CN103172829A - Preparation method of fluorescent waterborne polyurethane emulsion based on chromophore in diisocyanate - Google Patents
Preparation method of fluorescent waterborne polyurethane emulsion based on chromophore in diisocyanate Download PDFInfo
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- CN103172829A CN103172829A CN2013100928275A CN201310092827A CN103172829A CN 103172829 A CN103172829 A CN 103172829A CN 2013100928275 A CN2013100928275 A CN 2013100928275A CN 201310092827 A CN201310092827 A CN 201310092827A CN 103172829 A CN103172829 A CN 103172829A
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- vulcabond
- chromophore
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- aqueous polyurethane
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 67
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000839 emulsion Substances 0.000 title claims abstract description 24
- 125000005442 diisocyanate group Chemical group 0.000 title abstract 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004970 Chain extender Substances 0.000 claims abstract description 16
- 150000004985 diamines Chemical class 0.000 claims abstract description 9
- 239000012948 isocyanate Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 50
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 12
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical group O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 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 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 125000004427 diamine group Chemical group 0.000 claims description 6
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 4
- CFRFHWQYWJMEJN-UHFFFAOYSA-N 9h-fluoren-2-amine Chemical compound C1=CC=C2C3=CC=C(N)C=C3CC2=C1 CFRFHWQYWJMEJN-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 229920002521 macromolecule Polymers 0.000 claims description 4
- OARRHUQTFTUEOS-UHFFFAOYSA-N safranin Chemical group [Cl-].C=12C=C(N)C(C)=CC2=NC2=CC(C)=C(N)C=C2[N+]=1C1=CC=CC=C1 OARRHUQTFTUEOS-UHFFFAOYSA-N 0.000 claims description 4
- 229940095064 tartrate Drugs 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical group C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000003205 fragrance Substances 0.000 claims description 3
- SOUHUMACVWVDME-UHFFFAOYSA-N safranin O Chemical compound [Cl-].C12=CC(N)=CC=C2N=C2C=CC(N)=CC2=[N+]1C1=CC=CC=C1 SOUHUMACVWVDME-UHFFFAOYSA-N 0.000 claims description 3
- VFNKZQNIXUFLBC-UHFFFAOYSA-N 2',7'-dichlorofluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(Cl)=C(O)C=C1OC1=C2C=C(Cl)C(O)=C1 VFNKZQNIXUFLBC-UHFFFAOYSA-N 0.000 claims description 2
- CJIJXIFQYOPWTF-UHFFFAOYSA-N 7-hydroxycoumarin Natural products O1C(=O)C=CC2=CC(O)=CC=C21 CJIJXIFQYOPWTF-UHFFFAOYSA-N 0.000 claims description 2
- -1 PCDL Chemical compound 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- KXXXUIKPSVVSAW-UHFFFAOYSA-K pyranine Chemical compound [Na+].[Na+].[Na+].C1=C2C(O)=CC(S([O-])(=O)=O)=C(C=C3)C2=C2C3=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1 KXXXUIKPSVVSAW-UHFFFAOYSA-K 0.000 claims description 2
- 239000013638 trimer Substances 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical group C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 claims description 2
- HFTAFOQKODTIJY-UHFFFAOYSA-N umbelliferone Natural products Cc1cc2C=CC(=O)Oc2cc1OCC=CC(C)(C)O HFTAFOQKODTIJY-UHFFFAOYSA-N 0.000 claims description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 238000013508 migration Methods 0.000 description 7
- 239000000975 dye Substances 0.000 description 6
- 239000004816 latex Substances 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 150000003384 small molecules Chemical class 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- XDFNWJDGWJVGGN-UHFFFAOYSA-N 2-(2,7-dichloro-3,6-dihydroxy-9h-xanthen-9-yl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1C2=CC(Cl)=C(O)C=C2OC2=CC(O)=C(Cl)C=C21 XDFNWJDGWJVGGN-UHFFFAOYSA-N 0.000 description 1
- BZTDTCNHAFUJOG-UHFFFAOYSA-N 6-carboxyfluorescein Chemical compound C12=CC=C(O)C=C2OC2=CC(O)=CC=C2C11OC(=O)C2=CC=C(C(=O)O)C=C21 BZTDTCNHAFUJOG-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229920001109 fluorescent polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002457 helium discharge ionisation detection Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- XTBLDMQMUSHDEN-UHFFFAOYSA-N naphthalene-2,3-diamine Chemical compound C1=CC=C2C=C(N)C(N)=CC2=C1 XTBLDMQMUSHDEN-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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Images
Abstract
The invention discloses a preparation method of a fluorescent waterborne polyurethane emulsion based on chromophore in diisocyanate. The preparation method is characterized by comprising the following steps of: enabling monoamine or monohydric alcohol containing fluorescent chromophore to be reacted with isocyanate, or enabling diamine or dihydric alcohol containing the fluorescent chromophore to be reacted with diisocyanate with a symmetric structure to synthesize diisocyanate containing the fluorescent chromophore, and then combining the diisocyanate containing the fluorescent chromophore with common diisocyanate to partially or completely substitute for the common diisocyanate to prepare the fluorescent waterborne polyurethane. According to the preparation method disclosed by the invention, the hard segment content and type of the prepared fluorescent waterborne polyurethane and the content (2-40wt%) of the fluorescent chromophore are controllable by adjusting the types and proportions of the diisocyanate and a chain extender, and the prepared fluorescent waterborne polyurethane has the advantages that the fluorescent chromophore is uniformly distributed and difficult to migrate, the fluorescent intensity is good in durability, and improvement in terms of optical, thermal and certain functional characteristics can be achieved while the fluorescent property is achieved.
