CN112961341A - Photochromic azobenzene polyamide and preparation method thereof and photochromic nylon fiber - Google Patents
Photochromic azobenzene polyamide and preparation method thereof and photochromic nylon fiber Download PDFInfo
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Abstract
The invention provides a photochromic azobenzene polyamide, a preparation method thereof and photochromic nylon fibers. The photochromic azobenzene polyamide comprises a polyamide chain segment and an azobenzene derivative chain segment, wherein a benzene ring structure in the azobenzene derivative chain segment is arranged on the main chain of the photochromic azobenzene polyamide. Firstly, preparing a carboxyl azobenzene derivative containing alkyl and amino, wherein the amino and the carboxyl are on the same benzene ring, and performing melt polymerization on the carboxyl azobenzene derivative serving as a polymerization monomer and lactam or alkyl polyamine and alkyl polyacid to obtain azobenzene polyamide. According to the invention, the azobenzene structure is embedded into the nylon molecular chain, so that the polyamide has a photochromic function and a good melt spinning performance, and the nylon fiber obtained by melt spinning the polyamide has a good mechanical property and a photochromic function.
Description
Technical Field
The invention relates to the technical field of functional polymer materials, in particular to photochromic azobenzene polyamide and a preparation method thereof, and photochromic nylon fiber.
Background
Polyamide (nylon) as one of five engineering plastics has the characteristics of high tensile strength, large elastic modulus, excellent wear resistance and self-lubricating property and the like, and is widely applied to the industries of automobile manufacturing, electronic and electric appliance industry, mechanical equipment, packaging and the like. With the development of science and technology and the improvement of living standard of people, people put forward higher requirements on the color of clothes, and not only the proper color is needed, but also the color of patterns in the clothes can be expected to change along with light. Photochromic fibers are a new class of functional fibers that reversibly change color with different wavelengths of exposure to light. The fiber has the advantages of high application value, no toxicity, no harm, long service life and the like, and can be widely applied to various fields of national defense, military, national economy and the like, such as anti-counterfeiting trademarks, paper money, identity cards, color-changing windows, optical sensors, optical switches, information storages, camouflage clothes, military tents, weapon camouflage covers and the like.
Due to the existence of azo groups (-N ═ N-), azobenzene polymers can be converted from a trans structure to a cis structure under 365nm ultraviolet illumination, and can be returned to the trans configuration under the action of visible light or heat. Chinese patent CN201310411100.9 discloses a photochromic fiber and a preparation method thereof, wherein nylon 6, photochromic materials and the like are blended and electrostatically spun to obtain the photochromic nylon fiber. The method is not beneficial to large-scale industrial production, the preparation process is relatively complicated, and the durability of the color-changing performance of the photochromic fiber prepared by the blending method is also deficient. Chinese patent CN201310078996.3 discloses a method for manufacturing photochromic fibers, which comprises the steps of mixing low-photochromic master batches with low-melting-point nylon chips, and preparing the photochromic fibers by melt blending spinning. The method is only suitable for low-melting-point nylon or can be only used under the condition that the melt spinning temperature is not more than 180 ℃, and when the temperature is higher than 180 ℃, the photochromic agent loses activity and has no color change effect any more, so the method is not suitable any more. In addition, the fiber prepared by mixing the color-changing agent into nylon by adopting a blending method also has the defects of fading, poor hand feeling, poor wear resistance and the like.
Due to excellent optical activities such as photoinduced isomerization and photoinduced orientation, azobenzene polymers have wide application prospects in the fields of optical information storage, optoelectronics, molecular switches, nonlinear optical materials and the like. There are mainly 3 types of azobenzene polymers reported so far: host-guest doped, side-chain azo polymers, and host-chain azo polymers. The introduction of an azo group into a polymer plays a very important role in improving the performance of the polymer. Patent CN201811380342.5 discloses a photochromic polyacrylamide supramolecular hydrogel and a preparation method thereof, acrylamide and azobenzene spiropyran functionalized acrylamide are used as reaction monomers to be polymerized to obtain a photochromic polymer, and azobenzene in the scheme is in a polymer side chain and has poor thermal stability. Patent CN201910636018.3 discloses a N-linked main chain azobenzene polymer and a film preparation method thereof, dinitroaniline is used as a reaction monomer, and the polymer with the main chain azobenzene is obtained by polymerization under the action of a reducing agent, and the main chain of the polymer only contains an azobenzene structure, so that the processing performance is poor, and the function is single. Patent CN201910600051.0 discloses a photochromic hyperbranched azopolyamide and a preparation method thereof, wherein 4, 4' -diaminoazobenzene and trimesic acid are used as raw materials, and a low-temperature solution is subjected to polycondensation to obtain the photochromic hyperbranched azopolyamide, but the spinning processability of the hyperbranched polymer is poor, so that the photochromic hyperbranched azopolyamide is not suitable as a spinning raw material.
