-bis-isocyanate group alkyl caproate etc.].
As ester ring type polyisocyanates, such as diisocyanate [isophorone diisocyanate, bicyclo-can be enumerated Hexyl methane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate and hexamethylene 4-alkene-1,2- Dicarboxylic acids two (2-bis-isocyanatoethyl) ester etc.].
As aromatic polyisocyanate, can enumerate such as diisocyanate [2,4-or 2,6-toluene di-isocyanate(TDI), 4,4 '-, 2,4 '-or 2,2 '-methyl diphenylene diisocyanate (hereinafter methyl diphenylene diisocyanate is abbreviated as MDI) and naphthalene diisocyanate etc.] or there is the aromatic polyisocyanate of more than 3 NCOs [have 3 The poly methylene poly phenyl poly isocyanate etc. of individual above phenyl ring].
As aromatic-aliphatic polyisocyanates, can enumerate such as diisocyanate [XDI, α, α, α, ' α '-tetramethylxylylene diisocyanate and two (2-isocyanatoethyl) benzene etc.].
Within these organic multiple isocyanates (a1), from the viewpoint of reactivity, preferably aromatic series polyisocyanic acid Ester and modified body, further preferably 4,4 '-, 2,4 '-or 2,2 '-MDI and modified body thereof.
As the polyhydric alcohol used in NCO end polyurethane prepolymer (a2) in the present invention, number can be enumerated Low molecular polylol less than 300 of average molecular weight (hereafter abbreviated as Mn) or formula weight and Mn are more than 300 Macromolecule polyol.
Mn in the present invention passes through gel infiltration color with polypropylene glycol for standard substance as solvent by using THF Spectrum is measured.Can set as follows: sample concentration is fixed mutually for connecting TSKgel Super as 0.25 weight %, post Each 1 of H2000, TSKgel Super H3000, TSKgel Super H4000 (being Tosoh company to manufacture) form, Column temperature is 40 DEG C.
The low molecular polylol less than 300 as Mn or formula weight, can enumerate carbon number is more than 2～24 Unit alcohol (such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-HD, neopentyl glycol, glycerol, Trimethylolpropane, hexanetriol, tetramethylolmethane, Sorbitol, sucrose, hydrogenated bisphenol A)；And it is many with these 1 kind of polyhydric alcohol in unit's alcohol or epoxyalkane that mixture of more than two kinds is initiation material (hereafter abbreviated as AO) [carbon number is 2～12, such as oxirane (hereafter abbreviated as EO), expoxy propane (hereafter abbreviated as PO), epoxy butane and mixture of more than two kinds in them] Mn or the formula weight addition less than 300 in addition product Thing；Etc..Low molecular polylol both can use independent a kind, it is also possible to share two or more.
From the viewpoint of the mechanical performance of obtained polyurethane resin, Mn or formula weight are less than low point of 300 The hydroxyl value of sub-polyhydric alcohol is preferably 380～2000mgKOH/g, more preferably 400～1500mgKOH/g.
From the viewpoint of the mechanical performance of obtained polyurethane resin, Mn or formula weight are less than low point of 300 The functional group number of sub-polyhydric alcohol is preferably 2～8, more preferably 2～4.
It is the macromolecule polyol of more than 300 as Mn, polyether polyol and PEPA etc. can be enumerated.
It is the polyether polyol of more than 300 as Mn, can enumerate and be less than 300 with above-mentioned Mn or formula weight The AO addition product that one kind or two or more mixture is initial feed of low molecular polylol, specifically can enumerate poly- Ethylene glycol, polypropylene glycol (hereafter abbreviated as PPG) and polytetramethylene glycol etc..
