CN104945276A - Azo hydrophilic compound as well as preparation method and application thereof - Google Patents
Azo hydrophilic compound as well as preparation method and application thereof Download PDFInfo
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- CN104945276A CN104945276A CN201510311843.8A CN201510311843A CN104945276A CN 104945276 A CN104945276 A CN 104945276A CN 201510311843 A CN201510311843 A CN 201510311843A CN 104945276 A CN104945276 A CN 104945276A
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- -1 Azo hydrophilic compound Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004814 polyurethane Substances 0.000 claims abstract description 39
- 229920002635 polyurethane Polymers 0.000 claims abstract description 39
- 239000004970 Chain extender Substances 0.000 claims abstract description 33
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 46
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000012954 diazonium Substances 0.000 claims description 14
- 150000001989 diazonium salts Chemical class 0.000 claims description 14
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000005457 ice water Substances 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- 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 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 235000010288 sodium nitrite Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 230000001143 conditioned effect Effects 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- 238000007697 cis-trans-isomerization reaction Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 239000002539 nanocarrier Substances 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 10
- 235000011167 hydrochloric acid Nutrition 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 5
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- 229920000570 polyether Polymers 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 101150099549 azo1 gene Proteins 0.000 description 3
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000004936 stimulating effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000009736 wetting Methods 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical class CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical group [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 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 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an azo hydrophilic compound as well as a preparation method and application thereof. The azo hydrophilic compound comprises a carboxylic acid type azo hydrophilic compound or a sulfonic acid type azo hydrophilic compound. During the self-emulsifying process that the azo hydrophilic compound provided by the invention is used as a chain extender to form a polyurethane emulsion, the azo hydrophilic chain extender with good hydrophilic property is distributed on the surfaces of emulsified ball particles to form a stable double-electrode-layer structure, and the cis-trans isomerization efficiency can reach 100%; the variation of the particle diameter of the polyurethane emulsion under the ultraviolet irradiation shows that the functional material can be used as an ultraviolet responsive nano-carrier, and has potential application prospect in the aspect of forming azo water-soluble polyester and other color-changing polymer materials.
Description
One, technical field
The present invention relates to a kind of azo hydrophilic compounds and its production and use, azo hydrophilic compounds of the present invention can as the hydrophilic chain extender of aqueous polyurethane synthesis.
Two, background technology
Hydrophilic chain extender is one of raw material that must use in aqueous polyurethane synthesis preparation process, its object is to introduce hydrophilic radical in urethane, gives aqueous polyurethane wetting ability.Conventional hydrophilic chainextender mainly contains dimethylol propionic acid, dimethylolpropionic acid and quadrol base ethyl sulfonic acid sodium etc., usually containing carboxyl, sulfonic acid group or secondary amine in this kind of chainextender, make on urethane side chain or main chain with the ionizable characteristic group of energy when it is attached in polyurethane molecular, the effect of aqueous polyurethane hydrophilic radical is only provided, other can not be provided functional.At present, the hydrophilic chain extender kind that aqueous polyurethane uses is few, and hydrophilic chain extender is without other functional performance.Most conventional hydrophilic chain extender is produced complicated, and cost is high, and as conventional dimethylol propionic acid, a kind of conventional preparation method is formaldehyde and propionic aldehyde synthesis dihydroxymethyl propionic aldehyde, then becomes dimethylol propionic acid with hydrogen peroxide oxidation.
At present, research for novel hydrophilic chainextender more and more receives the concern of people, as novel hydrophilic chainextenders such as Chinese patent 2012102156119, disclosed sulfonic acid type, sulfonic acid/carboxylic acid type, the sulfonic acid/tertiary amine-type such as 201210045962X, 201310632545X, this hydrophilic chain extender is only the simple wetting ability that must increase resin, without other functional performance, synthesis technique is complicated, and molecular weight is large, and industrial prospect is undesirable.
