CN103172829B - 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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- CN103172829B CN103172829B CN201310092827.5A CN201310092827A CN103172829B CN 103172829 B CN103172829 B CN 103172829B CN 201310092827 A CN201310092827 A CN 201310092827A CN 103172829 B CN103172829 B CN 103172829B
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 66
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 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 47
- 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
- -1 amino pyrene-1 Chemical compound 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
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 239000003205 fragrance Substances 0.000 claims description 3
- XTBLDMQMUSHDEN-UHFFFAOYSA-N naphthalene-2,3-diamine Chemical compound C1=CC=C2C=C(N)C(N)=CC2=C1 XTBLDMQMUSHDEN-UHFFFAOYSA-N 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
- 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
- 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
- 230000005012 migration Effects 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
- 150000003384 small molecules Chemical class 0.000 description 5
- 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
- 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
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- 238000007639 printing Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 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
- JUKDRAILSZBHDW-UHFFFAOYSA-N CC(C=CC1)=CC1O Chemical compound CC(C=CC1)=CC1O JUKDRAILSZBHDW-UHFFFAOYSA-N 0.000 description 1
- 0 CC=CC=C1[C@@](C2)(C(CC=CC3)C3C2=*)C(CCC(C)=C2)C2OC1 Chemical compound CC=CC=C1[C@@](C2)(C(CC=CC3)C3C2=*)C(CCC(C)=C2)C2OC1 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
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002457 helium discharge ionisation detection Methods 0.000 description 1
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Landscapes
- Polyurethanes Or Polyureas (AREA)
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 water-base polyurethane material technical field, particularly there is the preparation method who synthesizes and apply the part or all of alternative conventional formed fluorescent type aqueous polyurethane emulsion of vulcabond of this vulcabond of the vulcabond of fluorescent chromophore.
Background technology
Because aqueous polyurethane is to take water as dispersion medium, therefore there is outstanding environment-friendly advantage and good over-all properties, started in recent years replace solvents type polyurethane gradually.To aqueous polyurethane, give fluorescent functional, 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.
The method of existing general synthesizing water-solubility fluorescent polymer have by small molecules fluorescent chemicals can reactive functionality and polymkeric substance on distinctive functional group reactions, preparation with the initiator of fluorophor, carry out initiated polymerization, and as chain-transfer agent, prepare molecule chain end with the fluorescence polymer of fluorophor etc. with the organic molecule that contains fluorophor.But not only reaction conditions is harsher for these existing methods, and be difficult to obtain the polymkeric substance of high fluorescent chromophore content, be not substantially suitable for the synthetic of aqueous polyurethane.And give fluorescent functional to aqueous polyurethane, the most frequently used way is first by dibasic alcohol or diamine compound, to be reacted and make aqueous polyurethane emulsion with conventional vulcabond (comprising tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate) at present, 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 subject to small molecules high-visibility pigment or dyestuff in water, high-visibility pigment or dye granule and aqueous polyurethane body, material affects, the resulting water-base polyurethane material with fluorescent functional is Shortcomings all at aspects such as color kind, fluorescent functional, vividness, resistance to 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 by introducing, there is hydrophobic conjugated main chain and hydrophilic ionic functional group side chain carries out, the multiple organic solvents such as acetone, ether, DMF and methyl alcohol in building-up process, have been used, 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 using when urethane is synthetic is given fluorescent functional, synthesize the vulcabond with fluorescent chromophore, partly or entirely substitute existing conventional vulcabond, make the aqueous polyurethane of preparing there is 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 conventional vulcabond to combine, partly or entirely substitute conventional vulcabond, react with dihydroxyl or diamino compound and generate fluorescent type aqueous polyurethane;
The preparation of the described vulcabond that contains fluorescent chromophore comprises:
Be to adopt the monoamine contain fluorescent chromophore (Fluorophore) or monohydroxy-alcohol to react with triisocyanate to make a fluorescent type vulcabond, its reaction formula can be expressed as:
R in formula
1for the agent structure except isocyanate groups in triisocyanate;