It is the PEPA of more than 300 as Mn, Castor Oil Fatty Acid ester polyol (such as Semen Ricini can be enumerated Oleum Ricini oily, partially dehydrated and by making above-mentioned low molecular polylol or polyether polyol hand over Oleum Ricini generation ester Change reaction or with Castor Oil Fatty Acid generation esterification and the Castor Oil Fatty Acid ester that obtains)；By polynary (n=2～ 3 or more) carboxylic acid [aliphatic is saturated or unsaturated polybasic carboxylic acid (carbon number is 2～40, such as oxalic acid, adipic acid, Azelaic Acid, lauric acid/dodecanoic acid, maleic acid, fumaric acid, itaconic acid and dimerization linoleic acid), containing aromatic ring polybasic carboxylic acid, (carbon is former Subnumber is 8～15, such as phthalic acid, M-phthalic acid, p-phthalic acid and NDA) and containing alicyclic ring Polybasic carboxylic acid (carbon number is 7～15, such as 1,3-pentanedicarboxylic acid and Isosorbide-5-Nitrae-hexane dicarboxylic acid) etc.] and polyhydric alcohol (on The low molecular polylol stated and/or polyether polyol) straight-chain that formed or branched PEPA；Many with polylactone Unit alcohol [the one kind or two or more mixture of the most above-mentioned low molecular polylol (2～3 yuan) is initiator so that it is with (have Substituent group) caprolactone (carbon number is 6～10, such as 6-caprolactone, Alpha-Methyl-6-caprolactone, ε-methyl-ε-oneself Lactone) send out in the presence of catalyst (organo-metallic compound, metal chelate compound, fatty acid metal acylate etc.) The polyhydric alcohol (such as polycaprolactone polyol) of raw addition polymerization]；Make AO (EO and PO etc.) and at end, there is carboxyl And/or the polyester generation addition polymerization of hydroxyl and the polyester ether polylol that obtains；Polycarbonate polyol；Etc..
Within above-mentioned polyhydric alcohol, from the viewpoint of the low viscosity of (a2), preferably polyether polyol and ricinolein Fat acid esters polyhydric alcohol, from the viewpoint of the transparency, it is further preferred that polyether polyol, and from mechanical performance Viewpoint is set out, it is further preferred that Oleum Ricini, partially dehydrated Oleum Ricini and Castor Oil Fatty Acid PPG ester.
Macromolecule polyol both can use independent a kind, it is also possible to share two or more.
From the viewpoint of the mechanical performance of obtained polyurethane resin, Mn is the macromolecule polyol of more than 300 Mn be preferably 300～5,000, more preferably 500～3,000.
From the viewpoint of the mechanical performance of obtained polyurethane resin, Mn is the macromolecule polyol of more than 300 Hydroxyl value be preferably 20～350mgKOH/g, more preferably 40～300mgKOH/g.
From the viewpoint of the mechanical performance of obtained polyurethane resin, Mn is the macromolecule polyol of more than 300 Functional group number be preferably 2～8, more preferably 2～4.
Manufacture NCO end polyurethane prepolymer time, generally according to equivalent proportion be (NCO/OH)=1.1/1～ The mode of 50/1 uses organic multiple isocyanate and polyhydric alcohol to manufacture.Equivalent proportion is the biggest, then viscosity is the lowest, but solid Contraction during change is the biggest, thus equivalent proportion is preferably 1.5/1～30/1, more preferably 2/1～10/1.Need Bright, in the case of equivalent proportion is big, organic multiple isocyanate (a1) and NCO end polyurethane can be obtained The mixture of prepolymer (a2).
As organic multiple isocyanate composition (A), can only use organic multiple isocyanate (a1) or only use Carbimide. Ester group end polyurethane prepolymer (a2), but from the viewpoint of the hardness of low viscosity and polyurethane resin, preferably close With (a1) and (a2).When share, (a2) content in organic multiple isocyanate composition (A) is preferably more than 20 weight % And less than 100 weight %, more preferably 30～90 weight %.
Manufacture method as (a2) is not particularly limited, and can enumerate and make organic multiple isocyanate (a1) and polyhydric alcohol exist The known method reacted under blanket of nitrogen.
Reaction temperature in prepolymerization is usually 30～140 DEG C, from reactive viewpoint and the sight preventing side reaction Point sets out, preferably 50～120 DEG C.It addition, reaction is generally carried out under condition of no solvent, but can also basis Need at solvent [the such as aromatic hydrocarbon (toluene and dimethylbenzene etc.), ketone (methyl second not having reactivity with NCO Base ketone and methyl iso-butyl ketone (MIBK) etc.) and mixture of more than two kinds in them] in carry out, then remove these by distillation Solvent.