The aqueous polyurethane coating mainly prepared aqueous high molecular dyestuff, aqueous pigmented coating, aqueous pigmented paint and have photoelectric characteristic applied by azoic dyestuff in aqueous polyurethane, the Oil Soluble Azo Dyes that uses passes through dispersant more at present, then blendedly join in aqueous polyurethane, complex manufacturing, the resistance to migration-type of the colored materials obtained is poor.Although can obtain the good azobenzene polymer of resistance to migration energy by response type azo-compound, azo-compound (azo dibasic alcohol) kind at present with two hydroxyl structure is few, and most based on phenolic hydroxyl group, reactive behavior is low.Chinese patent 201310572158.1,201310573640.7 are disclosed the azo dibasic alcohol of multiple hydroxyl structure symmetry and are prepared the method for azo-type aqueous polyurethane by these azo dibasic alcohol, the method prepares side chain azo polyurethane material by using azo glycol section or replacing whole small molecules glycol chain extender, but azo dibasic alcohol add-on affects very large by proportioning raw materials (in urethane synthesis, the mol ratio of isocyanic ester and hydroxyl is generally between 0.8-1.2) and the proportioning of small molecules dibasic alcohol in system, use hydrophilic chain extender and azo dibasic alcohol that manufacturing cost also can be caused to increase simultaneously, and due to add water tolerance azo dibasic alcohol after, after self-emulsifying process, the azo component of water tolerance enters the inside of aqueous polyurethane milk-globule double electrical layers, the UV-light that penetrance is weak or visible ray are difficult to be irradiated to the azo group being positioned at milk-globule inside, affect the cis-trans isomerization efficiency of azo group (under the UV-irradiation of specific wavelength, the nitrogen benzide of transconfiguration changes the per-cent of cis-configuration into), be difficult to reach 100%.
So synthesis one has hydroxyl structure symmetry, with the multi-functional diatomic alcohol compounds of the functional performance such as hydrophilic radical and azo, has great using value and prospect.
Three, summary of the invention
The object of the present invention is to provide a kind of azo hydrophilic compounds and its production and use, azo hydrophilic compounds of the present invention is a kind of functional dibasic alcohol, both has hydrophilic radical, and has azo chromophore again.This functional dibasic alcohol is in the self-emulsifying process forming aqueous polyurethane emulsion, the azo functional unit with strongly hydrophilic structure is distributed in milk-globule particle surface and forms stable double electrical layers, emulsion colorfulness is high, the functional group being positioned at electrostatic double layer surface has good stimulating responsive, improve cis-trans isomerization efficiency and the content of azo group in urethane, can as the nano-carrier of UV-light, thermal response, changed the size of urethane by stimuli responsive, Co ntrolled release etc. is carried out to the loaded article of carrier inside.In addition, this functional diatomic alcohol compounds not only can directly apply to synthesis azo-type aqueous polyurethane, in formation azo water-soluble polyester, polycarbonate, polyethers or polyether ester, also have potential application prospect.
Azo hydrophilic compounds of the present invention comprises carboxylic acid type azo hydrophilic compounds or sulfonic acid type azo hydrophilic compounds;
Carboxylic acid type azo hydrophilic compounds is N, N-dihydroxy ethyl-4-(3 ', 6 '-dicarboxyl acidic group phenylazo) aniline, and structure is as follows:
Sulfonic acid type azo hydrophilic compounds is N, N-dihydroxy ethyl-4-(2 ', 4 '-disulfonic acid base phenylazo) aniline, and structure is as follows:
The preparation method of carboxylic acid type azo hydrophilic compounds of the present invention comprises the steps:
1) amino for the 2-of 100 mass parts terephthalic acid is joined in there-necked flask, the water adding 500-1000 mass parts subsequently fully stirs formation solution, then 10-20 mass parts concentrated hydrochloric acid (mass concentration 36-38%) is slowly dripped in there-necked flask, hierarchy of control temperature is 0-5 DEG C, fast drop 38 mass parts 50wt% (mass concentration, sodium nitrite solution down together), keep ice-water bath conditioned response 1-2 hour, generate the diazonium salt solution of the amino terephthalic acid of 2-;
2) by 102 mass parts N, N-dihydroxyethylbenzenand amine solvent forms N in 100-300 mass parts Methanol and 0-10 mass parts acetic acid, N-dihydroxy ethyl aniline solution, dripping step 1 subsequently) diazonium salt solution of the obtained amino terephthalic acid of 2-is to N, in N-dihydroxy ethyl aniline solution, drip off in 0.5-1h; 1mol/L sodium hydroxide solution is utilized to regulate the pH value of mixing solutions to be 4-6, be added dropwise to complete at rear holder ties up to 0-5 DEG C and react 2-4 hour, last regulation system pH value is 4-8, by washing with alcohol and vacuum-drying to constant weight obtains carboxylic acid type azo hydrophilic compounds after filtration.