Description
Technical field
The invention belongs to the water-base polyurethane material technical field, particularly have the preparation method who synthesizes and use the part or all of alternative formed fluorescent type aqueous polyurethane emulsion of vulcabond commonly used of this vulcabond of the vulcabond of fluorescent chromophore.
Background technology
Because aqueous polyurethane is take water as dispersion medium, therefore have outstanding environment-friendly advantage and good over-all properties, begun in recent years replace solvents type polyurethane gradually.Give fluorescent functional to aqueous polyurethane, can greatly increase it in the application in the fields such as water-borne coatings, water soluble dyestuffs, water color ink, weaving, environment measuring, medical research.
Come initiated polymerization but the method for existing general synthesizing water-solubility fluorescent polymer has by distinctive functional group reactions on the reactive functionality on the small molecules fluorescent chemicals and polymkeric substance, the initiator for preparing with fluorophor, and prepare molecule chain end with the fluorescence polymer of fluorophor etc. with the organic molecule that contains fluorophor as chain-transfer agent.But not only reaction conditions is harsher for these existing methods, and is difficult to obtain the polymkeric substance of high fluorescent chromophore content, basically is not suitable for the synthetic of aqueous polyurethane.And give fluorescent functional to aqueous polyurethane, at present the most frequently used way is first to react by dibasic alcohol or diamine compound and vulcabond commonly used (comprising tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate) to make aqueous polyurethane emulsion, then small molecules high-visibility pigment or dyestuff are added in aqueous polyurethane emulsion.Because the in use migration etc. of high-visibility pigment or dye granule of the consistency of the solubility limits that is subjected to small molecules high-visibility pigment or dyestuff in water, high-visibility pigment or dye granule and aqueous polyurethane body, material affects, resulting water-base polyurethane material with fluorescent functional is Shortcomings all at aspects such as color kind, fluorescent functional, vividness, anti-migration and weathering resistancies, and the heavy metal in some small molecules high-visibility pigment or dyestuff also can bring certain environmental problem.
The disclosed a kind of water soluble fluorescent conjugated polymer of Chinese patent 200910308614.5 and synthetic method thereof, mainly has hydrophobic conjugated main chain by introducing and hydrophilic ionic functional group side chain carries out, the multiple organic solvents such as acetone, ether, DMF and methyl alcohol have been used in building-up process, the reaction more complicated, used time is longer, and fluorescence conjugated group content in polymkeric substance is uncontrollable.So this synthetic method is not suitable for the synthetic preparation of fluorescent type aqueous polyurethane substantially yet.
Summary of the invention
The object of the invention is to propose a kind of preparation method based on chromophoric fluorescent type aqueous polyurethane in vulcabond, the main raw material vulcabond that uses when urethane is synthetic is given fluorescent functional, synthesize the vulcabond with fluorescent chromophore, partly or entirely substitute existing vulcabond commonly used, make the aqueous polyurethane of preparing have fluorescent characteristic.
