CN113666939B

CN113666939B - Photochromic compound and preparation method and application thereof

Info

Publication number: CN113666939B
Application number: CN202110944760.8A
Authority: CN
Inventors: 孙昌; 薛惊理; 柳赟雯; 金光; 王潮霞; 陈文浩
Original assignee: Consinee Group Co ltd; Jiangnan University
Current assignee: Consinee Group Co ltd; Jiangnan University
Priority date: 2021-08-17
Filing date: 2021-08-17
Publication date: 2022-11-25
Anticipated expiration: 2041-08-17
Also published as: CN113666939A

Abstract

The invention relates to a photochromic compound and a preparation method and application thereof, belonging to the field of dyeing and finishing chemistry. The invention prepares the photochromic compound by dissolving indole derivatives and alkyl halides in organic solvent, adding salicylaldehyde derivatives, tertiary amine and phase transfer catalyst and heating. The photochromic compound contains spiropyran as effective component, and can undergo ring-opening reaction quickly after being irradiated by ultraviolet ray to change from colorless body to color body. The rate of decolorization in protic solvents is much higher than in aprotic solvents. The photochromic compound disclosed by the invention is quick in photoresponse and good in solubility, avoids using an organic solvent in the dyeing process, reduces the production cost and harm to human health, and is good in antibacterial performance and high in washing color fastness of dyed wool textiles.

Description

Photochromic compound and preparation method and application thereof

Technical Field

The invention relates to the technical field of dyeing and finishing chemistry, in particular to a photochromic compound and a preparation method and application thereof.

Background

Photochromic materials are those that cause a change in the wavelength of maximum absorption of a particular wavelength of light. The color change phenomenon is caused by the photophysical effect or photochemical reaction of the substance under the light with the specific wavelength, wherein the photophysical effect refers to the fact that when the substance is stimulated by the light with the specific wavelength, the electron generation energy level transition or the substance particle valence state change inside the substance, and the photochemical reaction refers to the fact that the substance is irradiated by the light with the specific wavelength, the self structure of the substance is changed.

The material generally has good chemical stability and optically variable selectivity, is beneficial to commercial application and has wide development prospect. At present, functional materials based on photochromic materials are applied and developed in various fields, and the photochromic mechanism of the functional materials is more comprehensively researched. Photochromic materials are various, and the initial research objects are mainly cis-trans isomeric photochromic materials and azo photochromic materials, which are relatively easy to synthesize, but have poor stability and fatigue resistance. Photochromic materials such as dithienylethylene, spiropyran and spirooxazine are favored by people due to more excellent fatigue resistance and stability, and become a new focus and direction for researching the photochromic materials.

In recent years, color-changing textiles with high added value, which have been rapidly developed, have been receiving more and more attention in various fields. The requirements of the color-changeable textile in the fields of clothes, textiles and the like are rapidly expanded, particularly, the increasing seeking of people for different psychology and the pursuit of fashion cumin are promoted, the development of the color-changeable textile is promoted, the colors of the textile clothes are more and more abundant and colorful, the textile clothes are more and more personalized, and the fashionable clothes greatly meet the pursuit of people for the visual sense.

The photochromic material can obtain novel visual impact when being applied to the fabric, and provides decoration and functionality for the fabric, but the photochromic material is sensitive to the action of a solvent and an auxiliary agent in the process of finishing and external factors in the use process, is easy to develop color due to the solvent, and is also easy to be influenced by conditions such as pH value, oxygen, illumination, temperature and the like, so that the photochromic material is oxidized or causes fatigue resistance and poor light stability. And the residual quantity of chemical reagents of the fabric treated by the traditional process is too high, so that the requirement of sanitation and safety is difficult to meet.

The spiropyran photochromic dye has quick reaction time and excellent stability in both open-loop and closed-loop states, and a series of functional color-changing fabrics can be produced by utilizing the properties. The existing photochromic dyes have the problems of few types, the mode of realizing coloring is generally that adhesives are used for pigment printing or the dyes are changed into reactive dyes for dyeing cotton and viscose, and the dyeing method aims at solving the problems of few dyes of wool textiles, poor antibacterial property, slow photoresponse, low washing color fastness of dyed textiles and the like.