The preparation method of sulfonic acid type azo hydrophilic compounds of the present invention comprises the steps:
1) by 100 mass parts aniline-2,4-disulfonic acid joins in there-necked flask, the water adding 500-1000 mass parts subsequently fully stirs formation solution, slow dropping 100-150 mass parts concentrated hydrochloric acid (mass concentration 36-38%) is in there-necked flask, hierarchy of control temperature is 0-5 DEG C, the sodium nitrite solution of fast drop 27 mass parts 50wt%, keeps ice-water bath conditioned response 1-2 hour, generate the diazonium salt solution of aniline-2,4-disulfonic acid;
2) by 74 mass parts N, N-dihydroxyethylbenzenand amine solvent forms N in 100-400 mass parts Methanol and 0-10 mass parts acetic acid, N-dihydroxy ethyl aniline solution, drip step 1 subsequently) obtained aniline-2, the diazonium salt solution of 4-disulfonic acid is to N, in N-dihydroxy ethyl aniline solution, drip off in 0.5-1h, 1mol/L sodium hydroxide solution is utilized to regulate the pH value of mixing solutions to be 4-6, be added dropwise to complete at rear holder ties up to 0-5 DEG C and react 2-4 hour, last regulation system pH value is 4-8, in-20 to-5 DEG C of cold filtrations after underpressure distillation at 55 DEG C, sulfonic acid type azo hydrophilic compounds is obtained after vacuum-drying to constant weight again by washing with alcohol.
The purposes of azo hydrophilic compounds of the present invention, it is characterized in that can some or all of alternative synthesis of polyurethane time the conventional hydrophilic chainextender that uses and small molecules glycol chain extender, improve the content of azo group in urethane, in the self-emulsifying process forming aqueous polyurethane emulsion, the azo functional unit distribution ball milk-globule particle surface with strongly hydrophilic structure is made to form stable double electrical layers, the functional group being positioned at electrostatic double layer surface has good stimulating responsive, then aqueous polyurethane is given to UV-light, the stimulating responsive of visible ray and heat, improve cis-trans isomerization efficiency simultaneously.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, azo hydrophilic compounds of the present invention is different from conventional hydrophilic chainextender, both polyurethane hydrophilic is given containing hydrophilic radical in its molecule, urethane azo photoelectric characteristic and color is given again containing the azo chromophore that dyefastness is higher, not only fill up the blank of functional type hydrophilic chain extender, and simplify the Production Flow Chart of functional type aqueous polyurethane, save or do not use conventional hydrophilic chain extender, reaching cost-saving object.
2, azo hydrophilic compounds of the present invention partly or entirely can replace the conventional hydrophilic chainextender that aqueous polyurethane synthesis uses, also can be used as common glycol chain extender to use, improve the content of azo chromophore in polyurethane molecular chain (0.2-20.87wt%), and azo chromophore is that chemistry is typed in molecular chain and urethane milk-globule outside in material, colorfulness is high, azo chromophore is evenly distributed, and not easily moves, and azo functional performance can keep lastingly.
3, azo hydrophilic compounds of the present invention obtains by there is diazotization and coupled reaction at low temperatures, production safety, and technique is simple, and purify convenient, productive rate higher (being greater than 80%), is convenient to suitability for industrialized production;
4, azo hydrophilic compounds of the present invention, containing two symmetrical configuration, hydroxyethyl that reactive behavior is identical in molecule, this azo hydrophilic compounds is used to synthesize the polyurethane material compound with regular structure obtained as chainextender, Stability Analysis of Structures, and azo hydrophilic compounds molecular weight (being respectively 373.37,445.46) of the present invention, except containing except two sulfonate radicals or carboxylate radical in individual molecule, also containing tertiary amine structure, itself can from salify, and wetting ability is stronger.
5, azo hydrophilic compounds of the present invention is used to be formed in the self-emulsifying process of aqueous polyurethane emulsion as chainextender, the azo monomer cell distribution with strongly hydrophilic sulfonate or carboxylate structure forms stable double electrical layers at milk-globule particle surface, by very low-energy UV-irradiation (6mW/cm
2), cis-trans isomerization efficiency can reach 100%, and the change of urethane particle diameter shows that such functional materials can as ultraviolet light response nano-carrier.