The preparation method of fluorescent type aqueous polyurethane of the present invention, it is characterized in that: comprise the preparation of the vulcabond that contains fluorescent chromophore, and use this fluorescent type vulcabond and vulcabond commonly used to make up, partly or entirely substitute vulcabond commonly used, generate the fluorescent type aqueous polyurethane with dihydroxyl or diamino compound reaction;
The described preparation that contains the vulcabond of fluorescent chromophore comprises:
A kind of is to adopt the monoamine contain fluorescent chromophore (Fluorophore) or monohydroxy-alcohol to react with triisocyanate to make the fluorescent type vulcabond, and its reaction formula can be expressed as:
R in formula
1Be the agent structure except isocyanate groups in triisocyanate;
When the material that contains fluorescent chromophore is monoamine, be the N of the triisocyanate of 20-50% with mass percent concentration, dinethylformamide solution joins in there-necked flask, stir and be warming up to 20-50 ℃, 0.5-1 dripping mass percent concentration in hour is the DMF solution of the monoamine of 20-50%; Wherein triisocyanate is 1:1 with the ratio of monoamine amount of substance; Under agitation keep 20-50 ℃ of reaction to finish reaction in 1-4 hour after being added dropwise to complete, cooling rear underpressure distillation desolventizing, product is dried to constant weight after with acetone or washed with dichloromethane in vacuum drying oven, obtain the fluorescent type vulcabond;
When the material that contains fluorescent chromophore is monohydroxy-alcohol, be the N of the triisocyanate of 20-50% with mass percent concentration, dinethylformamide solution joins in there-necked flask, stir and be warming up to 20-50 ℃, 0.5-1 dripping mass percent concentration in hour is the DMF solution of the monohydroxy-alcohol of 20-50%; Wherein triisocyanate is 1:1 with the ratio of monohydroxy-alcohol amount of substance; Adding by non-solvent constituent mass wherein is the dibutyl tin laurate (DBTDL) of benchmark 0.01-0.08%, under agitation keep 50-80 ℃ of reaction to finish reaction in 4-6 hour after being added dropwise to complete, cooling rear underpressure distillation desolventizing, product is dried to constant weight after with acetone or washed with dichloromethane in vacuum drying oven, obtain the fluorescent type vulcabond;
Or another kind is that the di-isocyanate reaction that contains diamine or the dibasic alcohol of fluorescent chromophore and have a symmetrical structure makes the fluorescent type vulcabond, and its reaction formula can be expressed as:
R in formula
2Be the agent structure except isocyanate groups in the vulcabond with symmetrical structure;
When the material that contains fluorescent chromophore is diamine, be the N of the vulcabond with symmetrical structure of 20-50% with mass percent concentration, dinethylformamide solution joins in there-necked flask, stir and be warming up to 20-50 ℃, 0.5-1 dripping mass percent concentration in hour is the DMF solution of the diamine of 20-50%; Vulcabond with symmetrical structure is 2:1 with the ratio of diamine amount of substance; Under agitation keep 20-50 ℃ of reaction to finish reaction in 1-4 hour after being added dropwise to complete, cooling rear underpressure distillation desolventizing, product is dried to constant weight after with acetone or washed with dichloromethane in vacuum drying oven, obtain the fluorescent type vulcabond;
when the material that contains fluorescent chromophore is dibasic alcohol, the vulcabond with symmetrical structure and the dibasic alcohol that are 2:1 with the ratio of amount of substance join in there-necked flask, add to have the vulcabond of symmetrical structure and the weight of dibasic alcohol is the N of benchmark 50-80%, dinethylformamide is as solvent, with the DBTDL of 0.01-0.08% be catalyzer, under keeping 50-80 ℃ under stirring, reaction finished to react in 4-6 hour, cooling rear underpressure distillation desolventizing, product is dried to constant weight after with acetone or washed with dichloromethane in vacuum drying oven, obtain the fluorescent type vulcabond,
then carry out the preparation of fluorescent type aqueous polyurethane emulsion, comprise: first the quality of non-aqueous in the aqueous polyurethane and non-solvent component is as benchmark, to dewater 0.5-1.5 hour at 110-120 ℃ by the macromolecule dihydric alcohol of this Reference mass 30-70%, add the vulcabond that contains fluorescent chromophore of 15-50% and the mixture of vulcabond commonly used by this Reference mass again, add the hydrophilic chain extender of 4-8% after 2-4 hour 70-100 ℃ of reaction, the dibasic alcohol chainextender of 1.5-11%, the DBTDL of 0.01-0.08% and 20-50% acetone or butanone, 60-90 ℃ of reaction 1-4 hour, then add the triethylamine of 3-6% under the condition of high speed shear and 0-40 ℃, react and add the diamine chain extenders of water and the 0-5% of 200-300% after 1-5 minute, stir and change reaction product over to Rotary Evaporators after 5-30 minute, at 40-50 ℃, 0.01MPa slough acetone or butanone under vacuum condition, obtain the fluorescent type aqueous polyurethane emulsion.
The described vulcabond of fluorescent chromophore and the mixture of vulcabond commonly used of containing, the molar constituent of the vulcabond that wherein contains fluorescent chromophore in mixture be than being 2-100%, and the vulcabond that contains fluorescent chromophore can be the combination of one or more arbitrary proportion.
