CN101153458B - Optical bleaching agent for phthalocyanines, preparation and application thereof - Google Patents
Optical bleaching agent for phthalocyanines, preparation and application thereof Download PDFInfo
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- CN101153458B CN101153458B CN200610047925A CN200610047925A CN101153458B CN 101153458 B CN101153458 B CN 101153458B CN 200610047925 A CN200610047925 A CN 200610047925A CN 200610047925 A CN200610047925 A CN 200610047925A CN 101153458 B CN101153458 B CN 101153458B
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- Prior art keywords
- phthalocyanine
- bleaching agent
- reaction
- optical bleaching
- phthalocyanines
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- 239000007844 bleaching agent Substances 0.000 title claims abstract description 32
- 238000009994 optical bleaching Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 6
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- 239000004411 aluminium Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- -1 dimethyl sodium Chemical compound 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 235000012970 cakes Nutrition 0.000 claims description 13
- 238000002386 leaching Methods 0.000 claims description 13
- 238000000967 suction filtration Methods 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 9
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 238000009413 insulation Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 235000011056 potassium acetate Nutrition 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 235000021463 dry cake Nutrition 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229940124530 sulfonamide Drugs 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 210000002374 sebum Anatomy 0.000 abstract description 10
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 6
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 230000002147 killing effect Effects 0.000 abstract description 2
- 229910018626 Al(OH) Inorganic materials 0.000 abstract 1
- 238000005286 illumination Methods 0.000 abstract 1
- 125000000565 sulfonamide group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- COMFSPSZVXMTCM-UHFFFAOYSA-N dodecane-1-sulfonimidic acid Chemical compound CCCCCCCCCCCCS(N)(=O)=O COMFSPSZVXMTCM-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000004061 bleaching Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 241000192125 Firmicutes Species 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 238000005202 decontamination Methods 0.000 description 4
- 230000003588 decontaminative effect Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ICGLOTCMOYCOTB-UHFFFAOYSA-N [Cl].[Zn] Chemical compound [Cl].[Zn] ICGLOTCMOYCOTB-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 3
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 241001122767 Theaceae Species 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000020095 red wine Nutrition 0.000 description 2
- BTTRMCQEPDPCPA-UHFFFAOYSA-N 4-chlorophthalic anhydride Chemical compound ClC1=CC=C2C(=O)OC(=O)C2=C1 BTTRMCQEPDPCPA-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- MPBRYMWMMKKRGC-UHFFFAOYSA-M carbocyanin DBTC Chemical compound [Br-].C1=CC=CC2=C([N+](=C(C=C(C)C=C3N(C4=C5C=CC=CC5=CC=C4S3)CC)S3)CC)C3=CC=C21 MPBRYMWMMKKRGC-UHFFFAOYSA-M 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention provides a phthalocyanine optical bleaching agent with long carbon chain sulfonamide group with a general structure as formula (1), wherein, PC represents phthalocyanine, M represents AlCl, Al(OH) or Zn, R1 is C7-C20 alkyl, R2 is a group of H, F, Cl, Br, I, CN, or etc., x is 1-4, y is 0-4. The optical bleaching agent of the invention has a good removal effect to sebum stains under illumination conditions of artificial lamp (infrared lamp, incandescent lamp, etc.) and sun light, meanwhile, the optical bleaching agent has a good killing or inhibiting effect togram-positive bacteriawhich takes staphylococcus aureus as a representative.
Description
Technical field
The present invention relates to phthalocyanine compound, specifically a kind of optical bleaching agent for phthalocyanines and preparation and application that contains long carbochain sulfuryl amine group.
Background technology
Bleaching agent is one of typical additives in the washing agent, and it not only can remove the intractable spot that phytochrome causes in washing process, and can make the fabric of washing pure white more bright-coloured.Traditional bleaching agent comprises that mainly chlorine system and oxygen are bleaching agent, and chlorine is that the representative products hypochlorite solutions of bleaching agent can be used for above-mentioned purpose.Oxygen is that peroxide such as sodium perborate, SODIUM PERCARBONATE has been used in laundry detergent and other cleaning product very at large in the bleaching agent.