6, azo hydrophilic compounds of the present invention is a kind of derivative of tropeolin-D structure, intramolecular alkaline dimethylamino can form the inner salt pattern (one-tenth para-quinoid structure) to dimethylamino phenyl azobanzoic acid in acid condition, add that there is reactive high symmetrical dihydroxyl structure, in the electrochromic polymer materials such as formation azo water-soluble polyester, polycarbonate, polyethers or polyether ester, also have potential application prospect.
Four, accompanying drawing explanation
Fig. 1 is the sulfonic acid type azo hydrophilic compounds AZO-1's of the embodiment of the present invention 1 preparation
1h-NMR spectrogram is (with D
2o is solvent);
Fig. 2 is the carboxylic acid type azo hydrophilic compounds AZO-2's of the embodiment of the present invention 2 preparation
1h-NMR spectrogram is (with DMSO-d
6for solvent).
Fig. 3 is the azo-type anion aqueous polyurethane latex A ZO1-AWPU1 prepared in Application Example is 6mW/cm in wavelength 365nm, exposure intensity
2different time illumination under the change spectrogram of 441nm place absorbancy that causes.
Fig. 4 is azo-type anion aqueous polyurethane latex A ZO1-AWPU2 prepared by Application Example is 6mW/cm in wavelength 365nm, intensity
2uV-irradiation before and after grain size distribution.
Five, embodiment
Embodiment 1:
1,15 grams of aniline-2 are got, 4-disulfonic acid joins the there-necked flask of 250 milliliters, add 60 ml waters under normal temperature and make it abundant dissolving, slow dropping 17.8 grams of concentrated hydrochloric acid (mass concentrations 36.5%, the concentrated hydrochloric acid below used is same) be placed in ice-water bath, keep reaction system 0-5 DEG C, dripping 4.1 grams of Sodium Nitrite mass percent concentrations is the aqueous solution of 50%, ice-water bath reaction 1h is kept to obtain the diazonium salt solution of aniline-2,4-disulfonic acid;
2,11.2 grams of N are got, N-dihydroxyethylbenzenand amine solvent forms N in 35 ml methanol and 0.5 gram of acetic acid, and N-dihydroxy ethyl aniline solution joins in 1000mL there-necked flask, there-necked flask is placed in ice-water bath, keep reaction system 0-5 DEG C, drip the diazonium salt solution of obtained aniline-2, the 4-disulfonic acid of step 1 to N, in N-dihydroxy ethyl aniline solution, drip off in 0.5h, keep reaction system pH to be 6 by the aqueous sodium hydroxide solution of 1mol/L, be added dropwise to complete rear maintenance reaction 2h; 1.3 grams of concentrated hydrochloric acids are added after reaction terminates, 55 DEG C, under 0.01MPa vacuum condition retort solution to saturated, in-10 DEG C of recrystallizations, filtration obtains product, and by washing with alcohol, vacuum-drying to constant weight obtains 22.5 grams of sulfonic acid type azo hydrophilic chain extender AZO-1, and theoretical yield is 26.4 grams, and productive rate is 85%.
Fig. 1 is the AZO-1's of the present embodiment synthesis preparation
1h-NMR NMR (Nuclear Magnetic Resonance) spectrum.Various hydrogen chemical shifts δ
h(300MHz, D
2o) ownership is expressed as follows: a (7.94ppm, s, 1H), b (7.73-7.76ppm, d, 1H), c (7.65-7.69ppm, d, 1H), d (7.27ppm, s, 2H), e (6.96-6.99ppm, d, 2H), f (3.83-3.84ppm, d, 4H), g (3.81-3.82ppm, d, 4H).In addition, the integrated value at all nuclear-magnetism peaks is consistent with theoretical value, can prove the structure of AZO-1.