In described reaction formula, fluorescent chromophore FluorophoreI structure can be one of lower array structure, comprising:
In described reaction formula, fluorescent chromophore FluorophoreII structure can be one of lower array structure, comprising:
In described reaction formula, fluorescent chromophore FluorophoreIII structure can be one of lower array structure, comprising:
In described reaction formula, fluorescent chromophore FluorophoreIV structure can be one of lower array structure, comprising:
Wherein, comprise R
1The triisocyanate of structure is selected from hexamethylene diisocyanate trimer (HDID), 4,4 ', 4 "-triphenylmethane triisocyanate (TPMTI);
Comprise R
2The vulcabond with symmetrical structure of structure is selected from hexamethylene diisocyanate (HDI), diphenylmethanediisocyanate (MDI), PPDI (PPDI) or naphthalene diisocyanate (NDI);
The monoamine that contains fluorescent chromophore is selected from naphthalidine (AN), 2-aminofluorene (2-AF), the luxuriant and rich with fragrance amine of reddish black A, 9-or the amino pyrene-1,3 of 8-, 6-trisulfonic acid trisodium salt (APTS);
The monohydroxy-alcohol that contains fluorescent chromophore is selected from umbelliferone or 8-hydroxyl pyrene-1,3,6-trisulfonic acid trisodium salt (HPTS);
The diamine that contains fluorescent chromophore is selected from safranine T (ST), Safranin B Extra, 63 ,DIS,PER,SE ,Vio,let, 63 26 or 2,3-diaminonaphthalene;
The dibasic alcohol that contains fluorescent chromophore is selected from fluorescein (FL), 6-Fluoresceincarboxylic acid (6-FAM), 2 ', 7 '-dichlorofluorescein (DCFH) or Pigment Yellow 73 101 (PY101);
Macromolecule dihydric alcohol is selected from poly-hexanodioic acid-BDO esterdiol (PBA), polycaprolactone dibasic alcohol (PCL), PCDL (PCDL), PTMG dibasic alcohol (PTMG) or polypropylene glycol (PPG);
Described vulcabond commonly used is selected from tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI) or hexamethylene diisocyanate (HDI);
Described hydrophilic chain extender is selected from dimethylol propionic acid (DMPA) or tartrate (TA);
Described dibasic alcohol chainextender is selected from ethylene glycol (EG), BDO (BDO), 1,6-hexylene glycol (HDO) or glycol ether (DEG);
Described diamine chain extenders is selected from quadrol (EDA) or isophorone diamine (IPDA).
Preparation method of the present invention compared with prior art has the following advantages:
1. the vulcabond that contains fluorescent chromophore is typed into the polyurethane molecular chain due to fluorescent chromophore chemistry when forming the fluorescent type aqueous polyurethane emulsion in, compare with the material of generally small molecules high-visibility pigment or dyestuff directly being sneaked into polyurethane body, adopt the fluorescent type polyurethane material fluorescent chromophore of polyaminoester emulsion formation after dehydration of the inventive method preparation to be evenly distributed, be difficult for migration, but the fluorescence Long-term Preservation;
2. in the situation that the fluorescent chromophore of same concentration is compared with the photoluminescent property of the vulcabond that contains fluorescent chromophore, the quantum yield of the fluorescent type aqueous polyurethane that employing the inventive method is prepared has increased by 25 30 times, and fluorescence intensity significantly strengthens;
3. because fluorescent chromophore is that chemistry is typed in the polyurethane molecular chain, not only the fluorescence intensity persistence is good therefore to adopt the fluorescent type aqueous polyurethane emulsion that the inventive method prepares, and stable storing, is difficult for cancellation;
4. adopt vulcabond that the inventive method preparation contains fluorescent chromophore when forming the fluorescent type aqueous polyurethane emulsion because the fluorescent chromophore structure belongs to hard section of polyurethane molecular chain, therefore can use the amount of fluorescent type vulcabond to control the structure of the hard section of fluorescent type polyurethane molecular chain by adjusting, when obtaining photoluminescent property, play the effect of performances such as regulating fluorescent type aqueous polyurethane optics, calorifics, mechanics and some functional performance.
Description of drawings
Fig. 1 is the vulcabond FLDI that contains fluorescent chromophore of synthetic preparation in the embodiment of the present invention 1 and the infrared spectrogram of fluorescent type aqueous polyurethane FLDI-WPU thereof;
Fig. 2 is that fluorescent chromophore concentration is all 1 * 10
-5The dibasic alcohol FL that contains fluorescent chromophore of mol/L and the fluorescence spectrum comparison diagram of fluorescent type aqueous polyurethane FLDI-WPU.
