CN104861148B - A kind of aqueous polyurethane preparation method based on anionic azo hydrophilic chain extender - Google Patents
A kind of aqueous polyurethane preparation method based on anionic azo hydrophilic chain extender Download PDFInfo
- Publication number
- CN104861148B CN104861148B CN201510311813.7A CN201510311813A CN104861148B CN 104861148 B CN104861148 B CN 104861148B CN 201510311813 A CN201510311813 A CN 201510311813A CN 104861148 B CN104861148 B CN 104861148B
- Authority
- CN
- China
- Prior art keywords
- azo
- chain extender
- hydrophilic chain
- aqueous polyurethane
- hydrophilic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 92
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 90
- 239000004970 Chain extender Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000839 emulsion Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 25
- 150000001450 anions Chemical class 0.000 claims abstract description 20
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 143
- 238000006243 chemical reaction Methods 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- 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 8
- -1 amido ethyl sulfonic acid sodium Chemical compound 0.000 claims description 7
- 150000003384 small molecules Chemical class 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 229920002521 macromolecule Polymers 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 125000004427 diamine group Chemical group 0.000 claims description 4
- 125000003827 glycol group Chemical group 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 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 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 125000003944 tolyl group Chemical group 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
- 239000004425 Makrolon Substances 0.000 claims 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 claims 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 claims 1
- 229920000515 polycarbonate Polymers 0.000 claims 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 abstract description 66
- 239000000463 material Substances 0.000 abstract description 19
- 239000002245 particle Substances 0.000 abstract description 16
- 230000008859 change Effects 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 5
- 239000002539 nanocarrier Substances 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 230000004298 light response Effects 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 230000005284 excitation Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 229920006264 polyurethane film Polymers 0.000 description 10
- 230000004044 response Effects 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 4
- 239000012954 diazonium Substances 0.000 description 4
- 150000001989 diazonium salts Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 3
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- IMUUNYPYNWXUBO-UHFFFAOYSA-N 4-aminobenzene-1,3-disulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1S(O)(=O)=O IMUUNYPYNWXUBO-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 2
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 2
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000013270 controlled release Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DMLAVOWQYNRWNQ-BUHFOSPRSA-N (E)-azobenzene Chemical compound C1=CC=CC=C1\N=N\C1=CC=CC=C1 DMLAVOWQYNRWNQ-BUHFOSPRSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- QDPMLKBAQOZXEF-UHFFFAOYSA-N ethanesulfonic acid;sodium Chemical compound [Na].CCS(O)(=O)=O QDPMLKBAQOZXEF-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000004540 pour-on Substances 0.000 description 1
- 150000004672 propanoic acids Chemical class 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3836—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing azo groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of aqueous polyurethane preparation method based on anionic azo hydrophilic chain extender, conventional hydrophilic chain extender is partly or entirely substituted by the anionic azo hydrophilic chain extender containing azo chromophore azo-type anion aqueous polyurethane is made.The increase of chromophore will not cause the problem of hydrophilic radical content is by considerable restraint or reduction in polyurethane system caused by traditional copolymerization process.Using azo-type anion aqueous polyurethane prepared by the inventive method because azo chromophore is located at polyurethane molecular chain side chain, during self-emulsifying, azo hydrophilic chain extender with strongly hydrophilic is distributed in milk-globule particle surface and forms stable double electrical layerses, reversible cis-trans isomerism change of configuration can occur under relatively low energy excitation, azo group access aqueous polyurethane amount is big, and the change of ultraviolet light polyaminoester emulsion particle diameter shows that such functional material can be used as ultraviolet light response nano-carrier.
Description
First, technical field
It is specifically a kind of hydrophilic based on anionic azo the present invention relates to a kind of preparation method of aqueous polyurethane
The aqueous polyurethane preparation method of chain extender, belongs to water-base polyurethane material technical field.
2nd, background technology
Aqueous polyurethane production at present uses the normal of the non-functionals such as bishydroxymethyl propionic acid, Diaminoalkyl sulfonate
With hydrophilic chain extender, production feature aqueous polyurethane, which is also needed to be blended or is copolymerized, adds other functional materials or monomer.