As the polyol component (B) in the present invention, can enumerate for above-mentioned NCO end polyurethane prepolymer The polyhydric alcohol of thing, amine polyol and mixture of more than two kinds etc. in them.
As above-mentioned amine polyol, (carbon number is alkylene polyol (n=2～6) amine can to enumerate " many (n=2～6) " AO addition product 2～20) [carbon number is more than 10 and Mn to be 2, less than 000, such as N, N, N ', N '-four (2- Hydroxypropyl) ethylenediamine, N, N, N ', N ", N "-five (2-hydroxypropyl) diethylenetriamines]；N, N-dialkyl group be (alkyl Carbon number is 1～3) the AO addition product of (many) alkylidenes (carbon number of alkylidene is 2～3) polyamine is (such as The PO addition product of N, N-dimethylated propyl diethylenetriamine)；AO addition product (the example of N-aminoalkyl (carbon number is 2～3) imidazoles Material as described in Japanese Unexamined Patent Publication 11-322881 publication)；Alkanolamine (carbon number is 4～12, such as two Ethanolamine, triethanolamine)；Deng.
As polyol component (B), from the viewpoint of low viscosity, preferably polyether polyol and Oleum Ricini fat Acid esters polyhydric alcohol, from the viewpoint of the transparency, it is further preferred that polyether polyol.It addition, from mechanical performance From the viewpoint of, preferably polyether polyol, Castor Oil Fatty Acid ester polyol and amine polyol, further preferably Be Oleum Ricini, partially dehydrated Oleum Ricini, Castor Oil Fatty Acid PPG ester and amine polyol.
By the organic multiple isocyanate composition (A) of the compositions constituting the present invention, polyol component (B) and two ring type amidine salt (C) when forming polyurethane resin, from reducing from the viewpoint of unreacted reactant, NCO/OH equivalent proportion be preferably 0.5/1～ 2.0/1, more preferably 0.7/1～1.5/1, particularly preferably 0.8/1～1.2/1.
The sealing material use polyurethane resin formative compositions of the membrane module of the present invention can be by distinguishing in use Gauge amount organic multiple isocyanate composition (A), polyol component (B) become with two ring type amidine salt (C) these three according to the rules Divide or two ring types amidine salt (C) are pre-mixed in organic multiple isocyanate composition (A) and/or polyol component (B) Two kinds of compositions, then utilize static mixer or mechanical mixer etc. to mix, thus manufacture, The most substantially start simultaneously at reaction with mixing, solidification occurs thus forms the sealing material use of the membrane module of the present invention Polyurethane resin.Carry out above-mentioned mixing, the reaction time till mobility disappears is usually 3～60 minutes, complete All solidstate needs, room temperature (20～30 DEG C) ripening 12～240 hours, not observe the firmness change of polyurethane resin Moment as being fully cured.It should be noted that polyurethane resin is not necessarily required to be fully cured in actual use, But preferably carry out ripening until hardness (Shore D: instantaneous value) reaches the scope of 20～100.It addition, also be able to lead to Cross raising curing temperature (such as 40～60 DEG C) and shorten the curing time.It should be noted that the hardness in the present invention depends on It is measured according to JISK7312, value when instantaneous value is just to be pressed onto on resin by scleroscopic pin.
By (A), (B) and (C) homoiothermic to 25 DEG C, then mixing, the viscosity of the mixed liquor after 30 seconds is (before injection Viscosity) from curable and injection property from the viewpoint of be preferably 50～10,000mPa s, more preferably 100～ 5,000mPa s, particularly preferably 200～2,000mPa s.It should be noted that (C) is blended in (A) in advance And/or time in (B), the preferred scope of the viscosity of the mixed liquor of (A) and (B) is the most as described above.