When the material containing fluorescent chromophore is monoamine, the N of the triisocyanate that is 20-50% by mass percent concentration, dinethylformamide solution joins in there-necked flask, stir and be warming up to 20-50 ℃, in 0.5-1 hour, dripping mass percent concentration is the DMF solution of the monoamine of 20-50%; Wherein triisocyanate is 1:1 with the ratio of monoamine amount of substance; After being added dropwise to complete, under agitation keep 20-50 ℃ of reaction to finish reaction in 1-4 hour, cooling rear underpressure distillation is except desolventizing, and product, be dried to constant weight after acetone or washed with dichloromethane in vacuum drying oven, obtains fluorescent type vulcabond;
When the material containing fluorescent chromophore is monohydroxy-alcohol, the N of the triisocyanate that is 20-50% by mass percent concentration, dinethylformamide solution joins in there-necked flask, stir and be warming up to 20-50 ℃, in 0.5-1 hour, dripping mass percent concentration 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 is wherein the dibutyl tin laurate (DBTDL) of benchmark 0.01-0.08%, after being added dropwise to complete, under agitation keep 50-80 ℃ of reaction within 4-6 hour, to finish reaction, cooling rear underpressure distillation is except desolventizing, product, be dried to constant weight after acetone or washed with dichloromethane in vacuum drying oven, obtains fluorescent type vulcabond;
Or another kind is that diamine or the dibasic alcohol that contains fluorescent chromophore and the di-isocyanate reaction with symmetrical structure make fluorescent type vulcabond, its reaction formula can be expressed as:
R in formula
2for thering is the agent structure except isocyanate groups in the vulcabond of symmetrical structure;
When the material containing fluorescent chromophore is diamine, the N of the vulcabond with symmetrical structure that is 20-50% by mass percent concentration, dinethylformamide solution joins in there-necked flask, stir and be warming up to 20-50 ℃, in 0.5-1 hour, dripping mass percent concentration is the DMF solution of the diamine of 20-50%; There is the vulcabond of symmetrical structure and the ratio of diamine amount of substance is 2:1; After being added dropwise to complete, under agitation keep 20-50 ℃ of reaction to finish reaction in 1-4 hour, cooling rear underpressure distillation is except desolventizing, and product, be dried to constant weight after acetone or washed with dichloromethane in vacuum drying oven, obtains fluorescent type vulcabond;
When the material containing fluorescent chromophore is dibasic alcohol, the vulcabond with symmetrical structure and the dibasic alcohol that by the ratio of amount of substance, are 2:1 join in there-necked flask, adding 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, at keeping 50-80 ℃ under stirring, react and within 4-6 hour, finish reaction, cooling rear underpressure distillation is except desolventizing, product is be dried to constant weight after acetone or washed with dichloromethane in vacuum drying oven, obtain fluorescent type vulcabond,
Then carry out the preparation of fluorescent type aqueous polyurethane emulsion, comprise: non-aqueous in aqueous polyurethane and quality non-solvent component of first take is benchmark, by by the macromolecule dihydric alcohol of this Reference mass 30-70% at 110-120 ℃ of dehydration 0.5-1.5 hour, by this Reference mass, add the vulcabond that contains fluorescent chromophore of 15-50% and the mixture of conventional vulcabond again, 70-100 ℃ of reaction, after 2-4 hour, add the hydrophilic chain extender of 4-8%, the dibasic alcohol chainextender of 1.5-11%, the DBTDL of 0.01-0.08% and 20-50% acetone or butanone, at 60-90 ℃ of reaction 1-4 hour, then under the condition of high speed shear and 0-40 ℃, add the triethylamine of 3-6%, react and after 1-5 minute, add the diamine chain extenders of water and the 0-5% of 200-300%, stir, after 5-30 minute, reaction product is proceeded to Rotary Evaporators, at 40-50 ℃, under 0.01MPa vacuum condition, slough acetone or butanone, obtain fluorescent type aqueous polyurethane emulsion.
The described vulcabond that contains fluorescent chromophore and the mixture of conventional vulcabond, the molar constituent of the vulcabond that wherein contains fluorescent chromophore in mixture is 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 amino pyrene-1 of 8-, 3,6-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 conventional vulcabond 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 when forming fluorescent type aqueous polyurethane emulsion because fluorescent chromophore chemistry is typed in polyurethane molecular chain, compare with the material of generally small molecules high-visibility pigment or dyestuff directly being sneaked into polyurethane body, the fluorescent type polyurethane material fluorescent chromophore that polyaminoester emulsion prepared by employing the inventive method forms after dehydration is evenly distributed, be difficult for migration, fluorescence can persist;
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 polyurethane molecular chain, not only 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 fluorescent type aqueous polyurethane emulsion because 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.
