CN116145423A - Preparation method of organic photosensitizer grafted photocatalysis self-cleaning type textile - Google Patents
Preparation method of organic photosensitizer grafted photocatalysis self-cleaning type textile Download PDFInfo
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- CN116145423A CN116145423A CN202211743767.4A CN202211743767A CN116145423A CN 116145423 A CN116145423 A CN 116145423A CN 202211743767 A CN202211743767 A CN 202211743767A CN 116145423 A CN116145423 A CN 116145423A
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- phthalocyanine dye
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- 239000004753 textile Substances 0.000 title claims abstract description 77
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 50
- 238000004140 cleaning Methods 0.000 title claims abstract description 38
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 26
- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000001007 phthalocyanine dye Substances 0.000 claims abstract description 37
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 34
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000004043 dyeing Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 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 20
- 239000012965 benzophenone Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 12
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 5
- 230000009514 concussion Effects 0.000 claims abstract description 3
- 238000007654 immersion Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000000975 dye Substances 0.000 claims description 29
- 239000004744 fabric Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 229920000742 Cotton Polymers 0.000 claims description 15
- YXZRCLVVNRLPTP-UHFFFAOYSA-J turquoise blue Chemical class [Na+].[Na+].[Na+].[Na+].[Cu+2].NC1=NC(Cl)=NC(NC=2C=C(NS(=O)(=O)C3=CC=4C(=C5NC=4NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)NC=4NC(=C6C=C(C=CC6=4)S([O-])(=O)=O)NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)N5)C=C3)C(=CC=2)S([O-])(=O)=O)=N1 YXZRCLVVNRLPTP-UHFFFAOYSA-J 0.000 claims description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229920000297 Rayon Polymers 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 210000002268 wool Anatomy 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 150000008366 benzophenones Chemical class 0.000 abstract description 8
- 239000000835 fiber Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 239000012452 mother liquor Substances 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 241000083869 Polyommatus dorylas Species 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- HFIYIRIMGZMCPC-YOLJWEMLSA-J remazole black-GR Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(\N=N\C=3C=CC(=CC=3)S(=O)(=O)CCOS([O-])(=O)=O)C(O)=C2C(N)=C1\N=N\C1=CC=C(S(=O)(=O)CCOS([O-])(=O)=O)C=C1 HFIYIRIMGZMCPC-YOLJWEMLSA-J 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 230000005283 ground state Effects 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
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- 230000002045 lasting effect Effects 0.000 description 1
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- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
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Images
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
The invention relates to the technical field of functional textile preparation, and discloses a preparation method of a photocatalysis self-cleaning type textile grafted by an organic photosensitizer, which comprises the following steps: (1) Adding inorganic salt and water into the phthalocyanine dye to obtain copper phthalocyanine dye liquor; immersing the textile into copper phthalocyanine dye solution for concussion dyeing, taking out, soaping, washing with water and drying to obtain phthalocyanine grafted textile; (2) Adding 3,3', 4' -benzophenone tetracarboxylic dianhydride into water, heating, stirring and dissolving, and adding sodium hypophosphite to obtain benzophenone finishing liquid; (3) Immersing the phthalocyanine grafted textile into a benzophenone finishing liquid, and sequentially performing twice immersion, twice padding, pre-drying and baking to obtain the photocatalysis self-cleaning textile. According to the invention, the phthalocyanine dye and the benzophenone derivative can be combined with textile fibers through covalent bonds, the photocatalysis effect is improved through the synergistic effect of the phthalocyanine dye and the benzophenone derivative, the preparation is easy in mass, and the product is easy to recycle after the use.
Description
Technical Field
The invention belongs to the technical field of functional textile preparation, and particularly relates to a preparation method of a photocatalysis self-cleaning type textile grafted by an organic photosensitizer.
Background
The photocatalytic oxidation method is a method of oxidizing and decomposing organic matters by generating active oxygen species by irradiation of light by a photocatalyst. Compared with the traditional treatment methods such as adsorption method, coagulation method, activated sludge method, physical method and the like, the photocatalytic oxidation degradation of organic pollutants in water has the outstanding advantages of low energy consumption, simple and convenient operation, mild reaction conditions, secondary pollution reduction and the like, and is increasingly valued by people. Photocatalysts which have been used in large numbers at present are mainly inorganic semiconductor catalysts, such as TiO 2 、ZnO、WO 3 、CdS、g-C 3 N 4 ZnS, etc., but most inorganic photocatalysts are difficult to recover, electron-hole pairs are easily recombined to be deactivated, and are difficult to be supported on other substrates or easily fall off during use because of no reactivity.