One class is generally used for laundering of textile fabrics, and under artificial lamp (infrared lamp, incandescent lamp etc.) and solar light irradiation condition, the bleaching agent that plant look stains such as red wine stain, tea stain and coffee stain is had fine removal effect is an optical bleaching agent.These valuable bleaching agents are relative gentle and safe to fabric and dyestuff, also are quite effective brightening and increasing aspect gorgeous.The effect of optical bleaching agent comprises from various light sources and to absorb energy and to change into bleaching species at fabric face.Various such materials (as patent GB1372035), especially zinc phthalocyanine sulfonate and aluminium phthalocyanine sulfonate, by industrialization be used in laundry detergent a lot of years.
Zinc phthalocyanine sulfonate and aluminium phthalocyanine Sulfonates optical bleaching agent, plant look stain all had well remove to steep bleaching effect, but sebum stain gone that to steep bleaching effect very poor, reason may be that this two classes optical bleaching agent all is water-soluble substanceses, and the sebum stain is oil soluble material, and phthalocyanine Sulfonates optical bleaching agent is difficult near the sebum stain.
Summary of the invention
The object of the present invention is to provide a kind of optical bleaching agent for phthalocyanines and preparation and application that contains long carbochain sulfuryl amine group, the introducing of long carbochain makes it have good effect of removing to the sebum stain, and to being that the gram-positive bacteria of representative has and well kills or inhibitory action with the staphylococcus aureus.
For achieving the above object, the technical solution used in the present invention is:
A kind of optical bleaching agent for phthalocyanines, its general structure as the formula (1),
Wherein: PC represents phthalocyanine, and M represents AlCl, Al (OH) or Zn, R
1Be C
7-C
20Alkyl, R
2Be H, F, Cl, Br, groups such as I or CN, x are 1～4, y is 0～4.
The preferred construction general formula is as follows,
The preparation of described optical bleaching agent for phthalocyanines can be operated according to the following procedure,
1) replaces aluminium phthalocyanine or replace the synthetic of zinc phthalocyanine: in 40～120ml trichloro-benzenes, add urea 0.30～2.00mol successively, phthalic anhydride 0.07～0.10mol, phthalic anhydride or have R
2Substituent phthalic anhydride 0.02～0.05mol, acid dimethyl sodium 0.01～0.1mol, zinc chloride or aluminium chloride 0.02～0.06mol, ammonium molybdate 0.01～0.80mmol, at 150～230 ℃ of reaction 4～28h, reaction finishes, and cools to room temperature, filter, 110～130ml carbon chain lengths is 1～8 fatty alcohol washing leaching cake; Use the sodium hydroxide solution of weight concentration 5～10% and 5～10% hydrochloric acid solution washing leaching cake respectively, dry cake gets blue powder;
2) synthesizing of replacement aluminium phthalocyanine or replacement zinc phthalocyanine sulfonamides: replacement aluminium phthalocyanine that step 1) is synthetic that 1～5g is synthetic or replacement zinc phthalocyanine pursue part and join in 10～25ml chlorosulfonic acid, under 130～135 ℃ of temperature, react 2～6h, be cooled to 60～80 ℃ then, drip 3～9ml thionyl chloride, be warming up to 85～90 ℃ again, stop reaction behind insulation reaction 0.5～5h, reactant liquor is added drop-wise in 10～40ml frozen water, suction filtration, frozen water washing leaching cake to filtrate pH value is 6～7, filter cake being joined temperature is controlled between 10～25 ℃ in 30～70g frozen water, is that 7～20 fatty amine joins reaction system with carbon chain lengths, regulates the pH value 6～8 with 5～10% sodium carbonate liquor then, behind reaction 10～24h, stop reaction, add 10～20g sodium chloride or potassium acetate, saltout, suction filtration, grind carefully after 50～70 ℃ of oven dry of filter cake, alcohol reflux obtains target compound.
The described optical bleaching agent for phthalocyanines that contains long carbochain sulfuryl amine group is used to bleach the soiled cotton that has sebum stain or tea stain, red wine stain isochrome stain; Or be used to prepare the bactericide of killing or suppressing gram-positive bacteria.
The present invention has following advantage:
1. good to sebum stain removal effect.Under artificial lamp (infrared lamp, incandescent lamp etc.) and solar light irradiation condition, the present invention has the aluminium of long carbochain sulfuryl amine group or zinc optical bleaching agent for phthalocyanines to have the sebum stain and well removes to steep bleaching effect.