Embodiment
Embodiment 1:
10.00 gram HDI and 9.88 gram FL are added in there-necked flask, add 60 milliliters of N, dinethylformamide is solvent, adding 0.01 gram DBTDL is catalyzer again, in 60 ℃ of reactions 5 hours, be cooled to 30 ℃ of underpressure distillation desolventizings under mechanical stirring, then wash product 3 times with acetone, washed product is placed in vacuum drying oven and is dried to constant weight, obtains fluorescent type vulcabond FLDI.
With 36.00 gram PTMG(M
n=2000) join in the there-necked flask of 500ml, be cooled to 50 ℃ in dehydration under 115 ℃ after 1 hour.get fluorescent type vulcabond FLDI7.95 gram and 15.60 gram IPDI add in there-necked flask, add 3.70 gram hydrophilic chain extender DMPA after 3 hours in 85 ℃ of stirring reactions, 2.80 gram BDO, 0.02 gram DBTDL and butanone 45.00 grams, constant temperature is cooled to 30 ℃ at 75 ℃ of stirring reactions after 3 hours, change reaction product over to the high speed shear dispersion machine, add 2.80 gram TEA under the condition of 3000 rev/mins, react and add 140 gram water after 5 minutes, stir again after 1 minute and change Rotary Evaporators over to, at 50 ℃, 0.01MPa slough butanone under vacuum condition, obtaining fluorophor content is 12.04% yellow fluorescence type aqueous polyurethane (FLDI – WPU) emulsion.
If other condition of the present embodiment is constant, change the add-on of FLDI and IPDI, can obtain the controlled stable fluorescent type aqueous polyurethane emulsion of fluorophor content 2-40wt% scope.
Accompanying drawing 1 is FLDI and the FLDI-WPU infrared spectrogram of the synthetic preparation of the present embodiment.Can find out that by FLDI – WPU spectrogram the charateristic avsorption band of urethane lays respectively at 3325cm
-1(ν
N-H), 2858-2932cm
-1(ν
CH2And ν
CH3), 1706cm
-1(ν
C=O), 1535cm
-1(δ
N-H) and 1110cm
-1(ν
C-O-C); Lay respectively at 1601cm in the FLDI spectrogram
-1(δ
C=C), 1110cm
-1(δ
Ph-O) and 772cm
-1(γ
C-H) the FLDI charateristic avsorption band also can find out in the FLDI-WPU spectrogram, and represent that isocyanate group NCO is positioned at 2271cm
-1(ν
C=O) charateristic avsorption band high-visible in the FLDI spectrogram, but disappear in FLDI – WPU spectrogram, illustrate that FLDI has participated in reaction when preparing urethane fully synthetic.
Accompanying drawing 2 is all 1 * 10 for fluorescent chromophore concentration
-5The FL aqueous solution of mol/L and the fluorescence spectrum comparison diagram of FLDI-WPU, both maximum fluorescence emission peaks all are positioned at 515nm, and peak shape is similar.Fig. 2 explanation fluorescence intensity after fluorophor is typed into the aqueous polyurethane molecular chain by chemistry strengthens greatly, has shown typical enhancement effect of fluorescence.
Embodiment 2:
6.00 gram PPDI and 20 milliliters of DMFs are added in there-necked flask, be warming up to 30 ℃, drip the solution of ST6.60 gram and 30 milliliters of DMFs under mechanical stirring, control dropwises half an hour.Keep 30 ℃ of reaction underpressure distillation desolventizings after 2 hours, then use the washed with dichloromethane product 1 time, washed product is placed in vacuum drying oven and is dried to constant weight, obtains fluorescent type vulcabond STDI.
10.00 gram HDI tripolymers and 20 milliliters of DMFs are added in there-necked flask, be warming up to 30 ℃, drip the solution of 2.84 gram AN and 6 milliliters of DMFs under mechanical stirring, control dropwises half an hour.Keep 30 ℃ of reaction underpressure distillation desolventizings after 2 hours, then use the washed with dichloromethane product 1 time, washed product is placed in vacuum drying oven and is dried to constant weight, obtains fluorescent type vulcabond ANDI.
With 20 gram PCL(M
n=1000) join in the there-necked flask of 500mL, be cooled to 50 ℃ in dehydration under 110 ℃ after 1 hour.get fluorescent type vulcabond STDI3.60 gram, ANDI3.40 gram and IPDI21.30 gram, the DBTDL0.03 gram adds in there-necked flask, add 3.36 gram hydrophilic chain extender TA after 2 hours in 85 ℃ of stirring reactions, 5.10 gram BDO and 55.00 gram butanone, constant temperature is cooled to 20 ℃ at 75 ℃ of stirring reactions after 4 hours, change reaction product over to the high speed shear dispersion machine, add 4.52 gram TEA under the condition of 3000 rev/mins, react and add 140 gram water after 5 minutes, stir again and add 0.30 gram EDA reaction 30 minutes after 1 minute, reaction product changes Rotary Evaporators over to, at 50 ℃, 0.01MPa slough butanone under vacuum condition, obtain fluorophor content and be 12.27% fluorescent type aqueous polyurethane emulsion.