As the existing method for making polyurethane have azo characteristic can be divided into two kinds of host-guest system type and response type.Host-guest system type side
, only need to be by mixing part azo micromolecular compound into polyurethane matrix, actually with this although method technique is simple
It is a mixture made from method, small molecule azo-compound therein is not only adulterated dense due to the consistency problem with matrix
The problems such as spending and be limited, and the migration in mixture material can often occur during use, oozed out from material, causes material property
Reduce；Response type method is the monomer using azo micromolecular compound as polymerisation, passes through the active official of azo-compound
It can roll into a ball to participate in polymerizeing and obtain the polyurethane containing azo chromophore structure.
Chinese patent 201310573640.7 discloses a kind of prepares azo-type aqueous polyurethane by azo dihydric alcohol
Method, this method substitute small molecule glycol chain extender using azo dihydric alcohol and prepare target material, solve blending azo
Compound causes the problems such as material resistance to migration difference, but azo dihydric alcohol addition by raw material proportioning (polyurethane synthesize in isocyanic acid
For the mol ratio of ester and hydroxyl typically between 0.8-1.2, the addition of azo dihydric alcohol can increase the hydroxyl in polyurethane proportioning rapidly
Base content) limitation it is very big, in the patent azo dihydric alcohol only partly or entirely substitute polyurethane synthesis small molecule dihydric alcohol,
Content is up to 15wt% to azo dihydric alcohol in non-aqueous non-solvent material in aqueous polyurethane.To ensure polyurethane material
Middle introducing more amount azo-compound, must now reduce the additions of other chain extenders such as hydrophilic chain extender to ensure W-response
Proportioning, the parameters such as aqueous polyurethane emulsion stability, particle diameter, outward appearance can be influenceed again by reducing hydrophilic chain extender addition.Due to adding
After the azo dihydric alcohol for entering water resistance, the azo component of water resistance enters aqueous polyurethane milk-globule electric double layer knot after self-emulsifying process
The inside of structure, the weak ultraviolet light of penetrability are difficult to be irradiated to the azo group inside milk-globule, influence the suitable anti-of azo group
Isomerization efficiency (under the ultraviolet light of specific wavelength, the azobenzene of anti-configuration is changed into the percentage of cis-configuration),
It is difficult to reach 100%.In a word, the method has certain limitation for synthesizing azo-type anion aqueous polyurethane.
3rd, the content of the invention
It is an object of the invention to provide a kind of aqueous polyurethane preparation side based on anionic azo hydrophilic chain extender
Method, using a kind of hydrophilic chain extender containing azo chromophore, this hydrophilic chain extender collection commonly uses hydrophilic chain extender and mill base, idol
Nitrogen functional characteristic partly or entirely substitutes conventional hydrophilic chain extender and small molecule glycol chain extender, so as to synthesize in one
Side chain azo-type anion aqueous polyurethane emulsion.The inventive method can not only substantially reduce the dosage of hydrophilic chain extender, and
And a kind of azo group can be obtained and be located at polyurethane side chain, during the self-emulsifying of aqueous polyurethane emulsion is formed, azo
Functional unit is distributed in the double electrical layerses surface of milk-globule particle formation, and emulsion colorfulness is high, and ultraviolet light can be easy to
It is irradiated to the azo functional group positioned at electric double layer surface and cis-trans isomerism effect occurs, there is good stimulating responsive, leads to
Stimulation oversaturation response change polyurethane milk-globule particle size, can as ultraviolet light, visible ray, thermal response nano-carrier.Such
Macromolecule emulsion has certain application prospect in terms of functional coating, off-color material, medicine even load thing are controlled release.
The preparation method of aqueous polyurethane of the present invention, it is characterised in that：With anionic azo hydrophilic chain extender part or
Replacing whole is cloudy with diisocyanate, macromolecule dihydric alcohol reaction generation azo-type often with hydrophilic chain extender, small molecule dihydric alcohol
Ion aqueous polyurethane.
