CN101885828B - Two-fluid polyurethane resin composition - Google Patents
Two-fluid polyurethane resin composition Download PDFInfo
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- CN101885828B CN101885828B CN2009101407086A CN200910140708A CN101885828B CN 101885828 B CN101885828 B CN 101885828B CN 2009101407086 A CN2009101407086 A CN 2009101407086A CN 200910140708 A CN200910140708 A CN 200910140708A CN 101885828 B CN101885828 B CN 101885828B
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- polyurethane resin
- resin composition
- hydroxyl value
- solidifying agent
- average hydroxyl
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 33
- 239000011342 resin composition Substances 0.000 title claims abstract description 31
- 239000012530 fluid Substances 0.000 title claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 70
- 239000000203 mixture Substances 0.000 claims abstract description 70
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 58
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 24
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- 239000012948 isocyanate Substances 0.000 claims abstract description 5
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 5
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 38
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 34
- 229920005862 polyol Polymers 0.000 claims description 32
- 150000003077 polyols Chemical class 0.000 claims description 27
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 23
- 235000011187 glycerol Nutrition 0.000 claims description 16
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 12
- 239000012510 hollow fiber Substances 0.000 claims description 12
- 239000003566 sealing material Substances 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 8
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 7
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 7
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 238000002156 mixing Methods 0.000 abstract description 13
- 229920001228 polyisocyanate Polymers 0.000 abstract description 8
- 125000002947 alkylene group Chemical group 0.000 abstract description 3
- 150000005846 sugar alcohols Polymers 0.000 abstract 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 229920001451 polypropylene glycol Polymers 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 150000001722 carbon compounds Chemical class 0.000 description 12
- -1 amine polyol Chemical class 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 229920006389 polyphenyl polymer Polymers 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 4
- 229910000071 diazene Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 241000345998 Calamus manan Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 235000012950 rattan cane Nutrition 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010729 system oil Substances 0.000 description 2
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a polyurethane resin composition, providing a polyurethane resin condensate which has excellent workability in early mixing stage, can be solidified in shorter time and reduces dissolution of an organic compound in water. The two-fluid polyurethane resin composition comprises an isocyanate-containing main agent (I) and a polyalcohol-containing curing agent (II), wherein the main agent (I) contains aromatic polyisocyanate (A) or urethane prepolymer which has an isocyanate group at the tail end; and the curing agent (II) contains caster oil (C), polypropylene glycol (D) with the molecular weight of between 100 and 300 and a polyalcohol mixture (E) which contains the following components with the average hydroxyl value of between 250 and 400mgKOH/g: caster oil (a), alkylene oxide affixture of sorbierite (b) with the average hydroxyl value of between 400 and 800mgKOH/g, and alkylene oxide affixture of glycerol (c) with the average hydroxyl value of between 400 and 800mgKOH/g.
Description
Technical field
The present invention relates to two-fluid polyurethane resin composition, said composition provides the solidfied material that operation is solidified well, in the short period of time and the stripping of carbon compound is inhibited; The composition and the solidfied material of the harness (end) that the invention still further relates to the encapsulant that is suitable for filter or be used for doughnut.
Background technology
The two-fluid polyurethane resin is widely used in various uses; When wherein being used for the sealing material of strainer or being used for the harness of tubular fibre; To need to shorten set time (hardness demonstration) in order boosting productivity,, to use amine polyol (amine polyol) etc. always as curing agent component.
For example disclose the tubular fibre that makes the reaction of polymeric polyisocyanate composition and solidifying agent and form in the patent documentation 1 with harness agent (end is cutd open), it is that compound more than 4 is the polyether glycol and the amine polyol of starting substance that wherein said solidifying agent contains with hydroxyl values such as poly-glycerol.
But if use the raw material of amine polyol as urethane resin, the carbon compound of stripping from resin is very many when then being immersed in the water, must after manufacturing, carefully clean.
Therefore, developing the polyurethane resin composition of not using above-mentioned amine polyol at present.For example disclose the sealing material that makes the reaction of polymeric polyisocyanate composition and solidifying agent and form in the patent documentation 2, wherein to contain the above nominal functional group number of 20 weight % be the polyether glycol more than 6 to this solidifying agent, and OH value is 370～680mgKOH/g.
But; In the compsn of patent documentation 2; Owing to cooperated the high polyvalent alcohol of hydroxyl value in a large number, therefore had following problem: from begin to be mixed into time till viscosity rises fast, large product before being filled into the end tackify just, thereby can't make etc.
In addition; Disclose the potting material that makes the host that is made up of carbamate prepolymer and solidifying agent reaction and form in the patent documentation 3, this solidifying agent is that high molecular weight polyols and the molecular weight of 50～200mgKOH/g is below 200 and two ends of hydrocarbon chain are that the glycol of hydroxyl constitutes by OH value.In addition, disclose in the patent documentation 4 and used 1, the 4-butyleneglycol is as solidifying agent.
