CN113832717A - Novel spiropyran photochromic cotton fabric and preparation method thereof - Google Patents
Novel spiropyran photochromic cotton fabric and preparation method thereof Download PDFInfo
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- CN113832717A CN113832717A CN202111300042.3A CN202111300042A CN113832717A CN 113832717 A CN113832717 A CN 113832717A CN 202111300042 A CN202111300042 A CN 202111300042A CN 113832717 A CN113832717 A CN 113832717A
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- 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
- D06M13/322—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 nitrogen
- D06M13/392—Nitroso compounds; Nitro compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Abstract
The invention provides a novel spiropyran photochromic cotton fabric and a preparation method thereof. The photochromic cotton fabric comprises a cotton fabric and a carboxyl modified spiropyran photochromic compound grafted on the cotton fabric through an esterification reaction, wherein the photochromic cotton fabric undergoes photochromism under ultraviolet light and can be reversibly restored to white under visible light. The preparation method comprises the steps of introducing carboxyl on a spiropyran structure, and grafting the carboxyl and rich hydroxyl on a cotton fabric in a solution of dicyclohexylcarbodiimide and 4-dimethylaminopyridine through an esterification reaction to prepare the novel spiropyran photochromic cotton fabric. The spiropyran molecule provided by the invention has simple structural design, few additionally introduced active groups, large proportion of the color-changing unit in the whole dye molecule and small influence on the ground color of the original fabric; the obtained photochromic cotton fabric has the advantages of small change of ground color, obvious reversible change under the action of light, high color fastness and 5-grade highest level of rubbing fastness and washing fastness.
Description
Technical Field
The invention relates to the technical field of preparation of photochromic fabrics, in particular to a novel spiropyran photochromic cotton fabric and a preparation method thereof.
Background
The color-changing fabric is a textile with the color changing along with the change of external environmental conditions, and can be divided into three types, namely thermochromism, photochromism and electrochromism according to different color changing principles. Among them, the photochromic material is low in cost and good in safety, and attracts people's wide attention. At present, photochromic materials are widely applied to the fields of intelligent anti-counterfeiting, information storage, textiles, daily necessities, characteristic photosensitive materials and the like.
With the rapid development of economy and science and technology, people have a stronger trend towards good life, and the pursuit of individualization and functionalization of fabrics is increasingly promoted. The photochromic fabric can present different colors under different light stimuli, caters to the pursuit of people on fashion and aesthetic, and has wide requirements in various fields such as high-grade fashion, entertainment decoration, anti-counterfeiting products and the like.
Photochromic materials are classified into organic and inorganic types. Inorganic photochromic materials are slow to photochromize, limiting their applications. The spiropyran and the derivatives thereof are the earliest and most widely researched organic photochromic materials, and can be converted into a colored open-loop-state part cyanine structure under the excitation of ultraviolet light and then can be converted into a colorless closed-loop spiropyran structure under the action of visible light, so that the photochromic effect is achieved. The spiropyran and the derivatives thereof have good color change and thermal stability, so the spiropyran derivative is an ideal dye for manufacturing photochromic fabrics.
The approaches for preparing photochromic fabrics using spiropyran-based dyes are generally classified into three types as follows: (1) the method is characterized in that a spinning technology is utilized to dissolve the spiropyran photochromic dye into spinning stock solutions of various chemical fibers for spinning to prepare the photochromic fibers, and the method has great limitation on the fibers. (2) The photochromic fabric is prepared by coating the spiropyran photochromic dye (microcapsule containing spiropyran structure, polyurethane containing spiropyran structure and the like) on the surface of the fabric through a binder by utilizing a coating and fixing technology. (3) The spiropyran photochromic dye with active groups is grafted on the surface of the fabric by utilizing a chemical modification technology, and the dye is combined with the fabric through a covalent bond (chemical bonding force). The photochromic fabric prepared by the method at present has a complex structure of designed photochromic dye, and the obtained fabric can not keep the original ground color, so that the application of the photochromic fabric in the actual scene is limited.
The patent with the application number of CN201710794396.5 discloses synthesis of a spiro inverse photochromic active dye, firstly, activated polyglycols monomethyl ether is introduced to an N atom of 2,3, 3-trimethylindole, then the activated polyglycols monomethyl ether and 4-nitro salicylaldehyde form an intermediate of a spiropyran structure, and finally, an s-triazine active group is introduced after reduction to prepare the photochromic active dye for dyeing cotton cloth. The structure and the preparation process of the photochromic reactive dye are complex, and the color fastness of the obtained photochromic cotton cloth is low.