From the mechanical strength that should possess as encapsulant and the cut-out connecting bundles of doughnut with polyurethane resin From the viewpoint of property, in the presence of (C), make the hard of the polyurethane resin after the solidification that (A) and (B) react and obtain Degree (Shore D: instantaneous value) is preferably 20～100, more preferably 30～80.
The above-mentioned polyurethane resin formative compositions of the present invention is suitable as the encapsulant of membrane module, especially as with Hollow fiber type blood processor or hollow fiber type water purifier membrane module in artificial organ (artificial kidney etc.) etc. Encapsulant and useful.
The compositions of the present invention is applied to hollow fiber type blood processor membrane module encapsulant is illustrated below Time an example of specifically used method.First, respectively to being pre-mixed the polynary of ormal weight two ring type amidine salt (C) Alcohol composition (B) and organic multiple isocyanate composition (A) carry out vacuum deaerator (0.1mmHg × 2 hour).Gauge according to the rules Amount both liquid, is stirred mixing, then puts into the container being provided with doughnut by centrifugal casting, Doughnut is fixed in a reservoir.As centrifugal casting, it is possible to use such as Japanese Patent Publication 57-58963 Method described in publication.
As the raw material of doughnut, generally can use cellulose, acrylic acid series, polyvinyl alcohol, polyamide and Polysulfones etc..As said vesse, Merlon system, ABS system or polystyrene container etc. generally can be used. Biliquid mixed liquor loses flowability after self seeding plays 3～60 minutes, can take out membrane module from forming machine.Then Carrying out ripening room temperature (20～30 DEG C)～60 DEG C makes it solidify, and then utilizes the cut-out polyurethane trees such as rotary cutter Fat connects bundles of hollow-fibre membrane and obtains the peristome of hollow-fibre membrane end.Afterwards, autoclave is used to pass through The steam heating in 1 hour of 120 DEG C carries out sterilization treatment thus commercialization.Sterilization treatment can also by steam heat with Outer method (such as gamma-rays irradiation) is implemented.
Embodiment
Below, further illustrate the present invention by embodiment, but the invention is not restricted to this.Hereinafter, part represents weight Amount part, % represents weight %.
Trade name and composition thereof as raw material are as described below.
" HS2P-080 ": Castor Oil Fatty Acid ester polyol [the rich state liquefaction strain formula meeting of Castor Oil Fatty Acid and PPG Society's system, hydroxyl value=84mgKOH/g, Mn=1,340]
" Sunnix PP-1000 ": PPG [Sanyo Chemical Industries, Ltd.'s system, hydroxyl value=112mgKOH/g, Mn =1,000]
" HS2G-120 ": partially dehydrated Oleum Ricini [Feng Guo liquefaction Co., Ltd. system, hydroxyl value=120mgKOH/g, Mn=935]
" ELA-DR ": Oleum Ricini [Feng Guo liquefaction Co., Ltd. system, hydroxyl value=160mgKOH/g, Mn=945]
" CO-FA ": Castor Oil Fatty Acid [Feng Guo liquefaction Co., Ltd. system, hydroxyl value=163mgKOH/g, Mn= 315]
" MILLIONATE MT ": 4,4 '-MDI [Nippon Polyurethane Industry Co., Ltd.]