But, above-mentioned 1, hydrocarbon chains such as 4-butyleneglycol two terminal for the glycol of hydroxyl have the crystallinity height, when particularly waiting coldcondition under preservation in the winter time, the easy problem of in solidifying agent, separating out etc. aspect the stability in storage.
In addition, cooperating hydrocarbon chain two end be the solidifying agent of the divalent alcohol of hydroxyl, though viscosity is low after just mixing, and tackify in the short period of time, thereby operation property is insufficient in loading levels such as large product product how.
Patent documentation 1: TOHKEMY 2000-128952 communique
Patent documentation 2: TOHKEMY 2002-128858 communique
Patent documentation 3: TOHKEMY 2001-300265 communique
Patent documentation 4: japanese kokai publication hei 7-53665 communique
Summary of the invention
The present invention provides a kind of polyurethane resin composition in order to address the above problem, and this resin combination provides the operation property at mixing initial stage to solidify and reduced the curable urethane resin thing of the stripping of carbon compound in water well, in the short period of time.
That is, the present invention relates to two-fluid polyurethane resin composition, said composition comprises: the solidifying agent (II) that contains the host (I) of isocyanate prepolymer composition and contain polyhydroxy reactant is characterized in that:
Host (I) contains
(I-1) aromatic poly-isocyanate (A) and/or
(I-2) making aromatic poly-isocyanate (A) and the end that Viscotrol C (B) reaction obtains is the carbamate prepolymer of NCO;
Solidifying agent (II) contains
(C) Viscotrol C,
(D) molecular weight be 100～300 W 166,
(E) the average hydroxyl value that comprises following (a)～(c) is the polyol blends of 250～400mgKOH/g:
(a) Viscotrol C,
(b) the average hydroxyl value be the sorbyl alcohol of 400～800mgKOH/g oxirane (alkylene oxide) affixture,
(c) the average hydroxyl value is the oxirane affixture of the glycerine of 400～800mgKOH/g,
Wherein the content of (C) is that the content of 30～90 weight %, (D) is that the content of 1～20 weight %, (E) is 1～60 weight %.
In the polyurethane resin composition of the present invention, be the oxirane affixture (F) of the glycerine of 50～200mgKOH/g, can further improve the intermiscibility of solidifying agent through making the average hydroxyl value that above-mentioned solidifying agent (II) further contains 1～10 weight %.
From the viscosity of solidifying agent, the operation property when mixing with host and the viewpoint of further improving the hardness of curable urethane resin thing, the average hydroxyl value of the above-mentioned solidifying agent (II) that uses in the polyurethane resin composition of the present invention is preferably 200～350mgKOH/g.
From with the reactivity of NCO, the hardness and the good viewpoint of elongation of curable urethane resin thing, above-mentioned W 166 (D) is preferably dipropylene glycol and/or tripropylene glycol.
The compsn that polyurethane resin composition of the present invention is used as the harness of the compsn of the sealing material use of strainer or tubular fibre is particularly useful.
The invention still further relates to polyurethane resin composition of the present invention is solidified the curable urethane resin thing that obtains.
In addition, the invention still further relates to and have the strainer of curable urethane resin thing of the present invention, perhaps have the hollow fiber film assembly (hollow yarn film モ ジ ユ one Le) of curable urethane resin thing of the present invention as the harness material as sealing material.
Polyurethane resin composition of the present invention has just been mixed back viscosity at host and solidifying agent and has been risen very slowly, so operation property is good.In addition, through behind the certain hour, viscosity takes place sharply rise, and fast setting, so productivity is also good.And, the curable urethane resin thing of gained in water in the dip test stripping quantity of carbon compound considerably less, the product after the manufacturing clean easily and safety relieved.
Embodiment
Polyurethane resin composition of the present invention is a two-fluid polyurethane resin composition, and said composition comprises: the solidifying agent (II) that contains the host (I) of specific isocyanate prepolymer composition and contain specific polyhydroxy reactant.
The host (I) that contains specific isocyanate prepolymer composition comprises:
(I-1) aromatic poly-isocyanate (A) and/or
(I-2) making aromatic poly-isocyanate (A) and the end that Viscotrol C (B) reaction obtains is the carbamate prepolymer of NCO;
When using aromatic poly-isocyanate (A), has reactive high advantage with reactive hydrogen as host (I).
As aromatic poly-isocyanate (A), can enumerate out: tolylene diisocyanate, diphenylmethanediisocyanate, polymethylene polyphenyl base polymeric polyisocyanate, or their part carried out the compound that carbodiimide modification, biuret modified, allophanate (or salt) modification, chlorinated isocyanurates (or salt) modification obtain.In these compounds; Consider from the aspect that has a hyperergy with hydroxyl, preferred diphenylmethanediisocyanate, polymethylene polyphenyl base polymeric polyisocyanate, or their part carried out in the compound that carbodiimide modification, biuret modified, allophanate (or salt) modification, chlorinated isocyanurates (or salt) modification obtain one or more.Wherein, stability in storage low from crystallinity, host (I) good aspect consideration, the more preferably diphenylmethanediisocyanate of polymethylene polyphenyl base polymeric polyisocyanate, partially carbonized diimine modification or their mixture.