The patent with the application number of CN201710392090.7 discloses a preparation method of a photochromic fabric, which comprises the steps of firstly carrying out reduction treatment on the fabric to form a thiol structure, then preparing a spirooxazine photochromic active dye containing halogen, and finally forming a covalent bond between the photochromic dye and the fabric through thiol-halogen click chemical reaction to obtain the photochromic fabric. The method needs to design a spiro dye molecule with a complex structure, the covalent connection process is complicated, and the existing modified cotton fabric is dark brown and cannot keep the original ground color of the cotton fabric.
In view of the above, there is a need to design an improved novel spiropyran-based photochromic cotton fabric and a preparation method thereof to solve the above problems.
Disclosure of Invention
The invention aims to provide a novel spiropyran photochromic cotton fabric and a preparation method thereof, and solves the problems of low color fastness and easy falling of a dye layer caused by a coating and fixing technology in the existing preparation method of the spiropyran photochromic cotton fabric, and the problems that the ground color of the grafted fiber is changed and the like.
In order to achieve the purpose, the invention provides a novel spiropyran photochromic cotton fabric which comprises a cotton fabric and a carboxyl modified spiropyran photochromic compound grafted on the cotton fabric through an esterification reaction.
As a further improvement of the invention, the chemical structure of the novel spiropyran photochromic cotton fabric is as follows:
in the formula, cotton represents cotton fabric.
As a further improvement of the invention, the K/S value of the novel spiropyran photochromic cotton fabric before photochromism or after reversibly restoring to white under visible light is less than 0.25.
The invention also provides a preparation method of the novel spiropyran photochromic cotton fabric, which comprises the following steps:
s1, pretreatment of cotton fabric: soaking the cotton fabric into a detergent, and stirring, washing and drying to obtain a clean cotton fabric;
s2, coloring cotton fabrics: and (3) dissolving the carboxyl modified spiropyran photochromic compound, dicyclohexylcarbodiimide and 4-dimethylaminopyridine in an organic solvent, adding the clean cotton fabric obtained in the step S1 into the obtained solution, fully reacting, washing and drying to obtain the novel spiropyran photochromic cotton fabric.
As a further improvement of the invention, the organic solvent in step S2 includes but is not limited to one of dichloromethane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide, and the ratio of the carboxyl modified spiropyran photochromic compound to the organic solvent is 1g (100-200) mL.
As a further improvement of the invention, the molar ratio of the carboxyl modified spiropyran photochromic compound, dicyclohexylcarbodiimide and 4-dimethylaminopyridine in the step S2 is 1 (4-6) to (0.5-1); the feeding mass ratio of the cotton fabric to the carboxyl modified spiropyran photochromic compound is 1 (2-4).
As a further improvement of the present invention, the structural formula of the carboxyl-modified spiropyran-based photochromic compound in step S2 is:
as a further improvement of the invention, the preparation method of the carboxyl modified spiropyran photochromic compound comprises the following steps:
s21, dissolving 2,3, 3-trimethylindole and 3-bromopropionic acid in acetonitrile, heating and refluxing for 10-12H at 85-95 ℃, removing the acetonitrile by rotary evaporation after the reaction is finished, washing with diethyl ether for 3 times, and recrystallizing the residual oily substance by using an ethyl acetate/dichloromethane mixed system to obtain 1- (2-carboxyethyl) -2,3, 3-trimethyl-3H-indole bromide powder.
S22, dissolving the obtained 1- (2-carboxyethyl) -2,3, 3-trimethyl-3H-indole bromide, 5-nitro salicylaldehyde and triethylamine in ethanol, heating and refluxing for 4-6H at 85-95 ℃, filtering after the reaction is finished, and washing for 3 times by using ethanol to obtain the carboxyl modified spiropyran photochromic compound.
As a further improvement of the invention, the detergent in the step S1 is a detergent prepared by sodium dodecyl benzene sulfonate or a common commercial detergent; the stirring is carried out for 2-3h at the temperature of 40-60 ℃; the washing is washing by using ethanol and deionized water in sequence; the drying is drying at 50-60 ℃.