2. the purposes that has kill bacteria.Optical bleaching agent of the present invention is to being that the gram-positive bacteria of representative has and well kills or inhibitory action with the staphylococcus aureus.
The specific embodiment
Embodiment 1
Synthesizing of aluminium phthalocyanine: mechanical agitation is being housed, in the 150ml four-hole bottle of condenser pipe and thermometer, is adding trichloro-benzenes 80ml, add urea 0.5mol then successively, phthalic anhydride 0.12mol, acid dimethyl sodium 0.04mol, aluminum trichloride (anhydrous) 0.03mol, ammonium molybdate 0.2mmol, react 16h under 200 ℃ of temperature conditions, reaction finishes, and cools to room temperature, filter 120ml washed with isopropyl alcohol filter cake.Use 10% sodium hydroxide solution and 10% hydrochloric acid solution washing leaching cake respectively, dry cake gets blue powder, and yield is 53.2%.
Synthesizing of aluminium phthalocyanine dodecyl sulfonamide (1): the aluminium phthalocyanine that 2.0g is synthetic joins in the 16ml chlorosulfonic acid by part, react 4h down at 130 ℃, be cooled to 70 ℃ then, Dropwise 5 ml thionyl chloride, be warming up to 85 ℃ again, stop reaction behind the insulation reaction 1h, reactant liquor is added drop-wise in the 20ml frozen water, suction filtration, frozen water washing leaching cake to filtrate pH value is 6～7.Filter cake joined temperature is controlled at below 20 ℃ in the 54.0g frozen water, the 1.0g lauryl amine is joined reaction system, regulate the pH value about 7 with 10% sodium carbonate liquor then, behind the reaction 24h, stop reaction, add the 18.0g potassium acetate, saltout, suction filtration, grind carefully after 70 ℃ of oven dry of filter cake, alcohol reflux obtains target compound 1.8g, structure is measured its maximum absorption wavelength λ as the formula (1) in the water
MaxBe 675.5nm.
IR (KBr, the cm of product (1)
-1): 1200 (SO
3H); 1160 (SO
2NH-); 2930,2850 (CH
3(CH
2)
10CH
2-); 1600,1500 (Ar, C=C); 1396,1319 (C-N).
Embodiment 2
Synthesizing of aluminium phthalocyanine octyl group sulfonamide (2): aluminium phthalocyanine 2.0g synthetic among the embodiment 1 is joined in the 16ml chlorosulfonic acid by part, react 4h down at 130 ℃, be cooled to 70 ℃ then, Dropwise 5 ml thionyl chloride, be warming up to 85 ℃ again, stop reaction behind the insulation reaction 1h, reactant liquor is added drop-wise in the 20ml frozen water, suction filtration, frozen water washing leaching cake to filtrate pH value is 6～7.Filter cake joined temperature is controlled at below 20 ℃ in the 54.0g frozen water, the 0.7g n-octyl amine is joined reaction system, regulate the pH value about 7 with 10% sodium carbonate liquor then, behind the reaction 24h, stop reaction, add the 18.0g potassium acetate, saltout, suction filtration, grind carefully after 70 ℃ of oven dry of filter cake, alcohol reflux obtains target compound 2.0g, structure is measured its maximum absorption wavelength λ as the formula (2) in the water
MaxBe 673.5nm.
IR (KBr, the cm of product (1)
-1): 1200 (SO
3H); 1165 (SO
2NH-); 2925,2850 (CH
3(CH
2)
6CH
2-); 1600,1500 (Ar, C=C); 1395,1320 (C-N).
Embodiment 3
Synthesizing of bromine aluminium phthalocyanine: mechanical agitation is being housed, in the 150ml four-hole bottle of condenser pipe and thermometer, is adding trichloro-benzenes 80ml, then successively to wherein adding urea 0.50mol, 4-phthalate bromine acid anhydride 0.03mol, phthalic anhydride 0.09mol, acid dimethyl sodium 0.04mol, aluminum trichloride (anhydrous) 0.03mol, ammonium molybdate 0.2mmol reacts 16h under 200 ℃ of temperature conditions, reaction finishes, cool to room temperature, filter 120ml washed with isopropyl alcohol filter cake.Get blue powder 12.50g with 10% sodium hydroxide solution and 10% hydrochloric acid solution washing leaching cake dry cake respectively, its fusing point is 63.8% greater than 300 ℃ by single bromo aluminium phthalocyanine calculated yield.