, have excellent storage stability aspect low from crystallinity consider, as host (I), also can use end that aromatic poly-isocyanate (A) and Viscotrol C (B) reaction the obtain carbamate prepolymer (I-2) as NCO.
Be used to prepare terminal aromatic poly-isocyanate (A) for the carbamate prepolymer of NCO (I-2), can with preferred example enumerate out together with (I-1) in the identical compound of aromatic poly-isocyanate (A) of use.
Conventional other Viscotrol C of level that Viscotrol C (B) uses in the time of can using the terminal carbamate prepolymer as NCO of preparation for example can be enumerated the Viscotrol C that the average hydroxyl value is 160mgKOH/g.
The reaction of aromatic poly-isocyanate (A) and Viscotrol C (B) can adopt existing known method to carry out.For example, can react with Viscotrol C (B) through the aromatic poly-isocyanate (A) that makes the free NCO that contains 20～48 weight %, thereby make the end of carbamate prepolymer have NCO.
Can be the carbamate prepolymer (I-2) of NCO with end also with aromatic poly-isocyanate (I-1).
Another composition of polyurethane resin composition of the present invention is that solidifying agent (II) contains following (C), (D) and (E) composition.
Below, each composition is described.
(C) Viscotrol C
Can enumerate and the identical Viscotrol C of Viscotrol C (B) that is used for synthetic host (I-2), can be identical or different with Viscotrol C (B).
The content of Viscotrol C (C) in solidifying agent (II) is 30～90 weight %.When content is in this scope, can play the effect that reduces the stripping quantity of carbon compound in water.From the less viewpoint of the stripping quantity of carbon compound water, the ratio of the Viscotrol C (C) in the solidifying agent (II) is preferably more than the 50 weight %.From the good viewpoint of the hardness of curable urethane resin thing, be limited to 90 weight % on preferred.
(D) molecular weight is 100～300 W 166
W 166 (D) has two secondary hydroxyls, and this point is different with the glycol in the patent documentation with primary hydroxyl 3 and 4.Consequently, the visbreaking effect of the short period of the glycol with primary hydroxyl is further continued, and play the effect that has excellent storage stability that makes solidifying agent.
In addition, molecular weight is in 100～300 scope the time, not only can fully guarantee time of rising since the mixing time viscosity of two liquid, and the length of usable time is also suitable, therefore can play the good effect of productivity.
It as molecular weight the preferred concrete example of 100～300 W 166 (D); For example can enumerate: (molecular weight is 134 to two W 166s; The average hydroxyl value is 837mgKOH/g), (molecular weight is 192 to tripropylene glycol; The average hydroxyl value is 584mgKOH/g), four Ucar 35 (molecular weight is 250, and the average hydroxyl value is 449mgKOH/g) etc. one or more, wherein; Aspect further shortening usable time suitable usable time, consider preferred dipropylene glycol, tripropylene glycol or their combination.
Following content is only for reference; The molecular weight of the Ucar 35 outside the scope of the invention is 76, the average hydroxyl value is 1477mgKOH/g, 1, and the molecular weight of 4-butyleneglycol is 90, the average hydroxyl value is 1247mgKOH/g; 1, the molecular weight of 6-pinakon is 118, the average hydroxyl value is 951mgKOH/g.
The W 166 (D) that in solidifying agent (II), contains 1～20 weight %.If this content is less than 1 weight %, then just and the mixed viscosity of host big, operation property variation.On the other hand, if this content surpasses 20 weight %, it is too soft then to solidify the resulting curable urethane resin thing in back, can't obtain sufficient hardness according to various objectives.Consider that from increasing visbreaking effect aspect the ratio of the W 166 (D) in the solidifying agent (II) is preferably more than the 3 weight %, more preferably more than the 5 weight %.From the good viewpoint of hardness that makes the curable urethane resin thing, preferably this ratio on be limited to 15 weight %.
(E) the average hydroxyl value that comprises (a)～(c) is the polyol blends of 250～400mgKOH/g
Good and can be easily and other cure component blended viewpoint from operation property, this polyol blends (E) be preferably in advance will (a)～(c) to mix the form cooperation of the mixture that forms.
The average hydroxyl value of polyol blends (E) is in the scope of 250～400mgKOH/g the time, and the mixing initial stage viscosity of host (I) and solidifying agent (II) is low, and plays the effect that increases curable urethane resin thing hardness and improve weather resistance.
(a) Viscotrol C
Can enumerate and above-mentioned Viscotrol C (B) or the identical Viscotrol C of Viscotrol C (C), can be identical or different with Viscotrol C (B) and Viscotrol C (C).