" Lupranate MM-103 ": modified 4,4 '-MDI [BASFINOAC polyurethane Co., Ltd. system, NCO Content is 29.5%, contains the 4 of about 25%, and the uretonimine of 4 '-MDI and/or carbodiimide modified body, containing about 75% 4,4 '-MDI]
" Lupranate MI ": mixture [the BASFINOAC polyurethane strain formula meeting of 2,4 '-MDI and 4,4 '-MDI Society's system, weight ratio is 50:50]
The caprylate [San-apro company system] of " U-CAT SA102 ": DBU
The caprylate [San-apro company system] of " U-CAT 1102 ": DBN
" dibutyl tin laurate ": [three are total to organic synthesis Co., Ltd. system]
" TEDA-L33 ": the 33% dipropylene glycol solution [Tosoh company system] of triethylenediamine
Manufacture example 1 [manufacture of polyether polyol]
To possessing agitating device, temperature control equipment, heat exchanger, raw material supply pipeline and row as condensing plant Input propylene glycol 150 parts and three (pentafluorophenyl group) borine 0.09 part in the stainless steel autoclave of gas pipeline, then, will Reaction temperature controls to be maintained at 70～80 DEG C, and 12 hours used times put into PO2 continuously to liquid phase simultaneously, 290 parts.At 70 DEG C Ripening 4 hours, then adds 200 parts of water, heats 1 hour at 130～140 DEG C.After heating in 1 hour, the used time 2 Water is fallen in hour air-distillation, is then followed by being passed through steam and pressure is maintained at 4～7kPa, the used time 3 Hour decompression distill remnants water and low-boiling compound.Afterwards, synthetic silicate [the consonance chemistry of 30 parts is added " KYOWAAD600 " of Industrial Co., Ltd] and 40 parts of water, process 3 hours at 60 DEG C, take out from autoclave After, utilize the filter of 1 micron to filter, be then dehydrated, obtained polyether polyol.Polyether polyol Hydroxyl value be 112mgKOH/g, viscosity be 150mPa s/25 DEG C.
Manufacture example 2 [manufacture of organic multiple isocyanate composition (A-1)]
Put in the reaction vessel possessing blender, thermometer and nitrogen ingress pipe " HS2P-080 " 29 parts and " MILLIONATE MT " 16 parts, stirs under nitrogen flowing, is simultaneously heated to 70～80 DEG C, reacts 4 hours, Obtain terminal isocyanate group polyurethane prepolymer.After reaction, add " Lupranate MM-103 " 34 parts and " Lupranate MI " 21 parts, stirs uniformly mixing in 30 minutes, has obtained organic multiple isocyanate composition (A-1).(A-1) NCO content be 20.6%, viscosity be 400mPa s/25 DEG C.
Manufacture example 3 [manufacture of organic multiple isocyanate composition (A-2)]
In the reaction vessel possessing blender, thermometer and nitrogen ingress pipe put into " Sunnix PP-1000 " 26 parts, " MILLIONATEMT " 15 parts and " Lupranate MI " 22 parts, stirs under nitrogen flowing, be simultaneously heated to 70～ 80 DEG C, react 4 hours, obtained terminal isocyanate group polyurethane prepolymer.After reaction, add " Lupranate MM-103 " 37 parts, stir uniformly mixing in 30 minutes, obtain organic multiple isocyanate composition (A-2).(A-2) NCO content is 21.2%, viscosity is 350mPa s/25 DEG C.
Manufacture example 4 [manufacture of polyol component (B-1)]
In the reaction vessel possessing blender, thermometer and nitrogen ingress pipe put into " HS2G-120 " 55 parts, " ELA-DR " 20 parts and N, N, N ', N '-four (2-hydroxypropyl) ethylenediamine 25 parts, nitrogen flows down 40～50 DEG C of stirrings Mix 1 hour, obtained polyhydric alcohol (B-1).(B-1) hydroxyl value is 287mgKOH/g, viscosity is 1,000mPa s/25℃。
Manufacture example 5 [manufacture of polyol component (B-2)]
The polyether polyol 75 parts manufacturing example 1 is become " HS2G-120 " 55 parts and " ELA-DR " 20 parts, except this with Polyol component (B-2) has been obtained outward in the same manner as manufacturing example 3.(B-2) hydroxyl value is 274mgKOH/g, viscosity is 430mPa·s/25℃。
Manufacture example 6 [manufactures of two ring types amidine salt (DBU-C)]
Input " DBU " 34 parts in the reaction vessel possessing blender, thermometer and nitrogen ingress pipe, under nitrogen flowing, Add " CO-FA " 66 parts under room temperature condition, stir 1 hour, obtained being made up of DBU and Castor Oil Fatty Acid Two ring types amidine salt (DBU-C).
Manufacture example 7 [manufactures of two ring types amidine salt (DBU-G)]
Input " DBU " 67 parts in the reaction vessel possessing blender, thermometer and nitrogen ingress pipe, under nitrogen flowing, Add glycolic 33 parts under room temperature condition, stir 1 hour, obtained the two ring type amidines being made up of DBU and glycolic Salt (DBU-G).