Accompanying drawing explanation
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 grams of HDI and 9.88 grams of FL are added in there-necked flask, add 60 milliliters of N, dinethylformamide is solvent, adding 0.01 gram of DBTDL is catalyzer again, under mechanical stirring, in 60 ℃ of reactions 5 hours, be cooled to 30 ℃ of underpressure distillation except desolventizing, then with acetone, wash product 3 times, washed product is placed in vacuum drying oven and is dried to constant weight, obtains fluorescent type vulcabond FLDI.
By 36.00 grams of PTMG(M
n=2000) join in the there-necked flask of 500ml, after dewatering 1 hour, be cooled to 50 ℃ at 115 ℃.Get FLDI7.95 gram of fluorescent type vulcabond and 15.60 grams of IPDI add in there-necked flask, in 85 ℃ of stirring reactions, after 3 hours, add 3.70 grams of hydrophilic chain extender DMPA, 2.80 gram BDO, 45.00 grams of 0.02 gram of DBTDL and butanone, constant temperature is cooled to 30 ℃ at 75 ℃ of stirring reactions after 3 hours, reaction product is proceeded to high speed shear dispersion machine, under the condition of 3000 revs/min, add 2.80 grams of TEA, react and after 5 minutes, add 140 grams of water, stir again after 1 minute and proceed to Rotary Evaporators, at 50 ℃, under 0.01MPa vacuum condition, slough butanone, 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.By FLDI – WPU spectrogram, can find out that 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); In FLDI spectrogram, lay respectively at 1601cm
-1(δ
c=C), 1110cm
-1(δ
ph-O) and 772cm
-1(γ
c-H) FLDI charateristic avsorption band also can in FLDI-WPU spectrogram, find out, and represent that isocyanate group NCO is positioned at 2271cm
-1(ν
c=O) charateristic avsorption band high-visible in FLDI spectrogram, in FLDI – WPU spectrogram, but disappear, illustrate that FLDI has participated in reaction while preparing urethane completely synthesizing.
Accompanying drawing 2 is that fluorescent chromophore concentration is all 1 * 10
-5the FL aqueous solution of mol/L and the fluorescence spectrum comparison diagram of FLDI-WPU, both maximum fluorescence emission peaks are all positioned at 515nm, and peak shape is similar.Fig. 2 explanation fluorescence intensity after fluorophor is typed into aqueous polyurethane molecular chain by chemistry strengthens greatly, has shown typical enhancement effect of fluorescence.
Embodiment 2:
6.00 grams of PPDI and 20 milliliters of DMFs are added in there-necked flask, be warming up to 30 ℃, under mechanical stirring, drip the ST6.60 gram of solution with 30 milliliters of DMFs, control and dropwise half an hour.Keep 30 ℃ of reactions after 2 hours underpressure distillation except desolventizing, then use 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 grams of HDI tripolymers and 20 milliliters of DMFs are added in there-necked flask, be warming up to 30 ℃, under mechanical stirring, drip the solution of 2.84 grams of AN and 6 milliliters of DMFs, control and dropwise half an hour.Keep 30 ℃ of reactions after 2 hours underpressure distillation except desolventizing, then use 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.
By 20 grams of PCL(M
n=1000) join in the there-necked flask of 500mL, after dewatering 1 hour, be cooled to 50 ℃ at 110 ℃.Get fluorescent type vulcabond STDI3.60 gram, ANDI3.40 gram and IPDI21.30 gram, DBTDL0.03 gram adds in there-necked flask, in 85 ℃ of stirring reactions, after 2 hours, add 3.36 grams of hydrophilic chain extender TA, 5.10 gram BDO and 55.00 grams of butanone, constant temperature is cooled to 20 ℃ at 75 ℃ of stirring reactions after 4 hours, reaction product is proceeded to high speed shear dispersion machine, under the condition of 3000 revs/min, add 4.52 grams of TEA, react and after 5 minutes, add 140 grams of water, stirring after 1 minute adds 0.30 gram of EDA to react 30 minutes again, reaction product proceeds to Rotary Evaporators, at 50 ℃, under 0.01MPa vacuum condition, slough butanone, 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 2,3-diaminonaphthalene, all can obtain the controlled stable fluorescent type aqueous polyurethane emulsion of fluorophor content.