Disclosure of Invention

In order to solve the technical problems, the invention provides a photochromic compound and a preparation method and application thereof. Starting from the synthesis process of the spiropyran, the novel spiropyran compound which has good antibacterial performance, quick photoresponse and high washing fastness after dyeing is prepared and can be used as photochromic dye with better performance to dye wool.

The first object of the present invention is to provide a photochromic compound C having the following structural formula:

wherein R is ₁ Is disubstituted C2-C4 alkyl; r ₂ is-CH ₃ or-CH ₂ -CH ₃ ；R ₃ is-NO ₂ or-Cl;

x is Cl, br or I.

Further, said compound C is selected from the following compounds:

the second object of the present invention is to provide a process for preparing photochromic compound C, comprising the steps of:

dissolving indole derivatives and alkyl halides in an organic solvent, adding salicylaldehyde derivatives, tertiary amine and a phase transfer catalyst, heating, and reacting to obtain the compound C.

Further, the preparation method specifically comprises the following steps:

s1: dissolving indole derivatives and alkyl halides in an organic solvent, heating, refluxing in a protective atmosphere, and reacting for 4-8h to obtain a compound A;

s2: dissolving the compound A obtained in the step S1 in an organic solvent, adding a salicylaldehyde derivative, heating, refluxing in a protective atmosphere, and reacting for 12-24 hours to obtain a compound B;

s3: and (3) dissolving the compound B obtained in the step (S2) in an organic solvent, adding tertiary amine and a phase transfer catalyst, refluxing in a protective atmosphere, and reacting for 48-72h to obtain the compound C.

Further, the indole derivative is 2, 3-trimethyl-3H-indole.

Further, the alkyl halide is dibromoethane, dichloroethane, diiodoethane, dibromopropane, dichloropropane, diiodopropane, dibromobutane, dichlorobutane or diiodobutane.

Further, the organic solvent is one or more of methanol, ethanol and acetonitrile.

Further, the salicylaldehyde derivative is 5-nitro salicylaldehyde or 5-chloro salicylaldehyde.

Further, the tertiary amine is trimethylamine or triethylamine.

Further, the phase transfer catalyst is tetra-n-butylammonium iodide or benzyltriethylammonium chloride.

Further, the molar ratio of the indole derivative, the alkyl halide, the salicylaldehyde derivative, the tertiary amine and the phase transfer catalyst is 1:0.8-5:1-5:1.2-3.5:0.01-1.6.

Further, the heating temperature is 70-80 ℃.

The third purpose of the invention is to provide the application of the photochromic compound C in dyeing wool textiles.

The fourth purpose of the invention is to provide a photochromic wool textile, which is obtained by dyeing and finishing the wool textile by using the photochromic compound C.

Compared with the prior art, the technical scheme of the invention has the following advantages:

(1) The spiropyran molecules in the photochromic compound have different maximum absorption wavelengths in different organic solvents. As the polarity of the solvent increases, the wavelength of maximum absorption shifts blue, while as the polarity decreases, the wavelength of maximum absorption shifts red. The less polar the solvent, the more blue the solution color and vice versa. The spiropyran molecules have different decoloring times after being irradiated by ultraviolet light to open the ring in different organic solvents. The decolorization process in an aprotic solvent follows a first order kinetic equation, with the rate of decolorization in an aprotic solvent being much higher than the rate of decolorization in a protic solvent.

(2) The photochromic compound provided by the invention utilizes the antibacterial property of the quaternary ammonium salt, introduces antibacterial groups while dyeing wool fabrics, improves the antibacterial property of wool, reduces the subsequent antibacterial finishing procedures and reduces the cost. The bacterial cell wall has negative charge, the quaternary ammonium salt is electropositive and can be combined with the bacterial cell wall by coulomb force, and the tail part of the lipophilic side chain is inserted into the bacterial cell membrane, so that the electrical balance of the cell membrane is disturbed, the integrity of the cell membrane is damaged, the cell content is leaked, and the bacterial death achieves the antibacterial purpose. The bacteriostatic performance on staphylococcus aureus ATCC6538 and escherichia coli 8099 reaches 97 percent.