Manufacture example 8 [manufactures of two ring type amidine compounds (HE-DBU)]
" DBU " 152 parts and oxolane 900 parts is put into, dry in the reaction vessel possessing blender and thermometer Ice/acetone bath is cooled to-20 DEG C.Liquid temperature less than-10 DEG C with within 3 hours, drip wherein n-BuLi 14.7% oneself Alkane solution 437 parts (pure component is 64 parts).Afterwards, after this temperature stirs 1 hour, in the temperature less than 0 DEG C 3 hours used times were passed through EO47.9 part.Further, stir 1 hour in this temperature, and then stir 1 hour at 20 DEG C, Then add 18.9 parts of water, be stirred at room temperature 1 hour, be filtered to remove the inorganic matter of precipitation.At normal pressure from filtrate Remove solvent, the most under reduced pressure distill unreacted DBU, obtained HE-DBU.
Manufacture example 9 [manufactures of two ring types amidine salt (HE-DBU-C)]
In the reaction vessel possessing blender, thermometer and nitrogen ingress pipe, input obtains in manufacturing example 8 " HE-DBU " 36 parts, under nitrogen flowing, adds " CO-FA " 64 parts under conditions of room temperature, stirs 1 hour, obtain Two ring types amidine salt (HE-DBU-C) that are made up of HE-DBU and Castor Oil Fatty Acid.
Manufacture example 10 [preparations of two ring types amidine salt (DBN-H)]
Input " DBN " 54 parts in the reaction vessel possessing blender, thermometer and nitrogen ingress pipe, under nitrogen flowing, Add 2-hydroxybutyric acid 46 parts under conditions of room temperature, stir 1 hour, obtained by DBN and 2-hydroxybutyric acid structure Two ring types amidine salt (DBN-H) become.
Embodiment 1～12 and comparative example 1～4
The isocyanate prepolymer composition (A-1) that obtains will be manufactured in example 2 as embodiment 1～10 and the host of comparative example 1～4, The isocyanate prepolymer composition (A-2) that the obtains host as embodiment 11～12 will be manufactured in example 3.It addition, according to table 1 Formula, first put in the reaction vessel possessing blender, thermometer and nitrogen ingress pipe two ring types amidine salt (C) or As comparing with " dibutyl tin laurate " or " TEDA-L33 " of catalyst, add polyol component (B) and exist 40～50 DEG C of stirring mixing 1 hour, make embodiment 1～12 and the firming agent of comparative example 1～3.Need explanation It is that the firming agent of comparative example 4 is only polyhydric alcohol (B-1).
By the homoiothermic respectively of host and firming agent to after 25 DEG C, utilize the blender with rotary spiral blade, by table 1 The host of shown number (being the number described in aggregate value hurdle about firming agent) and firming agent stirring mix 30 seconds Rear use, measure in accordance with the following methods or evaluate mixed liquor injection before viscosity, working life, the hardness of solidification resin, The flatness of the section in stannum stripping quantity, potassium permanganate consumption, resin outward appearance, resin turbidity, membrane module, its Result is listed in table 2.
＜ evaluation test method ＞
(1) viscosity before the injection of mixed liquor
Rotary viscosimeter (Brookfield viscometer) is utilized to measure the viscosity (mPa s) after mixing terminates 30 seconds.
(2) working life of mixed liquor
Mensuration mixing terminates the viscosity of rear mixed liquor and reaches the time till 10Pa s.
(3) resin hardness
After mixing terminates, it is centrifuged deaeration, the cup of polypropylene weighs mixed liquor 30 parts, 25 DEG C of ripenings 30 minutes, then take out from cup, hardness is measured.Stand in the room of homoiothermic to 25 DEG C further, Measure the hardness [Shore D: instantaneous value { Shore D hardness meter, height after 3 hours, 24 hours and 72 hours stand Molecule gauge Co., Ltd. system }].