Embodiment 2:
1, the there-necked flask that the amino terephthalic acid of 5 grams of 2-joins 150 milliliters is got, add 50 ml waters under normal temperature and make it abundant dissolving, slow dropping 9 grams of concentrated hydrochloric acids are placed in ice-water bath, keep reaction system 0-5 DEG C, dripping 1.89 grams of Sodium Nitrite mass percent concentrations is the aqueous solution of 50%, keeps ice-water bath reaction 1h to obtain the diazonium salt solution of the amino terephthalic acid of 2-;
2,5.11 grams of N are got, N-dihydroxyethylbenzenand amine solvent forms N in 10 ml methanol and 0.5 gram of acetic acid, and N-dihydroxy ethyl aniline solution joins in 500ml there-necked flask, there-necked flask is placed in ice-water bath, keep reaction system 0-5 DEG C, drip the diazonium salt solution of obtained aniline-2, the 4-disulfonic acid of step 1 to N, in N-dihydroxy ethyl aniline solution, drip off in 0.5h, keep reaction system pH to be 6 by the aqueous sodium hydroxide solution of 1mol/L, be added dropwise to complete rear maintenance reaction 2h; Add 0.3 gram of concentrated hydrochloric acid after reaction terminates, in-10 DEG C of freezing 2h, filter and obtain product, and by washing with alcohol, vacuum-drying to constant weight obtains 8.6 grams of carboxylic acid type azo hydrophilic chain extender AZO-2, and theoretical yield 10.3 grams, productive rate is 83%.
Fig. 2 is the carboxylic acid type azo hydrophilic chain extender AZO-2's of the present embodiment synthesis preparation
1h-NMR NMR (Nuclear Magnetic Resonance) spectrum.Various hydrogen chemical shifts δ
h(300MHz, DMSO-d
6) ownership be expressed as follows: a (8.15ppm, d, 1H), b (7.99ppm, d, 1H), c (7.97ppm, d, 1H), d (7.80-7.82ppm, d, 2H), e (7.74-7.76ppm, d, 2H), f (3.61ppm, d, 4H), g (3.59-3.60ppm, d, 4H).In addition, the integrated value at all nuclear-magnetism peaks is consistent with theoretical value, can prove the structure of AZO-2.
Embodiment 3:
1,300 grams of aniline-2 are got, 4-disulfonic acid joins in reactor, add 1 premium on currency under normal temperature and make it abundant dissolving, slow dropping 356 grams of concentrated hydrochloric acids are placed in ice-water bath, keep reaction system 0-5 DEG C, fast drop 82 grams of Sodium Nitrite mass percent concentrations are the aqueous solution of 50%, keep ice-water bath reaction 1h to obtain the diazonium salt solution of aniline-2,4-disulfonic acid;
2,222 grams of N are got, N-dihydroxyethylbenzenand amine solvent forms N in 600 ml methanol and 10 grams of acetic acid, and N-dihydroxy ethyl aniline solution, joins in reactor, there-necked flask is placed in ice-water bath, keep reaction system 0-5 DEG C, drip the diazonium salt solution of aniline-2,4-disulfonic acid prepared by step 1 to N, in N-dihydroxy ethyl aniline solution, drip off in 0.5h, keep reaction system pH to be 6 by the aqueous sodium hydroxide solution of 1mol/L, be added dropwise to complete rear maintenance reaction 3h; Add 20 grams of concentrated hydrochloric acids after reaction terminates, 55 DEG C, retort solution, to saturated, in-10 DEG C of recrystallizations, filtered and obtained product under 0.01MPa vacuum condition, and by washing with alcohol, vacuum-drying to constant weight obtains sulfonic acid type azo hydrophilic chain extender AZO-1.
Application Example:
By 56.00 grams average molecular weight M
nbe 2000 PTMG (PTMG) dewater 1 hour at 110 DEG C after be cooled to 50 DEG C, then 22.23 grams of isophorone diisocyanates (IPDI) are added, 6.03 grams of dimethylol propionic acids (DMPA), the AZO-1 of 0.45 gram of above-mentioned preparation, 1.89 grams of BDOs (BDO), 0.05 gram of dibutyl tin laurate, 0.05 gram of stannous octoate and 85.00 grams of butanone are added after 2 hours in 90 DEG C of stirring reactions, constant temperature is cooled to 25 DEG C at 70 DEG C of stirring reactions after 5 hours, reaction solution is proceeded to high speed shear dispersion machine, 4.80 grams of triethylamines (TEA) are added under the condition of 3000 revs/min, react and add 200 grams of water after 5 minutes, after stirring 5 minutes again, reaction product is proceeded to Rotary Evaporators, at 50 DEG C, butanone is sloughed under 0.01MPa vacuum condition, namely obtaining solid is 30.22% containing the mass ratio of non-aqueous non-solvent material and aqueous polyurethane emulsion (in the aqueous polyurethane), DMPA and azo hydrophilic chain extender in aqueous polyurethane in non-aqueous non-solvent material content (mass percent) be respectively the azo-type anion aqueous polyurethane latex A ZO1-AWPU1 of 6.96% and 0.51%.