As a further improvement of the invention, the washing in step S2 is washing with dichloromethane, ethanol and deionized water in sequence; the drying is vacuum drying at 30-40 deg.C for 10-12 h.
The invention has the beneficial effects that:
(1) according to the preparation method of the novel spiropyran photochromic cotton fabric, the carboxylated spiropyran and the hydroxyl on the cotton fabric are subjected to esterification reaction to realize grafting, so that the obtained photochromic fabric is subjected to photochromism under ultraviolet light and can be reversibly restored to white under visible light, and the K/S value is not changed greatly compared with that of the original cotton fabric. The spiropyran molecular structure is simple in design, the ratio of a color-changing unit (namely the spiropyran structure) in the whole dye molecule is large, the influence on the ground color of the original fabric is small, and reagents and auxiliaries which interfere with the color are not needed in the whole process, so that the ground color of the original fabric is maintained to the maximum extent. In addition, the method only needs to optimize the molecular structure of the spiropyrans through a simple process, and does not need to modify cotton fabrics, thereby simplifying the process flow of chemical grafting.
(2) According to the preparation method of the novel spiropyran photochromic cotton fabric, provided by the invention, the chemical grafting connection of the spiropyran photochromic dye and the fabric is realized by utilizing carboxyl on a spiropyran molecular structure and abundant hydroxyl on the cotton fabric through a simple esterification reaction, and the durability and the color fastness of the photochromic fabric are improved through the combination of a covalent bond (a chemical binding force), so that a new way for preparing the photochromic fabric is developed.
(3) The novel spiropyran photochromic cotton fabric provided by the invention has the advantages of small change of ground color, obvious reversible change under the action of light, high color fastness, and high rubbing fastness and washing fastness which both reach the highest level of grade 5, and meets the actual use requirements.
Drawings
FIG. 1 is a diagram showing the combination of the spiropyran-based photochromic compound of the present invention and cotton fabric.
FIG. 2 is a flow chart of the preparation of the carboxy-modified spiropyran photochromic dye of the present invention.
FIG. 3 is a flow chart of the preparation of the novel spiropyran-based photochromic cotton fabric.
FIG. 4 is a color-changing effect diagram of the novel spiropyran-based photochromic cotton fabric.
FIG. 5 is a color change principle diagram of the novel spiropyran photochromic cotton fabric.
FIG. 6 is a spectrogram of the novel spiropyran-based photochromic cotton fabric under ultraviolet light.
FIG. 7 is a spectrogram of the novel spiropyran-based photochromic cotton fabric under visible light.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Referring to fig. 1, the present invention provides a novel spiropyran-based photochromic cotton fabric, which comprises a cotton fabric and a carboxyl-modified spiropyran-based photochromic compound grafted to the cotton fabric through an esterification reaction, wherein the novel spiropyran-based photochromic cotton fabric undergoes photochromism under ultraviolet light and reversibly restores to white under visible light.
According to the photochromic cotton fabric, the terminal carboxyl of the functional molecule of the spiropyran derivative reacts with the abundant hydroxyl on the surface of the cotton fabric to generate an ester group, so that the spiropyran photochromic compound is combined with the cotton fabric through a covalent bond, and the durability and the color fastness of the photochromic fabric are improved; in addition, the spiropyran molecular structure is simple in design, the additionally introduced active groups are few, the proportion of a color-changing unit (namely the spiropyran structure) in the whole dye molecule is large, the influence on the ground color of the original fabric is small, a reagent and an auxiliary agent which interfere with the color are not needed in the whole process, and the ground color of the original fabric is kept to the maximum extent.
Referring to fig. 5, after being excited by ultraviolet light, the C-O bond in the molecular structure of the spiropyran-based photochromic compound is heterolytic, the molecular structure and the electronic configuration are isomerized and rearranged, the two rings are in the same plane, the whole molecule forms a large conjugated system, the absorption wavelength is red-shifted to the range of 400nm to 600nm, at this time, the molecule is in an open-loop type partially cyanine structure, and the cotton fabric is colored. And placing the cotton fabric under visible light again, enabling the open-loop system of the molecules to be closed to generate an original closed-loop structure, and enabling the conjugated system in the molecules to disappear, so that the cotton fabric is white.