The anionic azo hydrophilic chain extender includes carboxylic acid type azo hydrophilic chain extender and/or sulfonic acid type azo is hydrophilic
Chain extender；
The structural formula of the carboxylic acid type azo hydrophilic chain extender is：
The structural formula of the sulfonic acid type azo hydrophilic chain extender is：
The preparation method of aqueous polyurethane of the present invention, comprises the following steps：
Macromolecule dihydric alcohol is dehydrated 0.5-1.5 hours in 110-130 DEG C, diisocyanate is then added, in 70-100
Anionic azo hydrophilic chain extender, conventional hydrophilic chain extender, glycol chain extender, two bays are added after DEG C reaction 2-4 hours
Sour dibutyl tin (DBTDL) and stannous octoate, add solvent, are reacted 1-4 hours at 60-90 DEG C, and reaction end is cooled to 30-
60 DEG C, add ethylenediamine base ethyl sulfonic acid sodium and carry out chain extension, then add sodium hydroxide under conditions of high speed shear and 0-40 DEG C
And triethylamine, water and diamine chain extenders are added after reacting 1-5 minutes, reaction solution is transferred to rotary evaporation after stirring 5-30 minutes
Instrument, solvent is sloughed under 40-50 DEG C, 0.01MPa vacuum conditions, azo-type anion aqueous polyurethane emulsion is made；It is described molten
Agent is acetone or butanone；
The addition of each raw material is formed as follows by mass fraction：
The macromolecule dihydric alcohol is selected from polyadipate -1,4- butyl glycol ester diols (PBA), polycaprolactone diols
(PCL), PCDL (PCDL), PTMG dihydric alcohol (PTMG), poly (propylene carbonate) dihydric alcohol (PPC) or
Polypropylene glycol (PPG)；
The diisocyanate is selected from toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI), different Buddhist
That ketone diisocyanate (IPDI) or hexamethylene diisocyanate (HDI)；
The conventional hydrophilic chain extender is selected from dihydromethyl propionic acid (DMPA), bishydroxymethyl butyric acid (DMBA) or tartaric acid
(TA)；
The glycol chain extender is selected from ethylene glycol (EG), 1,4- butanediols (BDO), 1,6-HD (HDO) or a contracting
Diethylene glycol (DEG)；
The diamine chain extenders are selected from ethylenediamine (EDA) or IPD (IPDA).
The anionic azo hydrophilic chain extender that the present invention uses includes carboxylic acid type azo hydrophilic chain extender and/or sulfonic acid type
Azo hydrophilic chain extender；
The preparation process of carboxylic acid type azo hydrophilic chain extender is as follows：
1) the 2- amino terephthalic acid (TPA)s of 100 mass parts are added in there-necked flask, then add 500-1000 mass parts
Water be sufficiently stirred to form solution, 10-20 mass parts concentrated hydrochloric acids (mass concentration 36-38%) are then slowly added dropwise and arrive there-necked flask
In, control system temperature is 0-5 DEG C, the mass parts 50wt% of fast drop 38 (mass concentration, similarly hereinafter) sodium nitrite solution, is protected
Hold ice-water bath conditioned response 1-2 hours, generate the diazonium salt solution of 2- amino terephthalic acid (TPA)s；
2) by 102 mass parts N, N- dihydroxyethylbenzenands amine solvent is in 100-300 mass parts Methanols and 0-10 mass parts acetic acid
Middle formation N, N- dihydroxy ethyl aniline solution, the diazonium salt solution that 2- amino terephthalic acid (TPA)s made from step 1) are then added dropwise arrive
In N, N- dihydroxy ethyl aniline solution, dripped off in 0.5-1h；Utilize the pH value of 1mol/L sodium hydroxide solutions regulation mixed solution
For 4-6, it is added dropwise to complete rear keeping body and ties up to reaction 2-4 hours at 0-5 DEG C, last regulation system pH value is 4-8, and second is used after filtering
Alcohol, which washs and is dried under vacuum to constant weight, obtains carboxylic acid type azo hydrophilic chain extender, and its chemical name is N, N- dihydroxy ethyls -4-
(3 ', 6 '-dicarboxyl acidic group phenylazo) aniline.
The preparation process of sulfonic acid type azo hydrophilic chain extender is as follows：
1) 100 mass parts aniline -2,4- disulfonic acid are added in there-necked flask, then add the water of 500-1000 mass parts
It is sufficiently stirred to form solution, 100-150 mass parts concentrated hydrochloric acids (mass concentration 36-38%) is slowly added dropwise into there-necked flask, controls
System temperature is 0-5 DEG C, the mass parts 50wt% of fast drop 27 sodium nitrite solution, keeps ice-water bath conditioned response 1-2 small
When, the diazonium salt solution of generation aniline -2,4- disulfonic acid；
2) by 74 mass parts N, N- dihydroxyethylbenzenands amine solvent is in 100-400 mass parts Methanols and 0-10 mass parts acetic acid
Formation N, N- dihydroxy ethyl aniline solutions, the subsequent diazonium salt solution that aniline -2,4- disulfonic acid made from step 1) is added dropwise to N,
In N- dihydroxy ethyl aniline solutions, dripped off in 0.5-1h, the pH value that mixed solution is adjusted using 1mol/L sodium hydroxide solutions is
4-6, it is added dropwise to complete rear keeping body and ties up to reaction 2-4 hours at 0-5 DEG C, last regulation system pH value is 4-8, depressurizes and steams at 55 DEG C
Evaporate after -20 to -5 DEG C of cold filtrations, then washed with ethanol and obtain the hydrophilic chain extension of sulfonic acid type azo after being dried under vacuum to constant weight
Agent, its chemical name are N, N- dihydroxy ethyls -4- (2 ', 4 '-disulfonic acid base phenylazo) aniline.