The organic photosensitizer has various types, is easy to modify in structure, has good ultraviolet-visible absorption capacity, and can generate active oxygen species with oxidability under illumination, so that good effects of photoinduction antibacterial, pollutant degradation and the like are shown. At present, the main method for preparing the photocatalysis system based on the organic photosensitizer is to physically blend the organic photosensitizer with a substrate, but the method is prepared by electrostatic spinning or other film preparation methods, the process is complex, and the bonding fastness between the photosensitizer and the substrate is relatively poor. Even if some of the photosensitizer is grafted onto the substrate, it involves a complex synthetic process. For example, patent CN 111249931B discloses a preparation method of a metalloporphyrin covalent grafting photocatalytic film, which firstly uses chloroacetyl chloride to carry out chloroacetylation modification on a film material, and then reacts amino metalloporphyrin with the film material after chloroacetylation, so that metalloporphyrin is covalently grafted on the surface of the film material, but the method needs to use chloroacetyl chloride, which is not beneficial to environmental protection, has higher cost and is difficult to prepare in large scale. Therefore, the development of the textile photocatalysis system which has simple preparation process, low cost, high efficiency, durability and easy recovery has important significance.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide the preparation method of the photocatalysis self-cleaning textile grafted by the organic photosensitizer, which is simple, low in cost and mild in condition, and the obtained photocatalysis textile has lasting photocatalysis effect, is easy to prepare in large quantity and has larger practical application value.
In order to achieve the above purpose, the invention provides a preparation method of a photocatalysis self-cleaning textile grafted by an organic photosensitizer, which comprises the following steps:
(1) Adding inorganic salt and water into the phthalocyanine dye to obtain copper phthalocyanine dye liquor; immersing the textile into copper phthalocyanine dye solution for concussion dyeing, taking out, soaping, washing with water and drying to obtain phthalocyanine grafted textile;
(2) Adding 3,3', 4' -benzophenone tetracarboxylic dianhydride into water, heating, stirring and dissolving, and adding sodium hypophosphite to obtain benzophenone finishing liquid;
(3) Immersing the phthalocyanine grafted textile into a benzophenone finishing liquid, and sequentially performing twice immersion, twice padding, pre-drying and baking to obtain the photocatalysis self-cleaning textile.
The invention adopts common textile as base material, and the phthalocyanine dye and benzophenone derivative can be combined with textile fiber through covalent bond, so the invention has higher combination fastness. Under the condition of illumination, the copper phthalocyanine is excited to a singlet excited state in a molecular ground state, reaches a triplet excited state through intersystem crossing, and then reacts with a hydrogen donor substrate or oxygen to generate active oxygen such as hydroxyl radicals and singlet oxygen, so that the copper phthalocyanine has a strong oxidation effect. After being excited by light, the benzophenone group can be excited to a triplet excited state, and can also generate an electron transfer process with the copper phthalocyanine group, so that the active oxygen generation efficiency of the copper phthalocyanine group is improved, and the photocatalysis effect is improved. In addition, the dyeing and padding technology in the traditional textile field is used, special requirements on equipment are not met, the macro preparation is easy, and the product is easy to recycle after the use.
It is further preferred that in step (1), the bath ratio of the textile and copper phthalocyanine dye solution is 1:10-30 and the phthalocyanine dye concentration is not more than 12% based on the weight of the fabric.
The bath ratio and the concentration of the dye liquor directly influence the load of the dye on the fabric, the load is reduced when the bath ratio is too large, the molecules are easily accumulated on the fabric when the dye quantity is too large, and finally the photocatalysis effect is reduced.
Further preferably, in the step (1), the temperature of the oscillation dyeing is 60-90 ℃, the oscillation time is 60-80min, and the pH value is 9-11.
The covalent bond reaction between the phthalocyanine reactive dye and the fabric is affected by dyeing temperature, time and pH value, and if the covalent bond reaction exceeds the limit range, the dyeing of the fabric by the phthalocyanine dye is not facilitated.
Further preferably, in the step (1), the phthalocyanine dye includes at least one dye selected from the group consisting of reactive turquoise blue KNG, reactive turquoise blue KGL, reactive turquoise blue M-G and reactive turquoise blue KM-GB. The inorganic salt comprises at least one of anhydrous sodium sulfate, sodium chloride and potassium chloride.