If other condition of the present embodiment is constant, and changes respectively ST into Safranin B Extra, 63 ,DIS,PER,SE ,Vio,let, 63 26 or 2, the 3-diaminonaphthalene all can obtain the controlled stable fluorescent type aqueous polyurethane emulsion of fluorophor content.
Embodiment 3:
With 25.00 gram HDI tripolymers and 30 milliliters of N; dinethylformamide adds in the 250mL there-necked flask, is warming up to 30 ℃, and logical nitrogen protection also drips reddish black A14.50 gram and 30 milliliters of N under mechanical stirring; the solution of dinethylformamide, control dropwises half an hour.Keep 30 ℃ of reaction underpressure distillation desolventizings after 2 hours, then use the washing with acetone product 1 time, washed product is placed in vacuum drying oven and is dried to constant weight, obtains fluorescent type vulcabond AADI.
With 60.00 gram PPG(M
n=1000) join in the there-necked flask of 500mL, be cooled to 50 ℃ in dehydration under 120 ℃ after 1 hour.Get fluorescent type vulcabond AADI18.00 gram and TDI35.00 gram, the DBTDL0.03 gram adds in there-necked flask, add 7.20 gram hydrophilic chain extender DMPA, 8.60 gram DEG and 90.00 gram acetone after 3 hours in 80 ℃ of stirring reactions, constant temperature is cooled to 5 ℃ at 65 ℃ of stirring reactions after 4 hours.Change reaction product over to the high speed shear dispersion machine, add 5.50 gram TEA under the condition of 3000 rev/mins, react and add 240 gram water after 5 minutes, then stir and add 0.80 gram EDA reaction 30 minutes after 1 minute.Reaction product changes Rotary Evaporators over to, sloughs acetone under 40 ℃, 0.01MPa vacuum condition, obtains fluorophor content and be 13.89% blue-fluorescence type aqueous polyurethane emulsion.
If other condition of the present embodiment is constant, and changes respectively PPG into PBA, PCL, PCDL or PTMG, or the combination of any two kinds, three kinds wherein all can obtain the controlled stable fluorescent type aqueous polyurethane emulsion of fluorophor content.
If other condition of the present embodiment is constant, and change respectively reddish black A into naphthalidine, the luxuriant and rich with fragrance amine of 2-AF, 9-or APTS, all can obtain the controlled stable fluorescent type aqueous polyurethane emulsion of fluorophor content.
If other condition of the present embodiment is constant, and changes DEG into EG or HDO, or any two or three combination wherein all can obtain the controlled stable fluorescent type aqueous polyurethane emulsion of fluorophor content.
In the constant situation of other condition in the present embodiment, EDA is replaced to IPDA, also can obtain the controlled stable fluorescent type aqueous polyurethane emulsion of fluorophor content.
Embodiment 4: the assessment of fluorescent chromophore resistance to migration matter
The present embodiment is pressed the resistance to migration of fluorescent chromophore in U.S. textile chemist and printing and dyeing Shi Xiehui AATCCTestMethod140-2001 criterion evaluation latex film, and this testing method is described below:
Being to mark off regional A and the regional B that size equates on the 0.12mm latex film at the thickness that contains fluorescent chromophore on sheet glass, is that the 90mm watch-glass covers regional A with diameter, and regional B directly contacts with air.Whole system is placed in 60 ℃ of baking ovens and keeps taking out after 24 hours.Get respectively the regional A of identical weight and the latex film of regional B and be dissolved in METHYLPYRROLIDONE, being configured to concentration is 1 * 10
-5The solution of g/mL.Measure the uv-visible absorption spectroscopy of solution, the absorbancy during by maximum absorption obtains the concentration of corresponding fluorescent chromophore according to Law of Lambert-Beer.The mobility M of fluorescent chromophore in latex film
pCan be by formula M
p=[(C
B– C
A)/C
A] * 100% calculates, M
pValue is less shows that the fluorescent chromophore resistance to migration in latex film is better, C
A, C
BRespectively the concentration of regional A and regional B fluorescent chromophore.Utilize in U.S. textile chemist and the AATCCTechnicalManual (2006) that writes of printing and dyeing Shi Xiehui (AATCC) the 244th to 246 page, Fig. 1 in " AATCCTestMethod140 – 2001, DyeandPigmentMigrationinaPad-DryProcess:Evaluationof " schematic diagram.