(3) The photochromic compound of the invention utilizes the strong electron-withdrawing group nitryl to introduce the nitryl on the benzene ring adjacent to the pyran ring, so that the stability of the phenoxide anion is improved, and the photoresponse speed of the spiropyran molecules is increased. When an electron-withdrawing group is introduced to the benzopyran ring, the instability of C-O is increased, so that the photochromic performance of the photochromic compound is enhanced, and the stronger the electron-withdrawing capability of the introduced electron-withdrawing group is, the stronger the corresponding photoresponse is. The nitro group is a strongly electron withdrawing group and the chlorine is a weakly electron withdrawing group, so that the photoresponse of the nitro group is stronger than that of the chlorine. The method is characterized in that a standard light source lamp box is used for simulating outdoor sunlight, after the dyed wool textile is irradiated, an 'open loop' reaction is immediately carried out, a spiropyran colorless state is changed into a part cyanine colored state, a substituent in a benzopyran ring is nitro, the conversion balance is achieved within about 90s, and the substituent is chlorine, and the conversion balance can be achieved within 150 s.

(4) The photochromic compound provided by the invention changes the nitrogen atom substituent of the indoline ring, introduces short-chain quaternary ammonium salt, changes the polarity of the spiropyran molecules, enhances the solubility of the spiropyran molecules in water, avoids using an organic solvent in the dyeing process, and reduces the production cost and harm to human health.

(5) The invention provides a compound for low-temperature dyeing of wool. The dyeing rate of the wool textile can reach more than 65 percent by dyeing at the low temperature of 60 ℃.

Drawings

In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the present disclosure taken in conjunction with the accompanying drawings, in which:

FIG. 1 is a NMR spectrum of 1,3,3-dimethyl-N-bromopropyl-6-nitroindolinylspiropyran of example 2.

FIG. 2 is a mass spectrum of SPTEA of example 2.

FIG. 3 is a first order kinetic fit of the extinction process in each solvent of test example 1.

FIG. 4 is a graph showing the effect of pH on the color change of the SPTEA ethyl acetate solution in test example 2.

FIG. 5 is a graph showing K/S values before and after discoloration of wool in test example 3.

Detailed Description

The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.

Example 1

A photochromic compound and a preparation method thereof comprise the following steps:

1.2, 3-trimethyl-3H-indole (5.0 g, 31mmol) and 1, 3-dibromopropane (19.0 g, 94mmol) were dissolved in methanol, heated to 80 ℃ in a round-bottomed flask, and reacted for 4 hours under reflux under a nitrogen atmosphere.

2. The solid was washed with ethyl acetate and cyclohexane (v/v, 1), and suction filtered under reduced pressure to give 1- (3-bromopropyl) -2, 3-trimethyl-3H-indole-1-ammonium bromide.

3. 1- (3-bromopropyl) -2, 3-trimethyl-3H-indole-1-ammonium bromide (1.8g, 5 mmol) is dissolved in ethanol, 5-nitro salicylaldehyde (0.83g, 5 mmol) and trimethylamine (0.77mL, 5.5 mmol) are added dropwise, the mixture is heated to 80 ℃ in a round-bottom flask, refluxed under the protection of nitrogen atmosphere, and reacted for 12 hours in the dark, and filtered.

4. The filtrate was subjected to column chromatography (v/v, ethyl acetate: petroleum ether =1 = 9) to give 1' - (3 ' -bromopropyl) -3',3' -dimethyl-6-nitropyrrole [ (2H) -1-benzopyran-2, 2' -indole ] a.