Further preferably, in step (1), the textile comprises at least one of cotton fabric, wool fabric, viscose fabric.
It is further preferred that in step (2), the concentration of 3,3', 4' -benzophenone tetracarboxylic dianhydride added to water is 10 to 100g/L.
With the increase of the concentration, the loading of the benzophenone groups is gradually increased, the better the catalytic effect is, but the strength of the fabric is affected when the concentration exceeds 100g/L.
It is further preferred that in step (2), the molar ratio of 3,3', 4' -benzophenone tetracarboxylic dianhydride to sodium hypophosphite is 1:1.5-4.
It is further preferred that in step (3), the bath ratio of the textile and benzophenone finish is from 1:10 to 50.
Further preferably, in the step (3), the liquid carrying rate of the double padding is 80-120%; the temperature of the pre-baking is 80-90 ℃ and the pre-baking time is 2-8min; the baking temperature is 150-200 ℃ and the baking time is 1-4min.
In addition, the invention also provides the organic photosensitizer grafted photocatalysis self-cleaning type textile prepared by the preparation method.
Compared with the prior art, the invention has the following advantages: the common textile is adopted as a base material, and the phthalocyanine dye and the benzophenone derivative can be combined with textile fibers through covalent bonds, so that the textile has higher combination fastness. And the synergistic effect between the phthalocyanine group and the benzophenone group is beneficial to improving the photocatalysis effect, and the dyeing and padding technology in the traditional textile field is used, so that the device has no special requirement, the macro preparation is easy, and the product is easy to recycle after the use is finished.
Drawings
FIG. 1 is an SEM image of a self-cleaning textile prepared according to example 1 of the present invention;
FIG. 2 is a sample graph and absorption spectrum of the photocatalytic self-cleaning textile prepared in example 1 (example 1) and example 2 (example 2) of the present invention;
FIG. 3 is an infrared spectrum of the photo-catalytic self-cleaning textile prepared in example 3 of the present invention;
FIG. 4 shows the degradation rate of the photo-catalytic self-cleaning textile to reactive black 5 dye liquor in example 3 of the present invention;
fig. 5 is a graph showing the cyclic degradability of the photocatalytic self-cleaning textile to active black 5 in example 3 of the present invention.
Detailed Description
The technical contents and effects of the present invention will be further described in detail with reference to examples, but the present invention is not limited thereto.
Example 1
(1) 10g/L of dye mother liquor (active turquoise blue KNG) is prepared, 2mL of dye mother liquor is added into a conical flask, 1.2g of anhydrous sodium sulfate is added, and the water is supplemented to 20mL, so that the copper phthalocyanine dye liquor is obtained. According to the bath ratio of 1:20 immersing 1g of cotton fabric into copper phthalocyanine dye liquor at room temperature, wherein the dye concentration is 2% (o.w.f), placing in a vibration dyeing machine, heating to 60 ℃ for dyeing for 30min, adding 0.40g of sodium carbonate to adjust the pH to 11.5, continuing to keep warm and vibrate for 45min, taking out the cotton fabric after the dyeing process is finished, soaping, washing with water and drying to obtain the phthalocyanine grafted textile.
(2) 0.50g of 3,3', 4' -benzophenone tetracarboxylic dianhydride is taken to be added into 50mL of water, heated and dissolved, and then 0.32g of sodium hypophosphite is added to obtain benzophenone finishing liquid.
(3) Adding the phthalocyanine grafted textile into the benzophenone finishing liquid, performing twice soaking and twice rolling to obtain the liquid carrying rate of 80%, then pre-baking for 3min at 80 ℃, and then baking for 4min at 160 ℃ to obtain the photocatalysis self-cleaning textile.
Example 2
(1) 10g/L of dye mother liquor (active turquoise blue KNG) is prepared, 8mL of dye mother liquor is added into a conical flask, 1.6g of anhydrous sodium sulfate is added, and the water is supplemented to 20mL, so that the copper phthalocyanine dye liquor is obtained. Immersing 1g of cotton fabric into copper phthalocyanine dye solution at room temperature according to the bath ratio of 1:20, wherein the dye concentration is 8% (o.w.f), placing the copper phthalocyanine dye solution in a vibration dyeing machine, heating to 60 ℃ for dyeing for 30min, adding 0.40g of sodium carbonate to adjust the pH value to 11.5, continuing to keep the temperature and vibrate for 45min, taking out the cotton fabric after the dyeing process is finished, soaping, washing with water and drying to obtain the phthalocyanine grafted textile.