Referring to fig. 2-3, the present invention further provides a method for preparing a novel spiropyran-based photochromic cotton fabric, comprising the following steps:
s1, pretreatment of cotton fabric:
soaking cotton fabric (20 × 20cm) in detergent prepared from sodium dodecyl benzene sulfonate or common commercial detergent, and washing at 40-60 deg.C under stirring for 2-3 hr to remove oil stain on the surface of cotton fabric. The preparation method of the sodium dodecyl benzene sulfonate detergent comprises the following steps: 1g of sodium dodecyl sulfate is dissolved in 1L of water and stirred uniformly. Soaking the washed cotton fabric in ethanol for 1h to further remove impurities on the surface of the cotton fabric, washing with deionized water for 2-3 times to remove residual solvent in the cotton fabric, and drying at 50-60 ℃, preferably at 60 ℃ to obtain the clean cotton fabric.
S2, coloring cotton fabrics:
dissolving carboxyl-modified spiropyran photochromic compound, Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) in any one organic solvent of dichloromethane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide. Wherein the proportion of the spiropyran photochromic compound to the organic solvent is 1g (100-200) mL; the mol ratio of the spiropyran photochromic compound to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is 1 (4-6) to 0.5-1.
Adding the clean cotton fabric obtained in the step S1 into the obtained solution, fully reacting for 20-30h at 20-40 ℃, preferably fully reacting for 24h at 30 ℃, wherein the chemical equation of the esterification reaction is shown in figure 3, the carboxyl of the spiropyran photochromic compound and the hydroxyl on the surface of the cotton fabric are subjected to esterification reaction, and the photochromic cotton fabric is obtained after dehydration.
After the reaction is finished, the cotton fabric is placed in an ultrasonic cleaner filled with dichloromethane for washing for 2 times, each time lasts for 5-10min, and residual organic reagents in the cotton fabric are removed. The cotton fabric was then further freed from residual reagents by washing 1 time each with ethanol, deionized water. And (3) drying the cotton fabric in vacuum at 30-40 ℃ for 10-12h to obtain the novel spiropyran photochromic cotton fabric.
The carboxyl modified spiropyran photochromic compound used in the process is 1- (2-carboxyethyl) -3, 3-dimethyl-6-nitro spirocyclic- [ (2H) -1-benzopyran-2, 2-indole ], and the specific preparation method is as follows (the chemical equation of the reaction is shown in figure 2):
dissolving 2,3, 3-trimethylindole and 3-bromopropionic acid in acetonitrile, heating and refluxing for 10-12H at 85-95 ℃, removing the acetonitrile by rotary evaporation after the reaction is finished, washing with diethyl ether for 3 times, and recrystallizing the residual oily substance by using an ethyl acetate/dichloromethane mixed system to obtain pink 1- (2-carboxyethyl) -2,3, 3-trimethyl-3H-indole bromide powder. Wherein the molar ratio of the 2,3, 3-trimethylindole to the 3-bromopropionic acid is 1: 2.
Dissolving the obtained 1- (2-carboxyethyl) -2,3, 3-trimethyl-3H-indole bromide, 5-nitro salicylaldehyde and triethylamine in ethanol, heating and refluxing at 85-95 ℃ for 4-6H, filtering after the reaction is finished, and washing with ethanol for 3 times to obtain brown yellow 1- (2-carboxyethyl) -3, 3-dimethyl-6-nitro spiro- [ (2H) -1-benzopyran-2, 2-indole ] powder. Wherein the mol ratio of the 1- (2-carboxyethyl) -2,3, 3-trimethyl-3H-indole bromide to the 5-nitro salicylaldehyde to the triethylamine is 1:1: 1.2.
The invention is described in detail below by means of a number of examples:
example 1
S1, pretreatment of cotton fabric:
the cotton fabric (20X 20cm) was immersed in a detergent made of sodium dodecylbenzenesulfonate and washed at 50 ℃ for 2h with stirring. The preparation method of the sodium dodecyl benzene sulfonate detergent comprises the following steps: 1g of sodium dodecyl sulfate is dissolved in 1L of water and stirred uniformly. Soaking the washed cotton fabric in ethanol for 1h, washing with deionized water for 3 times, and drying at 60 deg.C to obtain clean cotton fabric.