For ease of comparing, following table has provided two kinds of result datas that sample carries out respectively 3 experiments:
In table, FLDI-WPU is the latex film of the fluorescent type aqueous polyurethane emulsion formation of preparation; FL+WPU is the mixture that the direct aqueous polyurethane with not containing fluorescent chromophore of FL forms.The quality of nonvolatile element is as benchmark in the aqueous polyurethane, and in two kinds of samples, the content of fluorescent chromophore is all 6%.Show the mobility M of FLDI-WPU in table
pMean value be only 1.3%, FL+WPU reach 31.6%.The mode that presentation of results is keyed in chemistry when fluorescent chromophore is fixed on polyurethane backbone and can greatly limits chromophoric migration, and the fluorescent type aqueous polyurethane of preparation in use fluorescent chromophore is difficult for being moved, and fluorescence and color and luster are kept for a long time.
Claims (9)
1. the preparation method of a fluorescent type aqueous polyurethane, it is characterized in that: comprise the preparation of the vulcabond that contains fluorescent chromophore, and use this fluorescent type vulcabond and vulcabond commonly used to make up, partly or entirely substitute vulcabond commonly used, generate the fluorescent type aqueous polyurethane with dihydroxyl or diamino compound reaction;
The described preparation that contains the vulcabond of fluorescent chromophore comprises:
A kind of is to adopt the monoamine contain fluorescent chromophore Fluorophore or monohydroxy-alcohol to react with triisocyanate to make the fluorescent type vulcabond, and its reaction formula is expressed as:
R in formula
1Be the agent structure except isocyanate groups in triisocyanate;
When the material that contains fluorescent chromophore is monoamine, be the N of the triisocyanate of 20-50% with mass percent concentration, dinethylformamide solution joins in there-necked flask, stir and be warming up to 20-50 ℃, 0.5-1 dripping mass percent concentration in hour is the DMF solution of the monoamine of 20-50%; Wherein triisocyanate is 1:1 with the ratio of monoamine amount of substance; Under agitation keep 20-50 ℃ of reaction to finish reaction in 1-4 hour after being added dropwise to complete, cooling rear underpressure distillation desolventizing, product is dried to constant weight after with acetone or washed with dichloromethane in vacuum drying oven, obtain the fluorescent type vulcabond;
When the material that contains fluorescent chromophore is monohydroxy-alcohol, be the N of the triisocyanate of 20-50% with mass percent concentration, dinethylformamide solution joins in there-necked flask, stir and be warming up to 20-50 ℃, 0.5-1 dripping mass percent concentration in hour is the DMF solution of the monohydroxy-alcohol of 20-50%; Wherein triisocyanate is 1:1 with the ratio of monohydroxy-alcohol amount of substance; Adding by non-solvent constituent mass wherein is the dibutyl tin laurate of benchmark 0.01-0.08%, under agitation keep 50-80 ℃ of reaction to finish reaction in 4-6 hour after being added dropwise to complete, cooling rear underpressure distillation desolventizing, product is dried to constant weight after with acetone or washed with dichloromethane in vacuum drying oven, obtain the fluorescent type vulcabond;
Or another kind is that the di-isocyanate reaction that contains diamine or the dibasic alcohol of fluorescent chromophore and have a symmetrical structure makes the fluorescent type vulcabond, and its reaction formula is expressed as:
R in formula
2Be the agent structure except isocyanate groups in the vulcabond with symmetrical structure;
When the material that contains fluorescent chromophore is diamine, be the N of the vulcabond with symmetrical structure of 20-50% with mass percent concentration, dinethylformamide solution joins in there-necked flask, stir and be warming up to 20-50 ℃, 0.5-1 dripping mass percent concentration in hour is the DMF solution of the diamine of 20-50%; Vulcabond with symmetrical structure is 2:1 with the ratio of diamine amount of substance; Under agitation keep 20-50 ℃ of reaction to finish reaction in 1-4 hour after being added dropwise to complete, cooling rear underpressure distillation desolventizing, product is dried to constant weight after with acetone or washed with dichloromethane in vacuum drying oven, obtain the fluorescent type vulcabond;
when the material that contains fluorescent chromophore is dibasic alcohol, the vulcabond with symmetrical structure and the dibasic alcohol that are 2:1 with the ratio of amount of substance join in there-necked flask, add to have the vulcabond of symmetrical structure and the weight of dibasic alcohol is the N of benchmark 50-80%, dinethylformamide is as solvent, with the dibutyl tin laurate of 0.01-0.08% be catalyzer, under keeping 50-80 ℃ under stirring, reaction finished to react in 4-6 hour, cooling rear underpressure distillation desolventizing, product is dried to constant weight after with acetone or washed with dichloromethane in vacuum drying oven, obtain the fluorescent type vulcabond,
then carry out the preparation of fluorescent type aqueous polyurethane emulsion, comprise: first the quality of non-aqueous in the aqueous polyurethane and non-solvent component is as benchmark, to dewater 0.5-1.5 hour at 110-120 ℃ by the macromolecule dihydric alcohol of this Reference mass 30-70%, add the vulcabond that contains fluorescent chromophore of 15-50% and the mixture of vulcabond commonly used by this Reference mass again, add the hydrophilic chain extender of 4-8% after 2-4 hour 70-100 ℃ of reaction, the dibasic alcohol chainextender of 1.5-11%, the dibutyl tin laurate of 0.01-0.08% and 20-50% acetone or butanone, 60-90 ℃ of reaction 1-4 hour, then add the triethylamine of 3-6% under the condition of high speed shear and 0-40 ℃, react and add the diamine chain extenders of water and the 0-5% of 200-300% after 1-5 minute, stir and change reaction product over to Rotary Evaporators after 5-30 minute, at 40-50 ℃, 0.01MPa slough acetone or butanone under vacuum condition, obtain the fluorescent type aqueous polyurethane emulsion.