(2) 0.50g of 3,3', 4' -benzophenone tetracarboxylic dianhydride is taken to be added into 50mL of water, heated and dissolved, and then 0.32g of sodium hypophosphite is added to obtain benzophenone finishing liquid.
(3) Adding the phthalocyanine grafted textile into the benzophenone finishing liquid, performing twice soaking and twice rolling to obtain the liquid carrying rate of 80%, then pre-baking for 3min at 80 ℃, and then baking for 4min at 160 ℃ to obtain the photocatalysis self-cleaning textile.
Example 3
(1) 10g/L of dye mother liquor (active turquoise blue KNG) is prepared, 8mL of dye mother liquor is added into a conical flask, 1.6g of anhydrous sodium sulfate is added, and the water is supplemented to 20mL, so that the copper phthalocyanine dye liquor is obtained. Immersing 1g of cotton fabric into copper phthalocyanine dye solution at room temperature according to the bath ratio of 1:20, wherein the dye concentration is 8% (o.w.f), placing the copper phthalocyanine dye solution in a vibration dyeing machine, heating to 60 ℃ for dyeing for 30min, adding 0.40g of sodium carbonate to adjust the pH value to 11.5, continuing to keep the temperature and vibrate for 45min, taking out the cotton fabric after the dyeing process is finished, soaping, washing with water and drying to obtain the phthalocyanine grafted textile.
(2) 1.50g of 3,3', 4' -benzophenone tetracarboxylic dianhydride is taken to be added into 50mL of water, heated and dissolved, and then 0.96g of sodium hypophosphite is added to obtain benzophenone finishing liquid.
(3) Adding the phthalocyanine grafted textile into the benzophenone finishing liquid, performing twice soaking and twice rolling to obtain the liquid carrying rate of 80%, then pre-baking for 3min at 80 ℃, and then baking for 4min at 160 ℃ to obtain the photocatalysis self-cleaning textile.
Example 4
(1) 10G/L of dye mother liquor (active turquoise blue M-G) is prepared, 8mL of dye mother liquor is added into a conical flask, 1.6G of anhydrous sodium sulfate is added, and the water is supplemented to 20mL, so that the copper phthalocyanine dye liquor is obtained. Immersing 1g of cotton fabric into copper phthalocyanine dye solution at room temperature according to the bath ratio of 1:20, wherein the dye concentration is 8% (o.w.f), placing the copper phthalocyanine dye solution in a vibration dyeing machine, heating to 60 ℃ for dyeing for 30min, adding 0.40g of sodium carbonate to adjust the pH value to 11.5, continuing to keep the temperature and vibrate for 45min, taking out the cotton fabric after the dyeing process is finished, soaping, washing with water and drying to obtain the phthalocyanine grafted textile.
(2) 1.50g of 3,3', 4' -benzophenone tetracarboxylic dianhydride is taken to be added into 50mL of water, heated and dissolved, and then 0.96g of sodium hypophosphite is added to obtain benzophenone finishing liquid.
(3) Adding the phthalocyanine grafted textile into the benzophenone finishing liquid, performing twice soaking and twice rolling to obtain the liquid carrying rate of 80%, then pre-baking for 3min at 80 ℃, and then baking for 4min at 160 ℃ to obtain the photocatalysis self-cleaning textile. Comparative example 1 (no benzophenone derivative was added, the remainder was the same as in example 3)
10g/L of dye mother liquor (active turquoise blue KNG) is prepared, 8mL of dye mother liquor is added into a conical flask, 1.6g of anhydrous sodium sulfate is added, and the water is supplemented to 20mL, so that the copper phthalocyanine dye liquor is obtained. Immersing 1g of cotton fabric into copper phthalocyanine dye solution at room temperature according to the bath ratio of 1:20, wherein the dye concentration is 8% (o.w.f), placing the copper phthalocyanine dye solution in a vibration dyeing machine, heating to 60 ℃ for dyeing for 30min, adding 0.40g of sodium carbonate to adjust the pH value to 11.5, continuing to keep the temperature and vibrate for 45min, taking out the cotton fabric after the dyeing process is finished, soaping, washing with water and drying to obtain the phthalocyanine grafted textile.