S2, coloring cotton fabrics:
1.5g of a carboxyl-modified spiropyran-based photochromic compound, 1- (2-carboxyethyl) -3, 3-dimethyl-6-nitrospiro- [ (2H) -1-benzopyran-2, 2-indole ], was dissolved in 150mL of dichloromethane, 4.0g of dicyclohexylcarbodiimide and 0.4g of 4-dimethylaminopyridine were added thereto, and then the clean cotton fabric (5X 5cm) obtained in step S1 was added thereto and reacted sufficiently at 30 ℃ for 24 hours. After the reaction is finished, the cotton fabric is placed in an ultrasonic cleaner filled with dichloromethane to be washed for 2 times, and each time lasts for 5 min. Followed by 1 wash with ethanol, deionized water each. And (3) drying the cotton fabric at 35 ℃ for 10 hours in vacuum to obtain the novel spiropyran photochromic cotton fabric.
Wherein, the preparation method of the 1- (2-carboxyethyl) -3, 3-dimethyl-6-nitro spiro- [ (2H) -1-benzopyran-2, 2-indole ] comprises the following steps:
10g of 2,3, 3-trimethylindole and 19.2g of 3-bromopropionic acid are dissolved in 100mL of acetonitrile and reacted at 90 ℃ under reflux for 12 h. After the reaction was completed, acetonitrile was removed by rotary evaporation, the obtained oil was washed with 30mL of diethyl ether for 3 times, the remaining crude product was recrystallized from a mixed system of ethyl acetate/dichloromethane, the solvent was filtered off, washed with ethyl acetate for 2 times, and dried at 60 ℃ for 10 hours to give 9.81g of 1- (2-carboxyethyl) -2,3, 3-trimethyl-3H-indolium bromide powder in a pink color with a yield of 46.6%.
9.68g of 1- (2-carboxyethyl) -2,3, 3-trimethyl-3H-indolium bromide, 5.25g of 5-nitrosalicylaldehyde and 5.25mL of triethylamine are dissolved in 100mL of ethanol and reacted at 90 ℃ for 6H under reflux. After the reaction was completed, the solvent was filtered off, and washed with ethanol 3 times to obtain 9.11g of a brown yellow powder of 1- (2-carboxyethyl) -3, 3-dimethyl-6-nitro-spiro- [ (2H) -1-benzopyran-2, 2-indole ] in a yield of 76.28%.
The photochromic cotton fabric prepared in the example 1 is respectively placed under ultraviolet light and visible light to observe the color of the fabric, as shown in figure 4, the cotton fabric in the left figure is placed under the visible light, and the cotton fabric is white; in the right picture, the cotton fabric is irradiated by ultraviolet light of a 365nm standard light source for 5min, and then the cotton fabric is mauve. As can be seen from the figure, the color of the cotton fabric is obviously contrasted before and after being irradiated by ultraviolet light, and the cotton fabric has excellent photochromic responsiveness.
The photochromic cotton fabric prepared in example 1 was measured for absorbance after UV/visible light irradiation with a UV-2600 UV-visible spectrophotometer to characterize its color characteristics and spectroscopic properties. As shown in figure 6, the spectrogram of the photochromic cotton fabric is placed under 365nm standard light source ultraviolet irradiation for different time, and the graph shows that the fabric shows obvious absorption at 550nm along with the increase of the ultraviolet irradiation time, which means that the color of the fabric is continuously enhanced and approaches to saturation in about 15min, and the fabric shows a purple red state at the moment. As shown in figure 7, the spectrogram of the photochromic cotton fabric is placed under the irradiation of visible light of a D65 standard light source for different times, and the graph shows that the absorption of the fabric at 550nm is continuously weakened along with the increase of the visible light irradiation time, which means that the color of the fabric is continuously faded, and the color of the fabric is gradually faded in about 20min, so that the fabric is in a white state.
The photochromic cotton fabric prepared in example 1 was subjected to color characteristic value measurement, and the color characteristic values before and after ultraviolet irradiation were measured using a color measuring and matching instrument, with the results shown in table 1: as can be seen from Table 1, the photochromic cotton fabric and the original cotton fabric have little change of various color characteristic values, especially a small change of K/S value, when not being irradiated by ultraviolet light, which indicates that the cotton fabric can still keep the white color of the original cotton fabric after being modified; after the ultraviolet light is irradiated for 15min, the photochromic cotton fabric and the original cotton fabric have obvious change of various color characteristic values and excellent photochromic performance.