5. Dissolving a (1.2g, 2.8mmol) and trimethylamine (0.33g, 5.6 mmol) in ethanol, dropwise adding a phase transfer catalyst tetra-n-butylammonium iodide (0.1g, 0.28mmol), heating to 70 ℃ in a round-bottomed flask, refluxing under the protection of nitrogen, and keeping out of light for reaction for 48h.

6. After filtration, the solid was washed with ethyl acetate to give 1' - (3 ' -trimethylaminopropyl) -3',3' -dimethyl-6-nitropyrrole [ (2H) -1-benzopyran-2, 2' -indole ] bromide (SPTMA).

Example 2

3. 1- (3-bromopropyl) -2, 3-trimethyl-3H-indole-1-ammonium bromide (1.8g, 5 mmol) is dissolved in ethanol, 5-nitro salicylaldehyde (0.83g, 5 mmol) and triethylamine (0.77mL, 5.5 mmol) are added dropwise, the mixture is heated to 80 ℃ in a round-bottom flask, refluxed under the protection of nitrogen atmosphere, and reacted for 12 hours in the dark, and filtered.

5. Dissolving a (1.2g, 2.8 mmol) and triethylamine (0.56g, 5.6 mmol) in ethanol, dropwise adding a phase transfer catalyst of benzyltriethylammonium chloride (0.1g, 0.28mmol), heating to 70 ℃ in a round-bottom flask, refluxing under the protection of nitrogen, and reacting for 48h in a dark place.

6. After filtration, the solid was washed with ethyl acetate to give 1' - (3 ' -triethylaminopropyl) -3',3' -dimethyl-6-nitropyrrole [ (2H) -1-benzopyran-2, 2' -indole ] bromide (SPTEA).

FIG. 1 shows the hydrogen nuclear magnetic resonance spectrum of example 2 a. Wherein the chemical shift is 1.19, and the chemical shift at 1.29ppm is-CH ₃ The proton signal of the middle 6H is-CH at 3.48-3.36,3.29,2.34-2.20,2.14-2.02ppm ₂ The proton signal of 6H in-1, the proton signal of 9H in the benzene ring at 5.87,6.64,6.75,6.97-6.86,7.10,7.20,8.04-8.00ppm, indicates that the ring closure reaction produces the desired intermediate, 1, 3-dimethyl-N-bromopropyl-6-nitroindoline spiropyran.

FIG. 2 is a mass spectrum of SPTEA of example 2. The peak at 450.2791m/z can be seen, the relative molecular mass of the SPTEA is calculated to be 450.60, and the existence of the target SPTEA in the product can be proved by matching with the mass spectrum result.

Example 3

1.2, 3-trimethyl-3H-indole (5.0 g, 31mmol) and 2, 2-dibromopropane (19.0 g, 94mmol) were dissolved in methanol, heated to 80 ℃ in a round-bottomed flask, and reacted for 4 hours under reflux under a nitrogen atmosphere.

2. The solid was washed with ethyl acetate and cyclohexane (v/v, 1), and suction filtered under reduced pressure to give 2- (2-bromopropyl) -2, 3-trimethyl-3H-indole-1-ammonium bromide.

3. 2- (2-bromopropyl) -2, 3-trimethyl-3H-indole-1-ammonium bromide (1.8g, 5 mmol) is dissolved in ethanol, 5-chlorosalicylaldehyde (0.83g, 5 mmol) and trimethylamine (0.77mL, 5.5 mmol) are added dropwise, the mixture is heated to 80 ℃ in a round-bottomed flask, refluxed under the protection of nitrogen atmosphere, reacted for 12H in the dark, and filtered.

4. The filtrate was subjected to column chromatography (v/v, ethyl acetate: petroleum ether =1 = 9) to give 2' - (2 ' -bromopropyl) -3',3' -dimethyl-6-chloropyrrole [ (2H) -1-benzopyran-2, 2' -indole ] b.