Comparative example 2 (benzophenone derivative was added in too small an amount, the remainder was the same as in example 3)
(1) 10g/L of dye mother liquor (active turquoise blue KNG) is prepared, 8mL of dye mother liquor is added into a conical flask, 1.6g of anhydrous sodium sulfate is added, and the water is supplemented to 20mL, so that the copper phthalocyanine dye liquor is obtained. Immersing 1g of cotton fabric into copper phthalocyanine dye solution at room temperature according to the bath ratio of 1:20, wherein the dye concentration is 8% (o.w.f), placing the copper phthalocyanine dye solution in a vibration dyeing machine, heating to 60 ℃ for dyeing for 30min, adding 0.40g of sodium carbonate to adjust the pH value to 11.5, continuing to keep the temperature and vibrate for 45min, taking out the cotton fabric after the dyeing process is finished, soaping, washing with water and drying to obtain the phthalocyanine grafted textile.
(2) 0.50g of 3,3', 4' -benzophenone tetracarboxylic dianhydride is taken to be added into 50mL of water, heated and dissolved, and then 0.32g of sodium hypophosphite is added to obtain benzophenone finishing liquid.
(3) Adding the phthalocyanine grafted textile into the benzophenone finishing liquid, performing twice soaking and twice rolling to obtain the liquid carrying rate of 80%, then pre-baking for 3min at 80 ℃, and then baking for 4min at 160 ℃ to obtain the photocatalysis self-cleaning textile.
As shown in fig. 1, which is an SEM image of the photocatalytic self-cleaning textile prepared in example 1, it can be seen that grafting of the organic photosensitizer has no obvious effect on the morphology of the cotton fabric itself, and the mildness of the preparation conditions is demonstrated.
As shown in fig. 2, which is a graph of a sample and an absorption spectrum of the photocatalytic self-cleaning textile prepared in example 1 (example 1) and example 2 (example 2), it can be seen that the fabric is still dense and blue after the grafting of the organic photosensitizer, and the fabric has a strong absorption in the visible region, which illustrates the successful grafting of the organic photosensitizer.
As shown in FIG. 3, which shows the infrared spectrum of the self-cleaning type textile prepared in example 3, cu-N vibration peaks in the copper phthalocyanine derivative and carbonyl stretching vibration peaks in the benzophenone derivative can be seen, and it is confirmed that both the copper phthalocyanine derivative and the benzophenone derivative are successfully grafted to the cellulose fiber.
The photocatalytic self-cleaning textile prepared in example 3 was subjected to a degradation test of printing and dyeing wastewater. Reactive black 5 was used as a degraded sample dye. The specific method comprises the following steps: 10mL of 20mg/L active black 5 dye solution is added into a quartz tube, and 3X 5cm of the active black 5 dye solution is added into the quartz tube 2 Placing the photocatalytic sample in a test tube, irradiating for 10, 20, 30, 60 and 90min under a photochemical reaction instrument, and evaluating change of dye liquor concentration by ultraviolet-visible spectrophotometerThe degradation rate was calculated and the results are shown in FIG. 4. As can be seen from fig. 4, the prepared photocatalysis self-cleaning textile has better photocatalysis degradation performance on active black 5, and the degradation rate is more than 99 percent. After each degradation, the sample was taken out and placed in a new waste liquid, and its recycling performance was evaluated, and the results are shown in fig. 5. As can be seen from FIG. 5, the prepared photocatalytic self-cleaning textile has better recycling performance.
Comparative examples 1-2 were tested for photocatalytic degradation performance and recycling performance in the manner described above for example 3. The results of the photocatalytic self-cleaning textiles prepared in comparative examples 1 and 2 on the dye liquor for 90min photocatalytic degradation and recycling are shown in table 1. As can be seen from Table 1, the photocatalytic self-cleaning type textile prepared in example 3 had a degradation rate of 99% for active black 5, whereas the textiles prepared in comparative examples 1 and 2 had degradation rates of only 10% and 42% for active black 5, and the cycle times were also low. The result shows that the synergistic effect between the diphenyl ketone and the phthalocyanine has great promotion effect on the photocatalytic effect.
TABLE 1
| Degradation rate | Number of times of cyclic use | |
| Example 3 | 99％ | 4 |
| Comparative example 1 | 10％ | 0 |
| Comparative example 2 | 42％ | 3 |
The above examples of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. Not all embodiments are exhaustive. Obvious changes and modifications which are extended by the technical proposal of the invention are still within the protection scope of the invention.