(4) stannum stripping quantity
After mixing terminates, it is centrifuged deaeration, according to resin in the box of the polystyrene of about 8cm × about 11cm Thickness reaches the mode of about 2mm and weighs mixed liquor, 40 DEG C of 1 weeks of ripening, then will solidification after resin from The box of polystyrene takes out, and is cut into the square size of 1cm.Sanction is taken in the conical flask that volume is 100mL Resin 10g after cutting and ethanol 50mL also seals.With agitator with the temperature oscillation 1 hour of 25 DEG C, so After take supernatant, utilize ICP-AES (ICP-AES) method measure tin concentration.
(5) potassium permanganate consumption
After mixing terminates, it is centrifuged deaeration, according to resin in the box of the polystyrene of about 8cm × about 11cm Thickness reaches the mode of about 2mm and weighs mixed liquor, 40 DEG C of 1 weeks of ripening, then will solidification after resin from The box of polystyrene takes out, cuts into the square size of 1cm.The beaker of volume 200mL takes after cutting The ion exchange water of resin 15g and 150ml, after standing 1 hour at 70 DEG C, cool down, resin will be removed After extract be transferred in other container, as experimental liquid.Possessing the triangle that volume is 100mL of cooling tube Flask takes experimental liquid 10mL, adds potassium permanganate solution 20mL and 10% weight percent sulfuric acid of 0.002mol/L 1.0mL, then seethes with excitement 3 minutes in the oil bath of 140 DEG C, adds potassium iodide 0.1g and carry out close after being cooled to room temperature Envelope, carries out vibration mixing, then places 10 minutes, then carries out dripping with the hypo solution of 0.01mol/L Fixed.As blank assay, change experimental liquid 10mL into ion exchange water 10mL, enter the most as described above Row test.
It should be noted that potassium permanganate consumption is the most, leachable is the most.
(6) resin outward appearance and resin turbidity (mist degree)
After mixing terminates, it is centrifuged deaeration, according to resin in the box of the polystyrene of about 8cm × about 11cm Thickness reaches the mode of about 1mm and weighs mixed liquor, after 25 DEG C of ripenings 72 hours, will solidify resin from polyphenyl second The box of alkene takes out, uses visual observations outward appearance, be evaluated according to following evaluation criterion, use haze meter further [BYKgardner society system (HAZE-GARDDUAL)] measures turbidity.
Evaluation criterion ＞ of ＜ outward appearance
Transparent be designated as zero, nebulousurine be designated as ×.
(7) flatness of the section in membrane module
To can two ends load onto the internal diameter of injection molding cover be 40mm, the Merlon rounding of a length of 300mm Filling polysulfones doughnut arranged in parallel (length 320mm, external diameter 280 μm, thickness 40 μm) 10,000 in cylinder container Root, loads onto injection molding cover at two ends.This membrane module is placed in centrifugal shaper, inject mixed liquor 60g carry out from Heart molding.From centrifugal forming start products formed is taken out from centrifugal shaper after 20 minutes, unload two ends Injection molding cover.The ripening of 30 minutes is carried out, then with the arranged direction of doughnut vertically to polyurethane at 25 DEG C Doughnut is connected bundles of part by resin to cut off.After cut-out, by membrane module in the room of homoiothermic to 25 DEG C In middle 1 week of standing, observe section with microscope [Olympus Co., Ltd's system " DSX500 ": multiplying power 100 times] Apparent condition.
The metewand ＞ of ＜ section
By unconfirmed being designated as zero to concavo-convex and smooth situation, will confirm that concavo-convex rather than smooth situation and be designated as ×.
Table 1
Table 2
Industrial applicibility
The reactive excellence of the sealing material use polyurethane resin formative compositions of the membrane module of the present invention, in the short time Embody the hardness that can well cut off, long-time its hardness of maintenance, viscosity is low and notes excellent plasticity, and by this combination The turbidity of polyurethane resin that thing is formed is low and transparent excellence, when the encapsulant of membrane module, and section flat Slip is excellent, and leachable is few and excellent in safety, thus at extensive use (blood processor and the water purification of membrane module Device etc.), very useful in the purposes such as hollow fiber type blood processor of especially artificial organ.