Preparation method of the present invention has advantages below compared with prior art：
1st, the present invention uses anion azo hydrophilic chain extender as raw material, partly or entirely substitutes conventional hydrophilic chain extender,
Also other small molecule chain extenders can be partly or entirely substituted to prepare coloured azo-type anion aqueous polyurethane.
2nd, anion azo-type aqueous polyurethane prepared by the present invention, uncle is contained because the azo hydrophilic chain extender used removes
Outside amine structure, also containing two sulfonic acid or hydroxy-acid group, itself can be with self-contained salt, and hydrophily is stronger, azo chromophore and hydrophilic
The increase of group is linear, will not mutually limit.So it will not cause in polyurethane system caused by conventional polycondensation method
The problem of hydrophilic radical, small molecule dihydric alcohol are fed intake by considerable restraint or reduction, azo dihydric alcohol is non-aqueous in aqueous polyurethane
Content can reach 20.87wt% in property non-solvent material.
3rd, preparation method of the present invention reduces the process of production azo-type aqueous polyurethane in process of production, and it is cloudy from
When forming coloured aqueous polyurethane emulsion, due to azo chromophore, chemistry is typed into polyurethane point to sub- azo hydrophilic chain extender
In subchain, compared with small molecule dyes or pigment are directly mixed in the material of polyurethane body by routine, the poly- ammonia of the invention prepared
The polyurethane material azo chromophore that ester emulsion is formed after dehydration is evenly distributed, and is not in that surface is faded, grown dim after film forming
Phenomena such as, azo functional characteristic can persistently be kept.
4th, few aqueous polyurethane hydrophilic monomer dosage, high solids content, resistance to can be prepared using sulfonic acid type azo hydrophilic chain extender
The good coloured aqueous polyurethane of acid-base property；The azo-type aqueous polyurethane emulsion prepared using carboxylic acid type azo hydrophilic chain extender is steady
Fixed, water-tolerant, the material that sulfonic acid type is mixed to prepare with sulfonic acid type azo hydrophilic chain extender has sulfonic acid type concurrently and carboxylic acid type is water-based
Some advantages of polyurethane.
5th, using azo-type aqueous polyurethane prepared by the inventive method because azo chromophore is located at polyurethane molecular chain
Side chain, during self-emulsifying, there is the azo monomer cell distribution of strongly hydrophilic sulfonate or carboxylate structure in milk-globule particle
Surface forms stable double electrical layerses, compared with low energy (6mW/cm2) excite down reversible cis-trans isomerization configuration can occur
Change (isomerization efficiency is up to 100%).
6th, using azo-type aqueous polyurethane prepared by the inventive method because azo chromophore is located at polyurethane molecular chain
Side chain, there is the azo monomer cell distribution of strongly hydrophilic sulfonate or carboxylate structure to form stabilization in milk-globule particle surface
Double electrical layerses, the particle size of polyurethane as ultraviolet light, the nano-carrier of thermal response, can be changed by stimuli responsive
(double electrical layerses have fine and closely woven micropore, can control micropore size by adjusting particle size), bears to carrier inside
Loading is controlled release etc., greatly expands the application of azo polyurethane.
4th, illustrate
Fig. 1 is based on the synthetically prepared azo-type anionic water of sulfonic acid type azo hydrophilic chain extender in the embodiment of the present invention 5
In Fu of property polyurethane (PU1, PU2, PU3) and the anion aqueous polyurethane (PU0) without sulfonic acid type azo hydrophilic chain extender
Leaf transformation infrared spectrogram.
Fig. 2 be in the embodiment of the present invention 5 the azo-type anion aqueous polyurethane emulsion (PU2) for preparing wavelength 365nm,
Radiant illumination is 6mW/cm2Different time illumination under at caused 443nm absorbance change spectrogram.