The amount of this Viscotrol C (a) is to make the amount of the average hydroxyl value of polyol blends (E) in the scope of 250～400mgKOH/g.
(b) the average hydroxyl value is the oxirane affixture of the sorbyl alcohol of 400～800mgKOH/g
The amount of the oxirane affixture (b) of this sorbyl alcohol is to make the amount of the average hydroxyl value of polyol blends (E) in the scope of 250～400mgKOH/g.
(c) the average hydroxyl value is the oxirane affixture of the glycerine of 400～800mgKOH/g
The content of the oxirane affixture (c) of this glycerine is to make the amount of the average hydroxyl value of polyol blends (E) in the scope of 250～400mgKOH/g.
In solidifying agent (II), the content of polyol blends (E) is 1～60 weight %.If this content is less than 1 weight %, it is too soft then to solidify the resulting curable urethane resin thing in back, can't obtain sufficient hardness according to various objectives.On the other hand, if this content surpasses 60 weight %, the hardness of the curable urethane resin thing that obtains after then causing solidifying is too big.From the hardness and the good viewpoint of weather resistance of curable urethane resin thing, the ratio of the polyol blends (E) in the solidifying agent (II) is preferably more than the 5 weight %.From the good viewpoint of the hardness of curable urethane resin thing, preferably this ratio on be limited to 50 weight %.
In the two-fluid polyurethane resin composition of the present invention, can make the average hydroxyl value that further contains 1～10 weight % in the solidifying agent (II) is that the oxirane affixture (F) of glycerine of 50～200mgKOH/g is as curing agent component.
When the oxirane affixture (F) of glycerine is in this scope, can improve the intermiscibility of host (I) and solidifying agent (II).From obtaining the viewpoint that sufficient intermiscibility improves effect, the ratio of the oxirane affixture (F) of the glycerine in the solidifying agent (II) is preferably more than the 3 weight %.From the few viewpoint of the stripping quantity of carbon compound water, preferably this ratio on be limited to 10 weight %.
From can further reducing the mixed viscosity of two liquid and can giving the viewpoint of the higher hardness of curable urethane resin thing, the average hydroxyl value of the above-mentioned solidifying agent (II) that uses in the polyurethane resin composition of the present invention is preferably 200～350mgKOH/g.Can adjust the average hydroxyl value of solidifying agent (II) through the cooperation ratio of adjustment curing agent component (C)～(E) and (F) that use as required.
Two-fluid polyurethane resin composition of the present invention comprises host (I) and solidifying agent (II), through the two mixing being begun solidify generation curable urethane resin thing.
According to two-fluid polyurethane resin composition of the present invention; Owing to contain W 166 (D) in the solidifying agent (II); Therefore having excellent storage stability of solidifying agent (II), and with host (I) thus can suppress when mixing viscosity sharply rising can guarantee the activity duration (usable time).
From the good viewpoint of solidified nature, host (I) is preferably 0.8～1.3 with the mixture ratio of solidifying agent (II) by the NCO/OH ratio.NCO/OH is than more preferably 0.9～1.2.
And; This curing is sharply carried out in case curing begins; Make cured article have necessary mechanical characteristics (hardness, elongation, tensile strength); And the carbon compound amount of stripping in water is reduced, therefore can accomplish cured article at short notice or use the washing of the various products of this cured article to handle.
Polyurethane resin composition of the present invention is particularly useful with compsn as the harness of the sealing material use compsn of strainer or tubular fibre.
As strainer, for example can enumerate the felt, fabric, non-woven fabrics of different shape etc., compsn of the present invention is useful as being used for the sealing material that edge with this strainer is bonded and sealed on the various devices.
As tubular fibre; For example can enumerate the tubular fibre that is made up of polysulfones, polyacrylonitrile, polymeric amide, rhodia, pvdf etc., it is used to various uses as hollow fiber film assembly that the end harness of this hollow fiber bundle is formed with the harness agent etc.Compsn of the present invention can be used as the harness agent with the end harness of these hollow fiber bundles.
Further, the invention still further relates to have curable urethane resin thing of the present invention as the strainer of sealing material, or have the hollow fiber film assembly of curable urethane resin thing of the present invention as the harness agent.
Strainer of the present invention can be used for fields such as foodstuffs industry, medical manufacturing, chemical industry, building, building, automobile, semi-conductor, machinery, precision instrument, optics, electronic component, space industry, printing, laser engineering, medical science; More specifically, be suitable as strainers such as air-conditioning, clean room (clean room), OA apparatus, kitchen apparatus, sack cleaner.
In addition; Hollow fiber film assembly of the present invention can be used for fields such as the manufacturing, coating, machinery, printing, fiber, medical science of foodstuffs industry, medical manufacturing, chemical industry, building, semi-conductor and electronic component; More specifically, be suitable as the hollow fiber film assembly of the sedimeter etc. of water, blood etc.
Embodiment
Below, enumerate embodiment etc. the present invention is specified.Can understand the present invention fully through relevant embodiment etc.