Synthesizing of bromine aluminium phthalocyanine dodecyl sulfonamide (3): the bromine aluminium phthalocyanine that 2.2g is synthetic joins in the 16ml chlorosulfonic acid by part, react 4h down at 130 ℃, be cooled to 70 ℃ then, Dropwise 5 ml thionyl chloride, be warming up to 85 ℃ again, stop reaction behind the insulation reaction 1h, reactant liquor is added drop-wise in the 20ml frozen water, suction filtration, frozen water washing leaching cake to filtrate pH value is 6～7.Filter cake joined temperature is controlled at below 20 ℃ in the 54.0g frozen water, the 1.0g lauryl amine is joined reaction system, regulate the pH value about 7 with 10% sodium carbonate liquor then, behind the reaction 24h, stop reaction, add the 18.0g potassium acetate, saltout, suction filtration, grind carefully after 70 ℃ of oven dry of filter cake, alcohol reflux obtains target compound 1.3g, structure is measured its maximum absorption wavelength λ as the formula (3) in the water
MaxBe 678.0nm.
The IR of product (1)
Embodiment 4
Synthesizing of chlorine zinc phthalocyanine: mechanical agitation is being housed, in the 120ml four-hole bottle of condenser pipe and thermometer, add trichloro-benzenes 30ml, urea 0.20mol, 4-chloro-phthalic anhydride 0.01mol, phthalic anhydride 0.03mol, acid dimethyl sodium 0.01mol, ammonium molybdate 0.08mmol, anhydrous zinc chloride 0.01mol, chlorobenzene 1ml slowly is warming up to 170 ℃, insulation reaction 12h then in 0.5h.When cooling to 70～80 ℃, in reaction bulb, add isopropyl alcohol 50ml, stop heating, after stirring 0.5h, suction filtration is used 10% sodium hydroxide solution and 10% hydrochloric acid solution washing leaching cake respectively, and dry cake gets blue powder 2.6g, its fusing point is 42.9% by monochloro for zinc phthalocyanine calculated yield greater than 300 ℃.
Synthesizing of chlorine zinc phthalocyanine dodecyl sulfonamide (3): the chlorine zinc phthalocyanine that 2.2g is synthetic joins in the 16ml chlorosulfonic acid by part, react 4h down at 130 ℃, be cooled to 70 ℃ then, Dropwise 5 ml thionyl chloride, be warming up to 85 ℃ again, stop reaction behind the insulation reaction 1h, reactant liquor is added drop-wise in the 20ml frozen water, suction filtration, frozen water washing leaching cake to filtrate pH value is 6～7.Filter cake joined temperature is controlled in 20 ℃ in the 54.0g frozen water, the 1.0g lauryl amine is joined reaction system, regulate the pH value about 7 with 10% sodium carbonate liquor then, behind the reaction 24h, stop reaction, add the 18.0g potassium acetate, saltout, suction filtration, grind carefully after 70 ℃ of oven dry of filter cake, alcohol reflux obtains target compound 1.4g, structure is measured its maximum absorption wavelength λ as the formula (4) in the water
MaxBe 671.0nm.
The IR of product (1)
Embodiment 5
Going to steep the bleaching experiment condition is: wash temperature is 45 ℃, wash time is 1h, standard washing powder working concentration is 2g/L, the optical bleaching agent working concentration is 0.75mg/L; bath raio is 1: 300; incandescent lamp irradiation (wick is apart from liquid level 10cm), and alr mode is a mechanical agitation, and the decontamination value is three test mean values.R (%) is the decontamination value, is the whiteness difference before the soiled cotton test piece is washed the back and washed, and P is a decontamination ratio, is the ratio of sample and standard washing powder decontamination value, and testing used sebum soiled cotton is the national standard soiled cotton.The contrast sample is aluminium phthalocyanine sulfonate (mixtures of three sulfonation and four sulfonated products), and it is as shown in table 1 to go to steep bleaching effect.