5. Dissolving b (1.2g, 2.8mmol) and trimethylamine (0.33g, 5.6 mmol) in ethanol, dropwise adding a phase transfer catalyst tetra-n-butylammonium iodide (0.1g, 0.28mmol), heating to 70 ℃ in a round-bottom flask, refluxing under the protection of nitrogen, and reacting for 48h in a dark place.

6. After filtration, the solid was washed with ethyl acetate to give 2' - (2 ' -trimethylaminopropyl) -3',3' -dimethyl-6-chloropyrrole [ (2H) -1-benzopyran-2, 2' -indole ] bromide (SPBMA).

Test example 1

The SPTEA compound synthesized in example 2 was formulated into 1X 10 using four solvents of petroleum ether, ethyl acetate, acetone, and methanol, respectively ^-4 Irradiating the diluted solution with 365nm ultraviolet lamp for 3min, measuring the absorption curve of the diluted solution immediately with an ultraviolet-visible spectrophotometer, irradiating the solution for 3min again, and measuring the change of the absorption intensity of the diluted solution at the maximum absorption wavelength every 10s, wherein the test results are shown in Table 1:

TABLE 1

	Petroleum ether	Acetic acid ethyl ester	Acetone (II)	Methanol
					Color before irradiation	Light yellow	Light yellow	Yellow colour	Light pink color
Color after irradiation	Blue colour	Blue color	Bluish violet	Pink colour
					Maximum absorption wavelength/nm	602	590	576	538
Fast and slow fading	Quick-acting tool	Quick-acting tool	Is quicker	Slow

As can be seen from table 1: as the polarity of the solvent increases, the absorption maximum wavelength of the SPTEA shifts blue, while the absorption maximum wavelength shifts red as the polarity decreases. The less polar the solvent, the more blue the solution color and vice versa.

Kinetic fitting results of the decolorization process as shown in fig. 3, the decolorization process of SPTEA in petroleum ether, ethyl acetate, and acetone conforms to the first order kinetic equation:

ln[(A _t -A _e )(A ₀ -A _e )]＝-kt

wherein A is ₀ 、A _t And A _e The absorbance of the solution at 0 moment, t moment and infinite moment respectively, and k is an extinction coefficient.

The extinction coefficient of SPTEA in petroleum ether is k _a ＝1.63×10 ^-2 S ^-1 Extinction coefficient in acetone is k _b ＝1.16×10 ^-2 S ^-1 Extinction coefficient in ethyl acetate is k _c ＝3.29×10 ^-2 S ^-1 Extinction coefficient in methanol of 5.00X 10 ^-3 S ^-1 . From this, it can be seen that the decoloring rate in the aprotic solvent is much higher than that in the protic solvent, and the decoloring rate of ethyl acetate is the fastest among the three aprotic solvents.

Test example 2

The SPTEA compound synthesized in example 2 was dissolved in ethyl acetate to prepare a 1X 10 solution ^-4 The solution was observed to change by adjusting the pH of the solution by mol/L with HCl/TEA and irradiating for 3min with a 365nm UV lamp, and the results are shown in FIG. 4.

As can be seen from FIG. 4, the color immediately changed to yellow and lost photochromic ability after adding dilute hydrochloric acid solution dropwise to the SPTEA ethyl acetate solution. After the subsequent addition of a dilute solution of TEA, the solution immediately turned dark blue and faded colorless after 30 s. Because the open ring position of the spiropyran is provided with oxygen anions, the spiropyran can be combined with hydrogen ions under the acidic environment, so that the spiropyran cannot be subjected to ring closing, and the photochromic capacity is lost; and the stability of oxygen anions can be enhanced under the alkaline condition, and the color-assisting effect is achieved.

Test example 3

The photochromic compounds prepared in examples 1, 2 and 3 were dissolved in ultrapure water, respectively, to prepare a dye solution of o.w.f2% with a pH of 7, wool pretreated in hot water at 70 ℃ for 5min was put into a dye bath, dyed at 60 ℃ for 1 hour, and a wool sample was taken out, washed with water, and naturally dried in the dark. The dye uptake was measured and calculated to be 70.13%, 78.92%, 65.35%, respectively.