1 (preparation of host (I)) of preparation example
The preparation of host (I-1)
As aromatic poly-isocyanate (A), with polymethylene polyphenyl base polymeric polyisocyanate (A1) (free NCO amount: 31 weight %.The ミ リ オ ネ one ト MR-200 that Japan's Port リ ウ レ タ Application (strain) is produced: trade(brand)name) 4 of 50 weight parts and partially carbonized diimine modification, 4 '-diphenylmethanediisocyanate (A2) (free NCO amount: 29 weight %.The ミ リ オ ネ one ト MTL that Japan's Port リ ウ レ タ Application (strain) is produced: trade(brand)name) 50 weight parts mix, preparation host (I-1).
The free NCO amount of the host of gained (I-1) is 30 weight %, is 60mPas 25 ℃ of viscosity of measuring down.
(mensuration of viscosity)
Determinator: (Block Le Star Network Off イ one Le De エ Application ジ ニ ア リ Application グ ラ ボ ラ ト リ one ズ company produces rotational viscosimeter, trade(brand)name: Brookfield viscometer BM)
Condition determination:, under 25 ℃, measure according to JIS Z8803.
The preparation of host (I-2A)
With 4 of partially carbonized diimine modification; 4 '-diphenylmethanediisocyanate (A2), 85 weight parts and Viscotrol C (B1) (average hydroxyl value: 160mgKOH/g; The Viscotrol C カ Network ト Network A that her rattan system oily (strain) is produced: trade(brand)name) 15 weight parts mix and make its reaction, and the preparation end is host (I-2A) for the carbamate prepolymer of NCO.
The free NCO amount of the host of gained (I-2A) is 23 weight %, is 400mPas 25 ℃ of viscosity of measuring down.
The preparation of host (I-2B)
With 4 of polymethylene polyphenyl base polymeric polyisocyanate (A1) 12.5 weight parts, partially carbonized diimine modification; 4 '-diphenylmethanediisocyanate (A2), 76.25 weight parts and Viscotrol C (B1) 11.25 weight parts mix and make it reaction, and the preparation end is host (I-2B) for the carbamate prepolymer of NCO.
The free NCO amount of the host of gained (I-2B) is 24.7 weight %, is 260mPas 25 ℃ of viscosity of measuring down.
2 (preparations of solidifying agent (II)) of preparation example
Composition shown in table 1～4 is pressed the mixed shown in table 1～4, and preparation solidifying agent (II-1)～(II-24) is measured average hydroxyl value, viscosity (25 ℃) and stability in storage.The result is shown in table 1～4.
Each composition that uses is as follows.
(C) Viscotrol C
C1: Viscotrol C (B1) used during with preparation host (I) identical (average hydroxyl value: 160mgKOH/g, the Viscotrol C カ Network ト Network A that her rattan system oil (strain) is produced: trade(brand)name).
(D) W 166
D1: dipropylene glycol (molecular weight is 134, and OH value is 837mgKOH/g)
D2: tripropylene glycol (molecular weight is 192, and OH value is 584mgKOH/g)
D3: Ucar 35 (molecular weight is 76, and OH value is 1477mgKOH/g)
D4: W 166 (molecular weight is 400, and OH value is 280mgKOH/g)
D5:1,4-butyleneglycol (molecular weight is 90, and OH value is 1247mgKOH/g)
D6:1,6-pinakon (molecular weight is 118, and OH value is 951mgKOH/g)
(E) polyol blends
E1: by the oxirane affixture of Viscotrol C (B1), sorbyl alcohol (average hydroxyl value: 478mgKOH/g) and the oxirane affixture of glycerine (average hydroxyl value: the polyol blends of 633mgKOH/g) forming (average hydroxyl value: 330mgKOH/g, the HS CM 075P that rich state system oil (strain) is produced: trade(brand)name)
E2: in polyol blends E1, further mix polyol blends (the average hydroxyl value: 260mgKOH/g) that above-mentioned Viscotrol C カ Network ト Network A processes
E3: polyol blends (the average hydroxyl value: 390mgKOH/g) that the further oxirane affixture that mixes above-mentioned sorbyl alcohol is processed in polyol blends E1
E4: in polyol blends E1, further mix polyol blends (the average hydroxyl value: 230mgKOH/g) that above-mentioned Viscotrol C カ Network ト Network A processes
E5: polyol blends (the average hydroxyl value: 420mgKOH/g) that the further oxirane affixture that mixes above-mentioned sorbyl alcohol is processed in polyol blends E1
(F) the oxirane affixture of glycerine
F1: oxirane affixture (the average hydroxyl value: 168mgKOH/g) of glycerine
F2: oxirane affixture (the average hydroxyl value: 56mgKOH/g) of glycerine
F3: oxirane affixture (the average hydroxyl value: 112mgKOH/g) of glycerine
In addition, adopt following method to measure, estimate average hydroxyl value and stability in storage.