Table 1 optical bleaching agent removes to steep bleachability
Embodiment 6
The sterilization experiment condition is: (1) is that 105～106cfu/ml staphylococcus aureus joins that to fill 9ml concentration be 10ppm with concentration, 1ppm, 0.1ppm in the beaker of light bleaching liquor. (2) with the 200W incandescent lamp at wick apart from the irradiates light bleaching liquor 30min of liquid level 18cm place, solution temperature rising scope is controlled in 0.5 ℃ behind the pre-irradiation. and (3) adopt 105～106cfu/ml staphylococcus aureus 1ml to add in the 9ml physiological saline simultaneously, the 200W incandescent lamp shines apart from liquid level 18cm, to do contrast. get 100 μ l liquid coated plates behind (4) irradiation 30min, put into 37 ℃ biochemical incubator, cultivate to take out after 24 hours and observe, calculate the clump count of surviving, data are the average of twice test in the table 2.
The research of table 2 optical bleaching agent bactericidal property
Annotate 1) former bacterium colony concentration 10
5～10
6Cfu/ml annotates 2) incandescent lamp (200w) is apart from liquid level 18cm irradiation 30min.
Optical bleaching agent of the present invention has good effect of removing to sebum stain under artificial lamp (infrared lamp, incandescent lamp etc.) and solar light irradiation condition, simultaneously to being that the gram-positive bacteria of representative has and well kills or inhibitory action with the staphylococcus aureus.
Claims (3)
1. optical bleaching agent for phthalocyanines is characterized in that: its general structure as the formula (1),
Wherein: PC represents phthalocyanine, and M represents AlCl, Al (OH) or Zn, R
1Be C
7-C
20Alkyl, R
2Be H, F, Cl, Br, I or CN group, x are 1～4, y is 0～4.
2. according to the described optical bleaching agent for phthalocyanines of claim 1, it is characterized in that: its general structure as the formula (2),
Wherein: PC represents phthalocyanine, and M represents Al (OH) or Zn, R
1Be C
10-C
16Alkyl, R
2Be H, Cl, Br, x are 2, y is 1.
3. the preparation method of the described optical bleaching agent for phthalocyanines of claim 1 is characterized in that: can operate according to the following procedure,
1) replaces aluminium phthalocyanine or replace the synthetic of zinc phthalocyanine: in 40～120ml trichloro-benzenes, add urea 0.30～2.00mol successively, phthalic anhydride 0.07～0.10mol, phthalic anhydride or have R
2Substituent phthalic anhydride 0.02～0.05mol, acid dimethyl sodium 0.01～0.1mol, zinc chloride or aluminium chloride 0.02～0.06mol, ammonium molybdate 0.01～0.80mmol, at 150～230 ℃ of reaction 4～28h, reaction finishes, and cools to room temperature, filter, 110～130ml carbon chain lengths is 1～8 fatty alcohol washing leaching cake; Use the sodium hydroxide solution of weight concentration 5～10% and 5～10% hydrochloric acid solution washing leaching cake respectively, dry cake gets blue powder;
2) synthesizing of replacement aluminium phthalocyanine or replacement zinc phthalocyanine sulfonamides: replacement aluminium phthalocyanine that step 1) is synthetic that 1～5g is synthetic or replacement zinc phthalocyanine pursue part and join in 10～25ml chlorosulfonic acid, under 130～135 ℃ of temperature, react 2～6h, be cooled to 60～80 ℃ then, drip 3～9ml thionyl chloride, be warming up to 85～90 ℃ again, stop reaction behind insulation reaction 0.5～5h, reactant liquor is added drop-wise in 10～40ml frozen water, suction filtration, frozen water washing leaching cake to filtrate pH value is 6～7, filter cake being joined temperature is controlled between 10～25 ℃ in 30～70g frozen water, is that 7～20 fatty amine joins reaction system with carbon chain lengths, regulates the pH value 6～8 with 5～10% sodium carbonate liquor then, behind reaction 10～24h, stop reaction, add 10～20g sodium chloride or potassium acetate, saltout, suction filtration, grind carefully after 50～70 ℃ of oven dry of filter cake, alcohol reflux obtains target compound.
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| CN109021614B (en) * | 2018-08-30 | 2021-03-19 | 东华大学 | Phthalocyanine azo-based double-chromophore reactive dye with high fixation rate and preparation method and application thereof |
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| US4540518A (en) * | 1980-02-29 | 1985-09-10 | Ciba-Geigy Corporation | Zinc and aluminum phthalocyanines |
| US4566874A (en) * | 1981-12-09 | 1986-01-28 | Ciba-Geigy Corporation | Water-soluble zinc and aluminium phthalocyanines and use thereof as photoactivators |
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