As kept other condition constant, change IPDI:PTMG:DMPA:BDO:AZO1 is 1.0:0.28:0.45:0.19:0.03, obtain azo hydrophilic chain extender in aqueous polyurethane in non-aqueous non-solvent material content (mass percent) be the azo-type anion aqueous polyurethane latex A ZO1-AWPU2 of 1.53%.
As kept other condition constant, change feeding intake of DMPA and AZO1 and be respectively 0 gram and 19.41 grams, neutralizing agent TEA is 10.52 grams.Azo-type anion aqueous polyurethane emulsion can be obtained equally, wherein not containing DMPA, azo hydrophilic chain extender in aqueous polyurethane in non-aqueous non-solvent material content be 20.87%.
As kept other condition constant, by regulating the ratio of amount of substance of PTMG, IPDI, DMPA and AZO1, obtain azo hydrophilic chain extender side chain azo-type anion aqueous polyurethane emulsion of content difference (0.2-20.87%) in non-aqueous non-solvent material in aqueous polyurethane.
Azo chromophore part in AZO1-AWPU1 molecular chain has typical photic configuration isomery characteristic.Accompanying drawing 3 is AZO1-AWPU1 emulsion is 6mW/cm in wavelength 365nm, radiant illumination
2illumination under because the trans-isomer(ide) of azobenzene structure part is to the transformation of configuration of cis-isomeride and the change of the 441nm place absorbancy caused.Along with the prolongation of irradiation time, the absorbance at 441nm place reduces gradually; Irradiate after 4 minutes, absorbance reduces rapidly; After 14 minutes, the cis and trans isomers in system reaches balance, and absorbancy substantially no longer changes, and at this moment the apparent colour of emulsion changes into colourless from orange-yellow when just irradiating.After self-emulsifying process, it is outside that azo component with hydrophilic radical is positioned at urethane milk-globule, the azo monomer cell distribution namely with strongly hydrophilic sulfonate structures forms stable double electrical layers at milk-globule particle surface, pass through UV-irradiation, in the extremely short time, the nitrogen benzide of transconfiguration all changes cis-configuration into, and cis-trans isomerization efficiency reaches 100%.After stopping irradiating, due to molecular thermalmotion, the cis-isomeride that azobenzene structure part is in energy higher state changes to trans-isomer(ide) again gradually, this reversible cis-trans isomerization change finally make again the apparent colour of emulsion from colourless change into orange-yellow.
Fig. 4 is the grain size distribution of azo-type anion aqueous polyurethane latex A ZO1-AWPU2 after UV-light (365nm) pre-irradiation prepared by this application embodiment, as can be seen from the figure the configuration of azo double bond is transformed into cis-configuration from trans, which results in the change of milk-globule particle diameter, illustrate that this emulsion has good ultraviolet light response.Because azo group is positioned at urethane side chain, in the self-emulsifying process forming aqueous polyurethane emulsion, azo functional unit is distributed in the double electrical layers surface that milk-globule particle is formed, and UV-light can be easy to be irradiated to the azo functional group that is positioned at electrostatic double layer surface and cis-trans isomerism effect occurs.Meanwhile, from the angle of packing of molecules, the transconfiguration of azo double bond more easily forms accumulation mode more closely.Otherwise cis-structure then.So after UV-irradiation, the particle diameter of emulsion particle increases, and size distribution broadens simultaneously.