(average hydroxyl value)
Measure according to JIS K1557
(stability in storage)
Solidifying agent was left standstill under 5 ℃ 24 hours, have or not crystal to separate out and have or not muddiness through visual observation.
Zero: do not have crystal to separate out and also do not have muddiness.
*: see that crystal is separated out or muddiness.
Table 1
*: owing in making the after fixing agent, separate out crystal at once, therefore can't measure.
Table 3
Table 4
From table 1, can draw to draw a conclusion.
In the solidifying agent (II), use 1 of non-propandiols, in the example (II-5) of 4-butyleneglycol (D5), stability in storage is low, and uses 1, and solidifying agent does not form homogeneous solution in the example (II-6) of 6-pinakon (D6), can't use as solidifying agent.
On the other hand, use molecular weight be 100～300 W 166 be the example (II-1) of dipropylene glycol (D1) and tripropylene glycol (D2) and (II-2) in, stability in storage is good.
Embodiment 1
Under 25 ℃, by ratio of mixture be 100/70 (weight ratio, NCO/OH=1.1), total amount be the 100g host (I-1) that will prepare preparation in the example 1 with preparation example 2 in the solidifying agent (II-1) for preparing mix, stirred 2 minutes.
At this moment; Through following method measure, estimate firm mixed admixture, mix after through the viscosity (25 ℃) of (after 3 minutes, after 10 minutes, after 15 minutes, after 20 minutes, after 25 minutes, after 30 minutes, after 35 minutes, after 40 minutes, after 45 minutes, after 50 minutes) after the specified time, measure usable time.The result is as shown in table 5.
Secondly; Inject metal pattern (150mm * 150mm * 2mm) with mixing mixed solution after 2 minutes through aforesaid method in addition; Making its curing 5 hours under 60 ℃, further under 25 ℃, making its curing obtain the curable urethane resin thing in 72 hours, adopt following method that hardness, mechanical characteristics (elongation, tensile strength) and the stripping quantity of carbon compound in water of this cured article are measured.The result is as shown in table 5.
(firm mixed admixture)
State through the visual valuation mixed solution.Estimate with standards.
◎: after stir finishing, the muddiness of mixed solution disappears in 5 minutes.
Zero: after stirring end, the muddiness with interior mixed solution disappeared in 10 minutes.
*: after stirring end, through the also disappearance of muddiness of 10 minutes mixed solutions.
(usable time)
With viscosity (25 ℃) reach time before the 10000mPas be usable time (minute).
If usable time is long, then the operation to large-scale plant injection polyurethane resin composition can have plenty of time etc., therefore from the long polyurethane resin composition of the preferred usable time of the viewpoint of operation property.But curing expends the too much time if usable time is long, and is therefore not preferred.In addition, usable time is different because of concrete composition, operating condition etc., under the composition of present embodiment and comparative example, condition, is about 30～40 minutes.
(hardness)
Use sclerometer (the ASKER D type that polymer gauge (strain) is produced), measure Shore D hardness according to JIS K6253-2006.
Suitable hardness is different because of purposes, and as the sealing material that strainer is used, hardness is preferably D20～D50; As the harness agent that hollow fiber film assembly is used, hardness is preferably D50～D80.
(mechanical characteristics)
Use autoplotter (5581 types that イ Application ス ト ロ Application ジ ヤ パ Application company produces), measure elongation and tensile strength according to JIS K7312-1996.
Suitable elongation is different because of purposes, and as the sealing material that strainer is used, elongation is preferably 50～200%; As the harness agent that hollow fiber film assembly is used, elongation is preferably 20～200%.
Suitable tensile strength is different because of purposes, and as the sealing material that strainer is used, tensile strength is preferably 50～150kgf/cm
2As the harness agent that hollow fiber film assembly is used, tensile strength is preferably 150kgf/cm
2More than.
(stripping quantity of carbon compound in water)
The curable urethane resin thing of 40mm * 40mm * 2mm flooded 16 hours in 100 ℃ of zero(ppm) water after; ((strain) Shimadzu Seisakusho Ltd. produces to use the total organic carbon survey meter; Trade(brand)name: TOC-V CPH), measure the total carbon in the steep water, calculate variable quantity (ppm) with respect to blank (blank).
Viewpoint from the pollution that reduces content; The preferred stripping quantity of carbon compound in water is few; In addition, if the stripping quantity of carbon compound in water is few, then can easily and carry out the washing of strainer, hollow fiber film assembly etc. simply; Also can reduce washing times in addition, so preferred.