Embodiment 3:
By 25.00 grams of HDI tripolymers and 30 milliliters of N; dinethylformamide adds in 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, controls and dropwises half an hour.Keep 30 ℃ of reactions after 2 hours underpressure distillation except desolventizing, then use 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.
By 60.00 grams of PPG(M
n=1000) join in the there-necked flask of 500mL, after dewatering 1 hour, be cooled to 50 ℃ at 120 ℃.Get AADI18.00 gram of fluorescent type vulcabond and TDI35.00 gram, DBTDL0.03 gram adds in there-necked flask, in 80 ℃ of stirring reactions, add 7.20 grams of hydrophilic chain extender DMPA, 8.60 grams of DEG and 90.00 grams of acetone after 3 hours, constant temperature is cooled to 5 ℃ at 65 ℃ of stirring reactions after 4 hours.Reaction product is proceeded to high speed shear dispersion machine, under the condition of 3000 revs/min, add 5.50 grams of TEA, react and after 5 minutes, add 240 grams of water, then stir and after 1 minute, add 0.80 gram of EDA reaction 30 minutes.Reaction product proceeds to Rotary Evaporators, under 40 ℃, 0.01MPa vacuum condition, sloughs acetone, 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:
The thickness that contains fluorescent chromophore on sheet glass is on 0.12mm latex film, to mark off region A and the region B that size is equal, with diameter, is that 90mm watch-glass covers region A, and region B directly contacts with air.Whole system is placed in 60 ℃ of baking ovens and keeps taking out after 24 hours.Get respectively the region A of identical weight and the latex film of region B is dissolved in METHYLPYRROLIDONE, being configured to concentration is 1 * 10
-5the solution of g/mL.The uv-visible absorption spectroscopy of measuring 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 region A and region 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 pages, Fig. 1 in " AATCCTestMethod140 – 2001, DyeandPigmentMigrationinaPad-DryProcess:Evaluationof " schematic diagram.
For ease of comparing, following table has provided two kinds of result datas that samples carry out respectively 3 experiments:
The latex film that the fluorescent type aqueous polyurethane emulsion that in table, FLDI-WPU is preparation forms; FL+WPU is the mixture that the direct aqueous polyurethane with not containing fluorescent chromophore of FL forms.The quality of nonvolatile element in aqueous polyurethane of take is benchmark, and in two kinds of samples, the content of fluorescent chromophore is all 6%.The mobility M that shows 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 in 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 can make fluorescence and color and luster keep 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 conventional vulcabond to combine, partly or entirely substitute conventional vulcabond, react with dihydroxyl or diamino compound and generate fluorescent type aqueous polyurethane;
The preparation of the described vulcabond that contains fluorescent chromophore comprises:
Be to adopt the monoamine contain fluorescent chromophore Fluorophore or monohydroxy-alcohol to react with triisocyanate to make a fluorescent type vulcabond, its reaction formula is expressed as:
R in formula
1for the agent structure except isocyanate groups in triisocyanate;
When the material containing fluorescent chromophore is monoamine, the N of the triisocyanate that is 20-50% by mass percent concentration, dinethylformamide solution joins in there-necked flask, stir and be warming up to 20-50 ℃, in 0.5-1 hour, dripping mass percent concentration is the DMF solution of the monoamine of 20-50%; Wherein triisocyanate is 1:1 with the ratio of monoamine amount of substance; After being added dropwise to complete, under agitation keep 20-50 ℃ of reaction to finish reaction in 1-4 hour, cooling rear underpressure distillation is except desolventizing, and product, be dried to constant weight after acetone or washed with dichloromethane in vacuum drying oven, obtains fluorescent type vulcabond;
When the material containing fluorescent chromophore is monohydroxy-alcohol, the N of the triisocyanate that is 20-50% by mass percent concentration, dinethylformamide solution joins in there-necked flask, stir and be warming up to 20-50 ℃, in 0.5-1 hour, dripping mass percent concentration 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 is wherein the dibutyl tin laurate of benchmark 0.01-0.08%, after being added dropwise to complete, under agitation keep 50-80 ℃ of reaction within 4-6 hour, to finish reaction, cooling rear underpressure distillation is except desolventizing, product, be dried to constant weight after acetone or washed with dichloromethane in vacuum drying oven, obtains fluorescent type vulcabond;