TABLE 1 color characteristic values of photochromic cotton fabrics
The photochromic cotton fabric prepared in example 1 was subjected to crocking and washing fastness measurements (reference standards AATCC 8-2007 and AATCC 61-2007) and the results are shown in table 2: as can be seen from Table 2, the rubbing fastness and the washing fastness both reach 5 levels (the highest level), which shows that the photochromic cotton fabric prepared by the method has good rubbing fastness and washing fastness, and solves the problems of insufficient durability and low color fastness of the traditional coating method.
TABLE 2 color fastness of photochromic cotton fabrics
Example 2
Compared with the example 1, the difference is that the charging amount of the spiropyran photochromic compound, dicyclohexylcarbodiimide and 4-dimethylaminopyridine is 0.5 times that of the example 1, the rest is approximately the same as that of the example 1, and the details are not repeated.
The photochromic cotton fabric prepared in example 2 has a good light color under visible light, and the color change is obvious after ultraviolet light irradiation. However, compared with example 1, the photochromic cotton fabric prepared in example 2 has obviously smaller color change before and after ultraviolet irradiation, and is not beneficial to practical application.
Example 3
Compared with the example 1, the difference is that the charging amount of the spiropyran photochromic compound, dicyclohexylcarbodiimide and 4-dimethylaminopyridine is 2 times that of the example 1, the rest is approximately the same as that of the example 1, and the details are not repeated.
The photochromic cotton fabric prepared in example 3 has a good light color under visible light, and the color change is obvious after ultraviolet light irradiation. However, the color change of the photochromic cotton fabric prepared in example 3 before and after the uv irradiation did not become significantly darker, despite the increased amount of the charge compared to example 1.
From the examples 1-3, the feeding amount of the example 1 is suitable for actual production, and the feeding amount is reduced, so that the photochromic performance of the cotton fabric is weakened; the material feeding amount is increased, the photochromic performance of the cotton fabric is not obviously improved, and the waste of raw materials is caused.
Comparative example 1
Compared with the example 1, the difference is that an esterification catalyst dicyclohexylcarbodiimide is replaced by 1-ethyl- (3-dimethylaminopropyl) carbonyl diimine hydrochloride with the same mass, and the rest is substantially the same as the example 1 and is not repeated.
The photochromic cotton fabric prepared in the comparative example 1 has a good light color under visible light, but after the ultraviolet light irradiation, the whole color change is shallow, the photochromic performance is not obvious, and the practical application is not facilitated.
Comparative example 2
Compared with the example 1, the difference is that an esterification catalyst dicyclohexylcarbodiimide is replaced by N, N' -carbonyldiimidazole with equal mass, and the rest is substantially the same as that in the example 1, so that the details are not repeated.
The photochromic cotton fabric prepared in the comparative example 2 shows light red under visible light, cannot keep the original color of the cotton fabric, has light overall color change and unobvious photochromic performance after being irradiated by ultraviolet light, and is not beneficial to practical application.
As can be seen from comparative examples 1-2, the catalyst of the esterification reaction has a great influence on the ground color and photochromic property of the cotton fabric, and dicyclohexylcarbodiimide is suitable for practical production. Therefore, the cotton fabric with obvious photochromic effect and good color retention effect can be prepared by simple molecular structure design of the spiropyran and matching with proper preparation process parameters.
In conclusion, according to the novel spiropyran photochromic cotton fabric and the preparation method thereof provided by the invention, the carboxylated spiropyran and the hydroxyl on the cotton fabric are subjected to esterification reaction to realize grafting, so that the obtained photochromic fabric has photochromic property under ultraviolet light and can be reversibly restored to white under visible light, and the K/S value is not changed greatly compared with that of the original cotton fabric; the method has the advantages that the structural design of the spiropyran molecules is simple, the additionally introduced active groups are few, the proportion of a color-changing unit (namely the spiropyran structure) in the whole dye molecule is large, the influence on the ground color of the original fabric is small, in addition, reagents and auxiliary agents which have interference on the color are not needed to be used in the whole process, and the ground color of the original fabric is kept to the maximum extent; in addition, the method only needs to optimize the molecular structure of the spiropyrans through a simple process, and does not need to modify the cotton fabric, so that the process flow of chemical grafting is simplified; the chemical grafting connection of the spiropyran photochromic dye and the fabric is realized by utilizing carboxyl on the spiropyran molecular structure and abundant hydroxyl on the cotton fabric through simple esterification reaction, and the durability and the color fastness of the photochromic fabric are improved through the combination of covalent bonds (chemical bonding force), so that a new way for preparing the photochromic fabric is developed; the obtained photochromic cotton fabric has the advantages of small change of ground color, obvious reversible change under the action of light, high color fastness, and high rubbing fastness and washing fastness which both reach the highest level of grade 5, and meets the actual use requirements.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. A novel spiropyran photochromic cotton fabric is characterized in that: the novel spiropyran photochromic cotton fabric is photochromic under ultraviolet light and can be reversibly restored to white under visible light.