Claims (8)

1. a sealing material use polyurethane resin formative compositions for membrane module, described polyurethane resin formative Compositions is made up of with the firming agent containing polyol component (B) the host containing organic multiple isocyanate composition (A), its Being characterised by, described host and/or described firming agent contain two ring types amidine salt (C) represented by formula (1),
[changing 1]
In formula, n is the integer of 2～6, R1Be hydrogen atom, carbon number be 1～5 straight chained alkyl or branched alkyl, The group represented by formula (2) or the group represented by formula (3), X-Be select free carbon number be 1～18 saturated Aliphatic hydroxyl carboxylic acid, carbon number be 3～18 unsaturated aliphatic hydroxy carboxylic acid, carbon number be 7～9 The anion removing proton from carboxyl of at least one acid in the group of aromatic hydroxy-carboxylic composition,
[changing 2]
In formula, R2And R4Separately represent hydrogen atom or the alkyl that carbon number is 1～3, R3Represent that hydrogen is former Son, carbon number are the alkyl or phenyl of 1～16, R2With R3It is mutually bonded and forms the ring that carbon number is 5～8, Or, R2And R3It is not mutually bonded, R5And R6Separately represent the straight chained alkyl that carbon number is 1～5 Or branched alkyl.
2. a sealing material use polyurethane resin formative compositions for membrane module, it is by by organic multiple isocyanate The host that composition (A) is constituted, the firming agent being made up of polyol component (B) and two ring types amidine salt (C) represented by formula (1) Constitute,
[changing 3]
In formula, n is the integer of 2～6, R1Be hydrogen atom, carbon number be 1～5 straight chained alkyl or branched alkyl, The group represented by formula (2) or the group represented by formula (3), X-Be select free carbon number be 1～18 saturated Aliphatic hydroxyl carboxylic acid, carbon number be 3～18 unsaturated aliphatic hydroxy carboxylic acid, carbon number be 7～9 The anion removing proton from carboxyl of at least one acid in the group of aromatic hydroxy-carboxylic composition,
[changing 4]
In formula, R2And R4Separately represent hydrogen atom or the alkyl that carbon number is 1～3, R3Represent that hydrogen is former Son, carbon number are the alkyl or phenyl of 1～16, R2And R3It is mutually bonded and forms the ring that carbon number is 5～8, Or, R2And R3It is not mutually bonded, R5And R6Separately represent the straight chained alkyl that carbon number is 1～5 Or branched alkyl.
3. compositions as claimed in claim 1 or 2, wherein, the n in described formula (1) is 2 or 4.
4. compositions as claimed in claim 1 or 2, wherein, the R in described formula (1)1For hydrogen atom, 2-hydroxyl Base ethyl, 2-hydroxypropyl or 2-hydroxyl-1-Methylethyl.
5. compositions as claimed in claim 1 or 2, wherein, the cation constituting described two ring types amidine salt (C) is To choosing free 1,5-diazabicyclo [4.3.0]-nonyl-5-alkene, 1,5-diazabicyclo [4.4.0]-decyl-5-alkene, 1,8-diaza Dicyclo [5.4.0]-ten one-7-alkene, 7-(2-ethoxy)-1,5-diazabicyclo [4.3.0]-nonyl-5-alkene, 7-(2-hydroxyl third Base)-1,5-diazabicyclo [4.3.0]-nonyl-5-alkene, 6-(2-hydroxyethyl)-1,8-diazabicyclo [5.4.0]-ten one-7-alkene and At least one two ring type amidine chemical combination in the group that 6-(2-hydroxypropyl)-1,8-diazabicyclo [5.4.0]-ten one-7-alkene is constituted The cation of thing addition proton.
6. an encapsulant for membrane module, it uses the compositions according to any one of claim 1～5 to form.
7. a membrane module, it uses the encapsulant described in claim 6 to form.
8. hollow fiber type blood processor or a water purifier, it uses the membrane module described in claim 7 to form.
CN201380009231.2A 2012-03-29 2013-03-13 The sealing material use polyurethane resin formative compositions of membrane module Expired - Fee Related CN104114262B (en)

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