Fig. 3 is the azo-type anion aqueous polyurethane film (PU1) prepared in the embodiment of the present invention 5 by ultraviolet lighting
Penetrate contact angle variation diagram.
Fig. 4 is the azo-type anion aqueous polyurethane emulsion PU3 prepared in the embodiment of the present invention 5 in ultraviolet light
Grain size distribution after (365nm) pre-irradiation.
5th, embodiment
Embodiment 1：
By 50.00g PBA (Mn=3200) it is added in 500mL three-necked flask, it is cold after being dehydrated 1 hour at 110 DEG C
But to 55 DEG C, take 11.10g TDI to add in three-necked flask, 9.60g sulfonic acid type azos are added after 3 hours in 80 DEG C of stirring reactions
Hydrophilic chain extender, 1.50g DEG, 0.01g DBTDL and 45.00g butanone, constant temperature are cooled to after 3 hours in 70 DEG C of stirring reactions
30 DEG C, reaction solution is transferred to high speed shear dispersion machine, 4.36g TEA are added under conditions of 3000 revs/min, after reacting 5 minutes
150g water is added, 0.35g EDA are added after being stirred for 1 minute and are reacted 30 minutes, reaction solution are transferred to Rotary Evaporators, 45
DEG C, slough butanone under 0.01MPa vacuum conditions, obtain sulfonic acid type azo aqueous polyurethane emulsion.
If other conditions of the present embodiment are constant, and PBA is changed into PCL, PCDL, PTMG or PPG respectively, can obtain steady
Fixed coloured aqueous polyaminoester emulsion.
Embodiment 2：
By 160.00g PPG (Mn=2000) it is added in 1000mL three-necked flask, after being dehydrated 1 hour at 120 DEG C
60 DEG C are cooled to, takes 62.10g IPDI to add in three-necked flask, 17.20g carboxylic acid types are added after 3 hours in 90 DEG C of stirring reactions
Azo hydrophilic chain extender, 6.90g BDO, 0.01g DBTDL and 120.00g acetone, constant temperature are dropped after 3 hours in 75 DEG C of stirring reactions
Reaction solution is transferred to high speed shear dispersion machine by temperature to 30 DEG C, and 14.66g TEA are added under conditions of 3000 revs/min, reacts 5 points
580g water is added after clock, 0.90g IPDA are added after being stirred for 1 minute and are reacted 30 minutes, reaction solution is transferred to Rotary Evaporators,
Acetone is sloughed under 40 DEG C, 0.01MPa vacuum conditions, obtains carboxylic acid type azo aqueous polyurethane emulsion.
If other conditions of the present embodiment are constant, and BDO is changed into HDO, EG or DEG respectively, what can be stablized has
Color aqueous polyurethane emulsion.
If other conditions of the present embodiment are constant, and change DA into TA or DMBA, what can be stablized is coloured aqueous poly-
Urethane emulsion.
Embodiment 3：
By 80.00g PTMG (Mn=2000) it is added in 500mL three-necked flask, it is cold after being dehydrated 1 hour at 120 DEG C
But to 60 DEG C, take 35.10g IPDI to add in three-necked flask, 2.30g carboxylic acid type azos are added after 3 hours in 90 DEG C of stirring reactions
Hydrophilic chain extender, 5.5g dihydromethyl propionic acids, 6.90g HDO, 0.01g DBTDL and 70.00g butanone, constant temperature is in 75 DEG C of stirrings
Reaction is cooled to 30 DEG C after 3 hours, and reaction solution is transferred into high speed shear dispersion machine, 5.39g is added under conditions of 3000 revs/min
TEA, reaction add 290g water after 5 minutes, Rotary Evaporators are transferred to after being stirred for 1 minute, in 45 DEG C, 0.01MPa vacuum conditions
Under slough butanone, obtain carboxylic acid/coloured aqueous polyaminoester emulsion of sulfonic acid mixed type.