The change of K/S value before and after SPTEA dyed fabric is tested, and the change of color of the fabric is tested by using a Datacolor 650 built-in color-changing color card according to the color change grade of the fabric dyed by AATCC 139-2005RA 50. The wash fastness after dyeing of wool fabrics was tested according to the standard GB/T3921-2008, the test results are shown in FIG. 5 below.

As can be seen from figure 5, after the dyed wool is irradiated by ultraviolet, the K/S value of the cloth sample is enhanced at 500-600nm, the enhancement is maximum at 550nm, and the K/S value is increased from 0.3882 to 0.8044, which proves that the color depth of the cloth sample in the wave band is deepened. And grading according to a Datacolor built-in color-changing color card, wherein the GS rating value is 2.25, and the GS evaluation grade is 2-3. The obvious color change capability after the fabric is dyed on the dye is proved. And SPTMA and SPTEA can reach the conversion equilibrium of spiropyran and part cyanine after the illumination for about 90s, and SPBMA reaches the conversion equilibrium after the illumination for 150 s. The fabric is subjected to a color fastness to washing test according to a method in the standard GB/T3921-2008, after washing for 30min, the color of the lining cloth on two sides and the washing liquid is not changed after 365nm ultraviolet radiation, and the compound has good bonding fastness with the fabric.

Test example 4

The method comprises the steps of measuring the antibacterial performance of the dyed fabrics of SPTMA and SPTEA in the test example 3 on staphylococcus aureus ATCC6538 and Escherichia coli 8099 by using an oscillating flask method according to GB/T20944.3-2008 part 3 oscillation method for evaluating antibacterial performance of textiles, and calculating the antibacterial rate according to the following formula, wherein the test results are shown in Table 2:

TABLE 2

Test specimen	Staphylococcus aureus	Escherichia coli
			Not finished	60.2％	62.3％
SPTMA	97.7％	97.1％
			SPTEA	99.2％	99.5％

As can be seen from Table 2, although the wool has a certain antibacterial property, the antibacterial rate of the dyed wool to Staphylococcus aureus and Escherichia coli is greatly improved, wherein the inhibition rate of the dyed wool textile to two strains is as high as 99%.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications derived therefrom are intended to be within the scope of the invention.

Claims

1. Photochromic compound C, characterized in that it is chosen from the following compounds:

2. the process for preparing photochromic compound C according to claim 1, comprising the steps of:

3. The method for preparing photochromic compound C according to claim 2, comprising the following steps:

s2: dissolving the compound A obtained in the step S1 in an organic solvent, adding a salicylaldehyde derivative, heating, refluxing under a protective atmosphere, and reacting for 12-24 hours to obtain a compound B;

4. The process for the preparation of photochromic compound C according to claim 2, characterized in that: the indole derivative is 2, 3-trimethyl-3H-indole.

5. The process for the preparation of photochromic compound C according to claim 2, characterized in that: the alkyl halide is dibromoethane, dichloroethane, diiodoethane, dibromopropane, dichloropropane, diiodopropane, dibromobutane, dichlorobutane or diiodobutane.

6. The process for the preparation of photochromic compound C according to claim 2, characterized in that: the organic solvent is one or more of methanol, ethanol and acetonitrile.

7. The process for preparing photochromic compound C according to claim 2, wherein: the salicylaldehyde derivative is 5-nitro salicylaldehyde or 5-chloro salicylaldehyde; the tertiary amine is trimethylamine or triethylamine; the phase transfer catalyst is tetra-n-butyl ammonium iodide or benzyltriethyl ammonium chloride.

8. The process for the preparation of photochromic compound C according to claim 2, characterized in that: the mol ratio of the indole derivative, the alkyl halide, the salicylaldehyde derivative, the tertiary amine and the phase transfer catalyst is 1:0.8-5:1-5:1.2-3.5:0.01-1.6.

9. Use of photochromic compound C according to claim 1 in the dyeing of wool textiles.