Embodiment 2～5 and comparative example 1～3
Use to change W 166 (D) composition in the preparation example 2 prepare (II-2) and (II-3)～(II-5) (with reference to table 1) (being respectively embodiment 2 and comparative example 1～3) and further append the oxirane affixture (F) of glycerine and (II-22) that prepare, (II-23) and (II-24) (with reference to table 4) (being respectively embodiment 3,4 and 5) as solidifying agent (II); In addition likewise mix with embodiment 1 and measure, estimate firm mixed admixture, mix after through the viscosity (25 ℃) of (after 3 minutes, after 10 minutes, after 15 minutes, after 20 minutes, after 25 minutes, after 30 minutes, after 35 minutes, after 40 minutes, after 45 minutes, after 50 minutes) after the specified time, measure usable time.Then make its curing obtain cured article, measure hardness, mechanical characteristics (elongation, tensile strength) and the stripping quantity of organism in water of gained cured article.The result is as shown in table 5.
Table 5
From table 5, can draw to draw a conclusion.
Among the embodiment 1 and 2, when to use molecular weight be 100～300 W 166 (D), can prolong since two liquid and mix the time till rising to viscosity, and can in suitable scope, shorten usable time.
In addition, shown in embodiment 3～5, when cooperating the average hydroxyl value to be the oxirane affixture (F) of glycerine of 50～200mgKOH/g, intermiscibility increases, and also can realize sufficient mixing even therefore shorten mixing time.
On the other hand, shown in comparative example 1, when using molecular weight less than 100 Ucar 35 (D3), the time of mixing till rising to viscosity since two liquid shortens.In addition, shown in comparative example 2, when using molecular weight, cause the serviceability ratio appropriate value also long greater than 300 W 166 (D4).In addition, shown in comparative example 3, when using 1 of non-propandiols, during 4-butyleneglycol (D5), the time of mixing till rising to viscosity since two liquid shortens.
Embodiment 6～10 and comparative example 4～9
The cooperation ratio that use to change each composition of solidifying agent (II) in the preparation example 2 prepares (II-7)～(II-11) and (II-12)～(II-17) (with reference to table 2) (being respectively embodiment 6～10 and comparative example 4～9) as solidifying agent (II); In addition likewise mix with embodiment 1 and measure, estimate firm mixed admixture, mix after through the viscosity (25 ℃) of (after 3 minutes, after 10 minutes, after 15 minutes, after 20 minutes, after 25 minutes, after 30 minutes, after 35 minutes, after 40 minutes, after 45 minutes, after 50 minutes) after the specified time, measure usable time.Then make its curing obtain cured article, measure hardness, mechanical characteristics (elongation, tensile strength) and the stripping quantity of organism in water of gained cured article.The result is as shown in table 6.In addition, the result who has put down in writing embodiment 1 in the lump for your guidance.
From table 6, can draw to draw a conclusion.
Shown in embodiment 1 and 6～10, when changing each composition within the scope of the invention, the hardness of curable urethane resin thing, elongation and tensile strength are in suitable scope.
But, shown in comparative example 4, when cooperating Viscotrol C (C) in a large number, cause usable time to prolong with the amount of 95 weight %.On the other hand, shown in comparative example 5, when cooperating Viscotrol C (C) on a small quantity with the amount of 25 weight %, the hardness of curable urethane resin thing is too high, and elongation is also low in addition.
In addition, shown in comparative example 6, when not cooperate molecular weight be 100～300 W 166 (D); Usable time is extremely long, on the other hand, and shown in comparative example 7; When to cooperate molecular weight in a large number be 100～300 W 166 (D) with the amount of 25 weight %; Not only usable time becomes very short, and the raising of the hardness of curable urethane resin thing, and elongation reduces.
Further, shown in comparative example 8, when not cooperating polyol blends (E); The hardness of curable urethane resin thing and tensile strength reduce, on the other hand, and shown in comparative example 9; When cooperating polyol blends (E) in a large number with the amount of 65 weight %, the hardness of curable urethane resin thing is too high.
Embodiment 11～12 and comparative example 10～11
Use to change polyol blends (E) in the preparation example 2 and (II-18)～(II-19) of preparation and (II-20)～(II-21) (with reference to table 3) (being respectively embodiment 11～12 and comparative example 10～11) as solidifying agent (II); In addition likewise mix with embodiment 1 and measure, estimate firm mixed admixture, mix after through the viscosity (25 ℃) of (after 3 minutes, after 10 minutes, after 15 minutes, after 20 minutes, after 25 minutes, after 30 minutes, after 35 minutes, after 40 minutes, after 45 minutes, after 50 minutes) after the specified time, measure usable time.Then make its curing obtain cured article, measure hardness, mechanical characteristics (elongation, tensile strength) and the stripping quantity of organism in water of gained cured article.The result is as shown in table 7.In addition, the result who has put down in writing embodiment 1 in the lump for your guidance.
Table 7
From table 7, can draw to draw a conclusion.
Shown in embodiment 1,11 and 12, when changing the average hydroxyl value of polyol blends (E) within the scope of the invention, the hardness of curable urethane resin thing, elongation and tensile strength are in suitable scope.
Shown in comparative example 10; When the average hydroxyl value of polyol blends (E) is the smaller value of 230mgKOH/g; The hardness of curable urethane resin thing reduces, on the other hand, and shown in comparative example 11; When the average hydroxyl value of polyol blends (E) was the higher value of 420mgKOH/g, the hardness of curable urethane resin thing was too high.