Or another kind is that diamine or the dibasic alcohol that contains fluorescent chromophore and the di-isocyanate reaction with symmetrical structure make fluorescent type vulcabond, its reaction formula is expressed as:
R in formula
2for thering is the agent structure except isocyanate groups in the vulcabond of symmetrical structure;
When the material containing fluorescent chromophore is diamine, the N of the vulcabond with symmetrical structure that is 20-50% by mass percent concentration, dinethylformamide solution joins in there-necked flask, stir and be warming up to 20-50 ℃, in 0.5-1 hour, dripping mass percent concentration is the DMF solution of the diamine of 20-50%; There is the vulcabond of symmetrical structure and the ratio of diamine amount of substance is 2:1; After being added dropwise to complete, under agitation keep 20-50 ℃ of reaction to finish reaction in 1-4 hour, cooling rear underpressure distillation is except desolventizing, and product, be dried to constant weight after acetone or washed with dichloromethane in vacuum drying oven, obtains fluorescent type vulcabond;
When the material containing fluorescent chromophore is dibasic alcohol, the vulcabond with symmetrical structure and the dibasic alcohol that by the ratio of amount of substance, are 2:1 join in there-necked flask, adding 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, at keeping 50-80 ℃ under stirring, react and within 4-6 hour, finish reaction, cooling rear underpressure distillation is except desolventizing, product is be dried to constant weight after acetone or washed with dichloromethane in vacuum drying oven, obtain fluorescent type vulcabond,
Then carry out the preparation of fluorescent type aqueous polyurethane emulsion, comprise: non-aqueous in aqueous polyurethane and quality non-solvent component of first take is benchmark, by by the macromolecule dihydric alcohol of this Reference mass 30-70% at 110-120 ℃ of dehydration 0.5-1.5 hour, by this Reference mass, add the vulcabond that contains fluorescent chromophore of 15-50% and the mixture of conventional vulcabond again, 70-100 ℃ of reaction, after 2-4 hour, add the hydrophilic chain extender of 4-8%, the dibasic alcohol chainextender of 1.5-11%, the dibutyl tin laurate of 0.01-0.08% and 20-50% acetone or butanone, at 60-90 ℃ of reaction 1-4 hour, then under the condition of high speed shear and 0-40 ℃, add the triethylamine of 3-6%, react and after 1-5 minute, add the diamine chain extenders of water and the 0-5% of 200-300%, stir, after 5-30 minute, reaction product is proceeded to Rotary Evaporators, at 40-50 ℃, under 0.01MPa vacuum condition, slough acetone or butanone, obtain fluorescent type aqueous polyurethane emulsion.
2. the preparation method of fluorescent type aqueous polyurethane as claimed in claim 1, described in being characterised in that, contain the vulcabond of fluorescent chromophore and the mixture of conventional vulcabond, the molar constituent of the vulcabond that wherein contains fluorescent chromophore in mixture be than being 2-100%, and the combination of the vulcabond that the contains fluorescent chromophore arbitrary proportion that is one or more.
3. the preparation method of fluorescent type aqueous polyurethane as claimed in claim 1, is characterised in that in described reaction formula, fluorescent chromophore Fluorophore I structure is:
4. the preparation method of fluorescent type aqueous polyurethane as claimed in claim 1, is characterised in that in described reaction formula, fluorescent chromophore Fluorophore II structure is
5. the preparation method of fluorescent type aqueous polyurethane as claimed in claim 1, is characterised in that in described reaction formula, fluorescent chromophore Fluorophore III structure is:
6. the preparation method of fluorescent type aqueous polyurethane as claimed in claim 1, is characterised in that in described reaction formula, fluorescent chromophore Fluorophore IV structure is:
7. the preparation method of fluorescent type aqueous polyurethane as claimed in claim 1, the triisocyanate that comprises R1 structure described in being characterised in that 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, the monoamine that contains fluorescent chromophore described in being characterised in that is selected from naphthalidine, 2-aminofluorene, the luxuriant and rich with fragrance amine of reddish black A, 9-or amino pyrene-1 of 8-, 3,6-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 2,3-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 conventional vulcabond 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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| CN110218292A (en) * | 2019-06-06 | 2019-09-10 | 苏州健雄职业技术学院 | A kind of preparation method of novel aqueous fluorescence polyurethane |
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