2. The novel spiropyran-based photochromic cotton fabric according to claim 1, characterized in that: the novel spiropyran photochromic cotton fabric has the following chemical structure:
in the formula, cotton represents cotton fabric.
3. The novel spiropyran-based photochromic cotton fabric according to claim 1, characterized in that: the K/S value of the novel spiropyran photochromic cotton fabric before photochromism or after the novel spiropyran photochromic cotton fabric is reversibly restored to white under visible light is less than 0.25.
4. A preparation method of a novel spiropyran photochromic cotton fabric is characterized by comprising the following steps: the method comprises the following steps:
s1, pretreatment of cotton fabric: soaking the cotton fabric into a detergent, and stirring, washing and drying to obtain a clean cotton fabric;
s2, coloring cotton fabrics: and (3) dissolving the carboxyl modified spiropyran photochromic compound, dicyclohexylcarbodiimide and 4-dimethylaminopyridine in an organic solvent, adding the clean cotton fabric obtained in the step S1 into the obtained solution, fully reacting, washing and drying to obtain the novel spiropyran photochromic cotton fabric.
5. The method for preparing the novel spiropyran-based photochromic cotton fabric according to claim 4, characterized in that: the organic solvent in step S2 includes, but is not limited to, one of dichloromethane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide; the ratio of the carboxyl modified spiropyran photochromic compound to the organic solvent is 1g (100-200) mL.
6. The method for preparing the novel spiropyran-based photochromic cotton fabric according to claim 4, characterized in that: in the step S2, the molar ratio of the carboxyl modified spiropyran photochromic compound to the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine is 1 (4-6) to (0.5-1); the feeding mass ratio of the cotton fabric to the carboxyl modified spiropyran photochromic compound is 1 (2-4).
7. The method for preparing the novel spiropyran-based photochromic cotton fabric according to claim 4, characterized in that: the structural formula of the carboxyl modified spiropyran photochromic compound in the step S2 is as follows:
8. the method for preparing the novel spiropyran-based photochromic cotton fabric according to claim 7, characterized in that: the preparation method of the carboxyl modified spiropyran photochromic compound comprises the following steps:
s21, dissolving 2,3, 3-trimethylindole and 3-bromopropionic acid in acetonitrile, heating and refluxing for 10-12H at 85-95 ℃, removing the acetonitrile by rotary evaporation after the reaction is finished, washing with diethyl ether for 3 times, and recrystallizing the residual oily substance by using an ethyl acetate/dichloromethane mixed system to obtain 1- (2-carboxyethyl) -2,3, 3-trimethyl-3H-indole bromide powder.
S22, dissolving the obtained 1- (2-carboxyethyl) -2,3, 3-trimethyl-3H-indole bromide, 5-nitro salicylaldehyde and triethylamine in ethanol, heating and refluxing for 4-6H at 85-95 ℃, filtering after the reaction is finished, and washing for 3 times by using ethanol to obtain the carboxyl modified spiropyran photochromic compound.
9. The method for preparing the novel spiropyran-based photochromic cotton fabric according to claim 4, characterized in that: the detergent in the step S1 is a detergent prepared by sodium dodecyl benzene sulfonate or a common commercial detergent; the stirring is carried out for 2-3h at the temperature of 40-60 ℃; the washing is washing by using ethanol and deionized water in sequence; the drying is drying at 50-60 ℃.
10. The method for preparing the novel spiropyran-based photochromic cotton fabric according to claim 4, characterized in that: washing in the step S2 is washing with dichloromethane, ethanol and deionized water in sequence; the drying is vacuum drying at 30-40 deg.C for 10-12 h.
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