Claims (10)
1. The preparation method of the organic photosensitizer grafted photocatalysis self-cleaning textile is characterized by comprising the following steps of:
(1) Adding inorganic salt and water into the phthalocyanine dye to obtain copper phthalocyanine dye liquor; immersing the textile into copper phthalocyanine dye solution for concussion dyeing, taking out, soaping, washing with water and drying to obtain phthalocyanine grafted textile;
(2) Adding 3,3', 4' -benzophenone tetracarboxylic dianhydride into water, heating, stirring and dissolving, and adding sodium hypophosphite to obtain benzophenone finishing liquid;
(3) Immersing the phthalocyanine grafted textile into a benzophenone finishing liquid, and sequentially performing twice immersion, twice padding, pre-drying and baking to obtain the photocatalysis self-cleaning textile.
2. The method for preparing a photocatalytic self-cleaning textile grafted with an organic photosensitizer according to claim 1, wherein in step (1), the bath ratio of the textile to the copper phthalocyanine dye solution is 1:10-30, and the concentration of the phthalocyanine dye is not more than 12% based on the weight of the fabric.
3. The method for preparing a photocatalytic self-cleaning textile grafted with an organic photosensitizer according to claim 1, wherein in the step (1), the temperature of the vibration dyeing is 60-90 ℃, the vibration time is 60-80min, and the pH value is 9-11.
4. A method of preparing an organic photosensitizer grafted photocatalytic self-cleaning textile according to any of claims 1-3, characterized in that in step (1) the phthalocyanine dye comprises at least one dye of the group consisting of activated turquoise blue KNG, activated turquoise blue KGL, activated turquoise blue M-G, activated turquoise blue KM-GB; the inorganic salt comprises at least one of anhydrous sodium sulfate, sodium chloride and potassium chloride.
5. A method of preparing a photocatalytic self-cleaning textile grafted with an organic photosensitizer according to any of claims 1-3, characterized in that in step (1), said textile comprises at least one of cotton fabric, wool fabric, viscose fabric.
6. The method for preparing a photocatalytic self-cleaning textile grafted with an organic photosensitizer according to claim 1, wherein in step (2), the concentration of 3,3', 4' -benzophenone tetracarboxylic dianhydride added to water is 10-100g/L.
7. The method for preparing a photocatalytic self-cleaning textile grafted with an organic photosensitizer according to claim 1 or 6, characterized in that in step (2), the molar ratio of 3,3', 4' -benzophenone tetracarboxylic dianhydride to sodium hypophosphite is 1:1.5-4.
8. The method of preparing a photocatalytic self-cleaning textile grafted with an organic photosensitizer according to claim 1, characterized in that in step (3), the bath ratio of the textile to the benzophenone finishing liquid is 1:10-50.
9. The method for preparing a photocatalytic self-cleaning textile grafted with an organic photosensitizer according to claim 1 or 8, characterized in that in step (3), the liquid carrying rate of the double dip and double roll is 80-120%; the temperature of the pre-baking is 80-90 ℃ and the pre-baking time is 2-8min; the baking temperature is 150-200 ℃ and the baking time is 1-4min.
10. An organic photosensitizer grafted photocatalytic self-cleaning textile produced by the method of preparation according to any of claims 1-9.
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|---|---|---|---|---|
| US3424544A (en) * | 1956-12-14 | 1969-01-28 | Ici Ltd | Process for the coloration of cellulosic textile materials with reactive phthalocyanine dyestuffs and the dyes therefor |
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|---|---|---|---|---|
| US3424544A (en) * | 1956-12-14 | 1969-01-28 | Ici Ltd | Process for the coloration of cellulosic textile materials with reactive phthalocyanine dyestuffs and the dyes therefor |
| US20070238660A1 (en) * | 2006-03-31 | 2007-10-11 | Stephen Michielsen | Light activated antiviral materials and devices and methods for decontaminating virus infected environments |
| CN105256539A (en) * | 2015-09-18 | 2016-01-20 | 浙江理工大学 | Preparation method of self-cleaning formaldehyde removing wall cloth |
| CN114656705A (en) * | 2020-12-23 | 2022-06-24 | 汕头市亨德利塑胶有限公司 | Ultraviolet-resistant fireproof wood-plastic composite material and preparation thereof |
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