2. the preparation method of fluorescent type aqueous polyurethane as claimed in claim 1, be characterised in that the described vulcabond of fluorescent chromophore and the mixture of vulcabond commonly used of containing, the molar constituent of the vulcabond that wherein contains fluorescent chromophore in mixture be than being 2-100%, and contain the vulcabond of fluorescent chromophore and be the combination of one or more arbitrary proportion.
3. the preparation method of fluorescent type aqueous polyurethane as claimed in claim 1 is characterised in that in described reaction formula, fluorescent chromophore FluorophoreI structure is:
4. the preparation method of fluorescent type aqueous polyurethane as claimed in claim 1, be characterised in that in described reaction formula, fluorescent chromophore FluorophoreII structure is
5. the preparation method of fluorescent type aqueous polyurethane as claimed in claim 1 is characterised in that in described reaction formula that fluorescent chromophore FluorophoreIII structure is 2. preparation methods of fluorescent type aqueous polyurethane as claimed in claim 1, is characterised in that:
6. the preparation method of fluorescent type aqueous polyurethane as claimed in claim 1 is characterised in that in described reaction formula, fluorescent chromophore FluorophoreIV structure is:
7. the preparation method of fluorescent type aqueous polyurethane as claimed in claim 1, be characterised in that the described R of comprising
1The triisocyanate of structure is selected from hexamethylene diisocyanate trimer, 4,4 ', 4 "-triphenylmethane triisocyanate;
The described R that comprises
2The vulcabond with symmetrical structure of structure is selected from hexamethylene diisocyanate, diphenylmethanediisocyanate, PPDI (PPDI) or naphthalene diisocyanate.
8. the preparation method of fluorescent type aqueous polyurethane as claimed in claim 1, be characterised in that the described monoamine that contains fluorescent chromophore is selected from naphthalidine, 2-aminofluorene, the luxuriant and rich with fragrance amine of reddish black A, 9-or the amino pyrene-1,3 of 8-, 6-trisulfonic acid trisodium salt;
The described monohydroxy-alcohol that contains fluorescent chromophore is selected from umbelliferone or 8-hydroxyl pyrene-1,3,6-trisulfonic acid trisodium salt;
The described diamine that contains fluorescent chromophore is selected from safranine T, Safranin B Extra, 63 ,DIS,PER,SE ,Vio,let, 63 26 or 2, the 3-diaminonaphthalene;
The described dibasic alcohol that contains fluorescent chromophore is selected from fluorescein, 6-Fluoresceincarboxylic acid, 2 ', 7 '-dichlorofluorescein or Pigment Yellow 73 101.
9. the preparation method of fluorescent type aqueous polyurethane as claimed in claim 1, be characterised in that described macromolecule dihydric alcohol is selected from poly-hexanodioic acid-BDO esterdiol (PBA), polycaprolactone dibasic alcohol, PCDL, PTMG dibasic alcohol or polypropylene glycol;
Described vulcabond commonly used is selected from tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate or hexamethylene diisocyanate;
Described hydrophilic chain extender is selected from dimethylol propionic acid or tartrate;
Described dibasic alcohol chainextender is selected from ethylene glycol, BDO, 1,6-hexylene glycol or glycol ether;
Described diamine chain extenders is selected from quadrol (EDA) or isophorone diamine.
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