Embodiment 13～16
The combination (embodiment 16) of combination (embodiment 15), host (I-2B) and the solidifying agent (II-22) of combination (being respectively embodiment 13～14), host (I-2A) and the solidifying agent (II-7) of (I-2A)～(I-2B) of preparation and solidifying agent (II-1) is as host (I) in the use preparation example 1; In addition likewise mix with embodiment 1 and measure, estimate firm mixed admixture, mix after through the viscosity (25 ℃) of (after 3 minutes, after 10 minutes, after 15 minutes, after 20 minutes, after 25 minutes, after 30 minutes, after 35 minutes, after 40 minutes, after 45 minutes, after 50 minutes) after the specified time, measure usable time.Then make its curing obtain cured article, measure hardness, mechanical characteristics (elongation, tensile strength) and the stripping quantity of organism in water of gained cured article.The result is as shown in table 8.In addition, the result who has put down in writing embodiment 1 in the lump for your guidance.
Table 8
From table 8, can draw to draw a conclusion.
Shown in embodiment 13～16; Use end that the reaction of aromatic poly-isocyanate (A) and Viscotrol C (B) obtains as the carbamate prepolymer of NCO during as host (I) composition; Firm mixed viscosity increases; But it is identical with embodiment 1 degree and be the length of proper range to mix the length of the time till rising to viscosity since two liquid, and hardness, elongation and the tensile strength of the curable urethane resin thing of gained are in suitable scope.
Claims (8)
1. two-fluid polyurethane resin composition, said composition comprises: the solidifying agent (II) that contains the host (I) of isocyanate prepolymer composition and contain polyhydroxy reactant is characterized in that:
Host (I) contains
(I-1) aromatic poly-isocyanate (A) and/or
(I-2) making aromatic poly-isocyanate (A) and the end that Viscotrol C (B) reaction obtains is the carbamate prepolymer of NCO;
Solidifying agent (II) contains
(C) Viscotrol C,
(D) dipropylene glycol and/or tripropylene glycol,
(E) the average hydroxyl value that comprises following (a)～(c) is the polyol blends of 250～400mgKOH/g:
(a) Viscotrol C,
(b) the average hydroxyl value be the sorbyl alcohol of 400～800mgKOH/g the oxirane affixture,
(c) the average hydroxyl value is the oxirane affixture of the glycerine of 400～800mgKOH/g,
Wherein the content of (C) is that the content of 30～90 weight %, (D) is that the content of 1～20 weight %, (E) is 1～60 weight % in the solidifying agent (II),
Host (I) counts 0.8～1.3 with the mixture ratio of solidifying agent (II) by the NCO/OH ratio.
2. the described polyurethane resin composition of claim 1, wherein, the average hydroxyl value that said solidifying agent (II) further contains 1～10 weight % is the oxirane affixture (F) of the glycerine of 50～200mgKOH/g.
3. claim 1 or 2 described polyurethane resin composition, wherein, the average hydroxyl value of said solidifying agent (II) is 200～350mgKOH/g.
4. claim 1 or 2 described polyurethane resin composition, wherein, said polyurethane resin composition is the compsn of the sealing material use of strainer.
5. claim 1 or 2 described polyurethane resin composition, wherein, said polyurethane resin composition is the compsn that the harness of tubular fibre is used.
6. each described polyurethane resin composition in the claim 1 to 5 is solidified the curable urethane resin thing that obtains.
7. have the strainer of the described curable urethane resin thing of claim 6 as sealing material.
8. have the hollow fiber film assembly of the described curable urethane resin thing of claim 6 as the harness material.
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| CN107629753A (en) * | 2017-08-23 | 2018-01-26 | 山东奥卓化学有限公司 | Water process curtain type film assembly polyurethane pouring sealant and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004037307A1 (en) * | 2002-10-25 | 2004-05-06 | Johnson & Johnson Medical Limited | Fluid wound dressing comprising partially cured polyurethane |
| CN101175786A (en) * | 2005-05-16 | 2008-05-07 | 旭硝子株式会社 | Hardenable composition |
| EP1967536A1 (en) * | 2005-12-27 | 2008-09-10 | Nippon Polyurethane Industry Co., Ltd. | Composition for polyurethane resin formation, sealing material, and hollow-fiber membrane module |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004037307A1 (en) * | 2002-10-25 | 2004-05-06 | Johnson & Johnson Medical Limited | Fluid wound dressing comprising partially cured polyurethane |
| CN101175786A (en) * | 2005-05-16 | 2008-05-07 | 旭硝子株式会社 | Hardenable composition |
| EP1967536A1 (en) * | 2005-12-27 | 2008-09-10 | Nippon Polyurethane Industry Co., Ltd. | Composition for polyurethane resin formation, sealing material, and hollow-fiber membrane module |
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