Embodiment 4：
By 50.00g PTMG (Mn=2000) it is added in 500mL three-necked flask, it is cold after being dehydrated 1 hour at 120 DEG C
But to 60 DEG C, take 25.10g IPDI to add in three-necked flask, 3.80g carboxylic acid type azos are added after 3 hours in 90 DEG C of stirring reactions
Hydrophilic chain extender, 8.4g carboxylic acid type azos hydrophilic chain extender, 4.10g BDO, 0.01g DBTDL and butanone 35.00g, constant temperature exist
75 DEG C of stirring reactions are cooled to 30 DEG C after 3 hours, reaction solution are transferred into high speed shear dispersion machine, under conditions of 3000 revs/min
5.86g TEA are added, reaction adds 210g water after 5 minutes, and 0.28g EDA are added after being stirred for 1 minute and are reacted 30 minutes, will be anti-
Answer liquid to be transferred to Rotary Evaporators, butanone is sloughed under 45 DEG C, 0.01MPa vacuum conditions, obtain carboxylic acid/sulfonic acid mixed type colored water
Property polyaminoester emulsion.
If other conditions of the present embodiment are constant, and change TEA into sodium hydroxides, what can be stablized is coloured aqueous poly-
Urethane emulsion.
If other conditions of the present embodiment are constant, and change IPDI into MDI, TDI or HDI, what can be stablized is coloured
Aqueous polyurethane emulsion.
Embodiment 5：
By 56.00g number-average molecular weights MnFor 2000 PTMG be dehydrated 1 hour at 110 DEG C after be cooled to 50 DEG C, Ran Houjia
Enter 22.23g IPDI, 6.03g DMPA, 0.89g sulfonic acid type azo hydrophilic chain extenders are added after 2 hours in 90 DEG C of stirring reactions
(BAPBDA), 1.80g BDO, 0.05g dibutyl tin laurates, 0.05g stannous octoates and 85.00g butanone.Constant temperature is at 70 DEG C
Stirring reaction is cooled to 25 DEG C after 5 hours, reaction solution is transferred into high speed shear dispersion machine, added under conditions of 3000 revs/min
5.0g TEA, reaction 5 minutes after add 200g water, be stirred for that reaction solution is transferred into Rotary Evaporators after 5 minutes, 50 DEG C,
Butanone is sloughed under 0.01MPa vacuum conditions, that is, is obtained solid containing (non-aqueous non-solvent material and water-based poly- ammonia in aqueous polyurethane
The mass ratio of ester emulsion) it is 30.3%, DMPA and azo the hydrophilic chain extender non-aqueous non-solvent material in aqueous polyurethane
Middle content is respectively 6.94% and 1.02% azo-type anion aqueous polyurethane emulsion PU2.
Table 1
Such as keep other conditions constant, BAPBDA replacing wholes DMPA (mol ratio replacement) can equally be obtained into azo-type
Anion aqueous polyurethane emulsion PU4.Such as keep other conditions constant, according to the formula rate of table 1, adjust BDO's and BAPBDA
The ratio between amount of material, it is respectively 0.51% and 1.53% that aqueous polyurethane PU0 and the BAPBDA content without BAPBDA, which is made,
Anion azo aqueous polyurethane PU1, PU3.Wt% is that BAPBDA accounts for non-aqueous non-solvent material in aqueous polyurethane in table 1
The percentage of quality.Such as keep other conditions constant, can by adjust PTMG, IPDI, DMPA and BAPBDA material amount it
Than the side chain for obtaining BAPBDA content differences (0.2-20.87%) in non-aqueous non-solvent material in aqueous polyurethane is even
Nitrogen type anion aqueous polyurethane emulsion.
Fig. 1 is for the synthetically prepared azo-type anion aqueous polyurethane (PU1, PU2, PU3) of the present embodiment and without sulfonic acid
The Fourier transform infrared spectroscopy figure of the anion aqueous polyurethane (PU0) of type azo hydrophilic chain extender.Find out the spy of polyurethane
Sign absworption peak is located at 3334cm respectively-1(νN-H)、2856-2949cm-1(νCH2andνCH3)、1714cm-1(νC=O) and 1114cm-1
(νC-O-C) place；In azo-type anion aqueous polyurethane spectrogram, all characteristic absorption peaks of polyurethane are not only can be seen that, it is also aobvious
1570cm is shown-1And 1415cm-1The characteristic absorption peak at (phenyl ring in azo-compound structure) place, illustrates that sulfonic acid type azo is hydrophilic
Chain extender take part in reaction in synthetically prepared polyurethane completely.