Claims (4)
1. an azo hydrophilic compounds, is characterized in that: described azo hydrophilic compounds comprises carboxylic acid type azo hydrophilic compounds or sulfonic acid type azo hydrophilic compounds;
The structural formula of described carboxylic acid type azo hydrophilic compounds is:
The structural formula of described sulfonic acid type azo hydrophilic compounds is:
2. a preparation method for azo hydrophilic compounds according to claim 1, is characterized in that comprising the steps:
1) amino for the 2-of 100 mass parts terephthalic acid is joined in there-necked flask, the water adding 500-1000 mass parts subsequently fully stirs formation solution, then 10-20 mass parts concentrated hydrochloric acid is dripped in there-necked flask, hierarchy of control temperature is 0-5 DEG C, drip the sodium nitrite solution of 38 mass parts 50wt%, keep ice-water bath conditioned response 1-2 hour, generate the diazonium salt solution of the amino terephthalic acid of 2-;
2) by 102 mass parts N, N-dihydroxyethylbenzenand amine solvent forms N in 100-300 mass parts Methanol and 0-10 mass parts acetic acid, N-dihydroxy ethyl aniline solution, dripping step 1 subsequently) diazonium salt solution of the obtained amino terephthalic acid of 2-is to N, in N-dihydroxy ethyl aniline solution, drip off in 0.5-1h; The pH value of regulation system is 4-6, and be added dropwise to complete at rear holder ties up to 0-5 DEG C and react 2-4 hour, last regulation system pH value is 4-8, by washing with alcohol and vacuum-drying to constant weight obtains carboxylic acid type azo hydrophilic compounds after filtration.
3. a preparation method for azo hydrophilic compounds according to claim 1, is characterized in that comprising the steps:
1) by 100 mass parts aniline-2,4-disulfonic acid joins in there-necked flask, the water adding 500-1000 mass parts subsequently fully stirs formation solution, drip 100-150 mass parts concentrated hydrochloric acid in there-necked flask, hierarchy of control temperature is 0-5 DEG C, drips the sodium nitrite solution of 27 mass parts 50wt%, keeps ice-water bath conditioned response 1-2 hour, generate the diazonium salt solution of aniline-2,4-disulfonic acid;
2) by 74 mass parts N, N-dihydroxyethylbenzenand amine solvent forms N in 100-400 mass parts Methanol and 0-10 mass parts acetic acid, N-dihydroxy ethyl aniline solution, drip step 1 subsequently) obtained aniline-2, the diazonium salt solution of 4-disulfonic acid is to N, in N-dihydroxy ethyl aniline solution, drip off in 0.5-1h; The pH value of regulation system is 4-6, be added dropwise to complete at rear holder ties up to 0-5 DEG C and react 2-4 hour, last regulation system pH value is 4-8, in-20 to-5 DEG C of cold filtrations after underpressure distillation at 55 DEG C, then obtains sulfonic acid type azo hydrophilic compounds after vacuum-drying to constant weight by washing with alcohol.
4. a purposes for azo hydrophilic compounds according to claim 1, is characterized in that: can some or all of alternative synthesis of polyurethane time the conventional hydrophilic chainextender that uses and small molecules glycol chain extender.
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| CN108892768A (en) * | 2018-05-24 | 2018-11-27 | 华中科技大学 | One kind can the light-operated plastic polyurethane elastomeric material of self-healing, its preparation and application |
| CN109535361A (en) * | 2018-11-12 | 2019-03-29 | 中山大学 | A kind of ultraviolet light irradiation mechanical response aqueous polyurethane and preparation method thereof |
| 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 |
| CN112779789A (en) * | 2021-01-26 | 2021-05-11 | 花好南 | Color-changing sun-proof fabric and preparation method thereof |
| CN115415931A (en) * | 2022-07-26 | 2022-12-02 | 安徽禾臣新材料有限公司 | Chemical mechanical polishing pad for semiconductor processing |
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| CN103626674A (en) * | 2013-11-15 | 2014-03-12 | 中国科学技术大学 | Azo dibasic alcohol in symmetrical structure and preparation method thereof |
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| CN103626674A (en) * | 2013-11-15 | 2014-03-12 | 中国科学技术大学 | Azo dibasic alcohol in symmetrical structure and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892768A (en) * | 2018-05-24 | 2018-11-27 | 华中科技大学 | One kind can the light-operated plastic polyurethane elastomeric material of self-healing, its preparation and application |
| CN109535361A (en) * | 2018-11-12 | 2019-03-29 | 中山大学 | A kind of ultraviolet light irradiation mechanical response aqueous polyurethane and preparation method thereof |
| 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 |
| CN112779789A (en) * | 2021-01-26 | 2021-05-11 | 花好南 | Color-changing sun-proof fabric and preparation method thereof |
| CN115415931A (en) * | 2022-07-26 | 2022-12-02 | 安徽禾臣新材料有限公司 | Chemical mechanical polishing pad for semiconductor processing |
| CN115415931B (en) * | 2022-07-26 | 2024-03-15 | 安徽禾臣新材料有限公司 | Chemical mechanical polishing pad for semiconductor processing |
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