Azo chromophore part in azo anion aqueous polyurethane PU2 strands has typical photic configuration isomery
Characteristic.Accompanying drawing 2 is azo anion aqueous polyurethane emulsion PU2 in wavelength 365nm, radiant illumination 6mW/cm2Illumination under
443nm or so place's absorbances caused by the transisomer of azobenzene structure part changes to the configuration of cis-isomer
Change.As the absorbance at extension, 443nm or so the place of irradiation time is gradually reduced；Irradiate in 0-10 minutes, absorbance
Value is rapid to be reduced；About after 16 minutes, absorbance change very little, at the 34th minute, the apparent colour of emulsion was from during firm irradiation
Orange-yellow to be changed into colourless, absorbance no longer changes substantially.After self-emulsifying process, the azo component position with hydrophilic radical
Outside polyurethane milk-globule, i.e., the azo monomer cell distribution with strongly hydrophilic sulfonate structures is formed in milk-globule particle surface
Stable double electrical layerses, by ultraviolet light, the azobenzene of anti-configuration is completely reformed into cis structure in the extremely short time
Type, cis-trans isomerization efficiency reach 100%.Stop irradiation after, due to molecular thermalmotion, azobenzene structure be partially in energy compared with
The cis-isomer of high state gradually changes to transisomer again, and this reversible cis-trans isomerization change is final to make emulsion again
Apparent colour from it is colourless be changed into it is orange-yellow.Azo in description of test azo polyurethane strand manufactured in the present embodiment
Chromophore has typical photic configuration isomery characteristic, and with 100% isomerization efficiency.
Take a certain amount of azo aqueous polyurethane emulsion to pour on clean glass plate, be put at level and place one week, allow breast
Moisture in liquid slowly volatilizees, and is then placed in baking oven 60 DEG C of dryings two days to constant weight, azo aqueous polyurethane milk-globule film is made,
Its thickness is between 100-120 μm.Table 2 is azo-type anion aqueous polyurethane film (PU1, PU2, PU3 manufactured in the present embodiment
And PU4), after by 365nm ultraviolet lights 20 minutes, the contact angle of film reduces polyurethane film.Fig. 3 is this implementation
PU1 films prepared by example pass through ultraviolet lighting polyurethane film contact angle variation diagram, and polymer film is made to locate under 365nm ultraviolet lightings
For reason after 10 minutes, contact angle is reduced to 77.84 ° from 81.31 °.Milk-globule film is after the irradiation of 365nm ultraviolets, due to cis-structure
Formation, cis isomeric effect molecule and the dipole moment change and structural rearrangement effect of trans-azobenzene, cause Static Water to connect
Feeler reduces.
Table 2
Fig. 4 is particle diameters of the azo aqueous polyurethane emulsion PU4 manufactured in the present embodiment after ultraviolet light (365nm) pre-irradiation
Distribution map, as can be seen from the figure the configuration of azo double bond be transformed into cis-configuration from trans, which results in milk-globule particle
The change in footpath, illustrate that the emulsion has good ultraviolet light response.It is water-based being formed because azo group is located at polyurethane side chain
During the self-emulsifying of polyaminoester emulsion, azo functional unit is distributed in the double electrical layerses surface of milk-globule particle formation, ultraviolet
Light can be easy to the azo functional group being irradiated to positioned at electric double layer surface and cis-trans isomerism effect occurs.Meanwhile from molecule
From the perspective of accumulation, even closer accumulation mode is more readily formed in the anti-configuration of azo double bond.And cis-structure is then anti-
It.So after ultraviolet light, the particle diameter of emulsion particle increases, while particle diameter distribution broadens.
Claims (7)
- A kind of 1. aqueous polyurethane preparation method based on anionic azo hydrophilic chain extender, it is characterised in that：With anion Type azo hydrophilic chain extender partly or entirely substitutes conventional hydrophilic chain extender and small molecule dihydric alcohol, synthesizes azo-type anionic water Property polyurethane；The anionic azo hydrophilic chain extender includes carboxylic acid type azo hydrophilic chain extender and/or the hydrophilic chain extension of sulfonic acid type azo Agent；The structural formula of the carboxylic acid type azo hydrophilic chain extender is：The structural formula of the sulfonic acid type azo hydrophilic chain extender is：Specifically comprise the following steps：Macromolecule dihydric alcohol is dehydrated 0.5-1.5 hours in 110-130 DEG C, then adds diisocyanate, it is anti-in 70-100 DEG C Anionic azo hydrophilic chain extender, conventional hydrophilic chain extender, glycol chain extender, tin dilaurate two are added after answering 2-4 hours Butyl tin and stannous octoate, add solvent, are reacted 1-4 hours at 60-90 DEG C, and reaction end is cooled to 30-60 DEG C, adds second Two amido ethyl sulfonic acid sodium carry out chain extension, sodium hydroxide and triethylamine are then added under conditions of high speed shear and 0-40 DEG C, instead Water and diamine chain extenders are added after answering 1-5 minutes, reaction solution are transferred to Rotary Evaporators after stirring 5-30 minutes, in 40-50 DEG C, slough solvent under 0.01MPa vacuum conditions, azo-type anion aqueous polyurethane emulsion is made；The addition of each raw material is formed as follows by mass fraction：
- 2. according to the method for claim 1, it is characterised in that：The macromolecule dihydric alcohol is selected from polyadipate -1,4- butyl glycol ester diols, polycaprolactone diols, makrolon binary Alcohol, PTMG dihydric alcohol, poly (propylene carbonate) dihydric alcohol or polypropylene glycol.
- 3. according to the method for claim 1, it is characterised in that：The diisocyanate is selected from toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, IPDI Or hexamethylene diisocyanate.
- 4. according to the method for claim 1, it is characterised in that：The conventional hydrophilic chain extender is selected from dihydromethyl propionic acid, bishydroxymethyl butyric acid or tartaric acid.
- 5. according to the method for claim 1, it is characterised in that：The glycol chain extender is selected from ethylene glycol, 1,4- butanediols, 1,6-HD or diglycol.
- 6. according to the method for claim 1, it is characterised in that：The diamine chain extenders are selected from ethylenediamine or IPD.
- 7. according to the method for claim 1, it is characterised in that：The solvent is acetone or butanone.
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| CN105111910B (en) * | 2015-09-17 | 2018-01-23 | 黑龙江大学 | A kind of method of the isocyanate component of anionic method synthesis aqueous polyurethane coating with bi component |
| CN109535361B (en) * | 2018-11-12 | 2021-09-03 | 中山大学 | Ultraviolet light irradiation mechanical response waterborne polyurethane and preparation method thereof |
| CN109880049A (en) * | 2019-02-26 | 2019-06-14 | 安徽清彩科技有限公司 | A kind of colored preparation method and application for covering polyaminoester emulsion of copolymerization |
| CN109912775A (en) * | 2019-04-04 | 2019-06-21 | 北京材华科技有限公司 | A kind of double stimuli responsive Water-based polyurethane elastomer and preparation method thereof |
| CN114133505A (en) * | 2021-12-30 | 2022-03-04 | 盐城工学院 | Preparation method of photochromic film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653585A (en) * | 2012-05-15 | 2012-09-05 | 陕西科技大学 | Method for preparing sulfoacid/carboxylic acid waterborne polyurethane |
| CN102924682A (en) * | 2012-09-29 | 2013-02-13 | 嘉兴禾欣化学工业有限公司 | Preparation method of colorful polyurethane emulsion |
| CN103641973A (en) * | 2013-11-15 | 2014-03-19 | 宏元(江门)化工科技有限公司 | Preparation method for side-chain azo-type aqueous polyurethane |
-
2015
- 2015-06-08 CN CN201510311813.7A patent/CN104861148B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653585A (en) * | 2012-05-15 | 2012-09-05 | 陕西科技大学 | Method for preparing sulfoacid/carboxylic acid waterborne polyurethane |
| CN102924682A (en) * | 2012-09-29 | 2013-02-13 | 嘉兴禾欣化学工业有限公司 | Preparation method of colorful polyurethane emulsion |
| CN103641973A (en) * | 2013-11-15 | 2014-03-19 | 宏元(江门)化工科技有限公司 | Preparation method for side-chain azo-type aqueous polyurethane |
Non-Patent Citations (3)
| Title |
|---|
| New azo dyes as colored isoelectric point markers for isoelectric focusing in acidic pH region;Miroslava Štastná et al.;《Electrophoresis》;20041229;第26卷(第01期);第53-59页 * |
| 一种偶氮染料接枝聚氨酯的合成与表征;易文辉等;《西安交通大学学报》;20021020;第36卷(第10期);第1024-1027页 * |
| 系列聚氨酯偶氮发色团的合成、表征及合成路线的探讨;杨有清等;《中南民族大学学报(自然科学版)》;20060630;第25卷(第02期);第22-24页 * |
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