In view of the above, there is a need to design an improved photochromic polyamide fiber to solve the above problems.
Disclosure of Invention
The invention aims to provide a photochromic azobenzene polyamide, a preparation method thereof and a photochromic nylon fiber. According to the invention, the azobenzene structure is embedded into the nylon molecular chain, so that the polyamide has a photochromic function and a good melt spinning performance, and the nylon fiber obtained by melt spinning the polyamide has good mechanical properties and a photochromic function, and the photosensitive durability is obviously improved.
In order to achieve the above object, the present invention provides a photochromic azobenzene polyamide, wherein the photochromic azobenzene polyamide comprises a polyamide segment and an azobenzene derivative segment, and one benzene ring structure in the azobenzene derivative segment is on the main chain of the photochromic azobenzene polyamide, and the other benzene ring structure is on the side chain; the structural formula of the photochromic azobenzene polyamide is shown as a formula I or a formula II:
wherein R is1Is an alkyl group having 4 to 12 carbon atoms, R2Is an alkyl group with 2-10 carbon atoms, R3Is an alkyl group having 5 to 10 carbon atoms, R4Is an alkyl group having 6 to 12 carbon atoms, m is 50 to 1500, and n is a positive integer of 10 to 50.
As a further improvement of the invention, the mass content of the azobenzene derivative chain segment in the photochromic azobenzene polyamide is 1-20%.
As a further improvement of the invention, R1Is an alkyl group having 4 to 8 carbon atoms, R3Is an alkyl group having 5 to 8 carbon atoms, R4Is an alkyl group having 6 to 8 carbon atoms.
The preparation method of the photochromic azobenzene polyamide comprises the following steps:
s1, preparing azobenzene containing carboxyl: placing the 3-amino-5-nitrobenzoic acid suspension in a hydrochloric acid solution, cooling the solution in a water-ice bath at 0-5 ℃, adding a nitrite aqueous solution under the stirring condition, and stirring to obtain a diazonium salt suspension;
then adding a solution consisting of sodium acetate and phenol, and stirring and reacting for 20-40 min at 5 ℃; then adding the red orange azo compound into an acidic aqueous solution to obtain a red orange azo compound precipitate;
then filtering and taking a precipitate, washing the precipitate by using a sodium bicarbonate aqueous solution, then drying the precipitate, and recrystallizing the dried precipitate in boiling n-octane to obtain red-orange azobenzene containing carboxyl;
s2, preparing carboxyazobenzene containing alkyl groups: the azobenzene and K containing carboxyl obtained in the step S12CO3Adding KI, acetonitrile and bromoalkane into a round-bottom flask, refluxing for 3-10 h, pouring the reaction liquid into water, performing suction filtration, and recrystallizing in a mixed solvent consisting of ethanol and water to obtain yellow carboxyl azobenzene containing alkane groups;
s3, preparing carboxyl azobenzene containing alkyl and amino: amination is carried out on the carboxyazo benzene containing the alkyl group obtained in the step S2 under the condition of a catalyst Pd/C and hydrogen to obtain carboxyazo benzene containing the alkyl group and amino;
s4, preparing azobenzene polyamide: and (4) performing melt polycondensation by using the carboxyazobenzene containing the alkyl group and the amino group obtained in the step (S3) and lactam or alkyl polyamine and alkyl polyacid as polymerization monomers to obtain the azobenzene polyamide.
As a further improvement of the present invention, in step S4, the melt polycondensation includes: introducing nitrogen into a condensation reaction container to remove air, then adding 1-3% of lactam or alkyl polyamine and alkyl polyacid, water and concentrated phosphoric acid into the condensation reaction container according to the mass percentage of 100%, 1-2%, and continuously introducing nitrogen, and stirring and reacting for 3-4 hours at 230-250 ℃;
and then adding the carboxyazobenzene containing the alkyl group and the amino group, which accounts for 0.05-1.0% of the lactam or the sum of the alkyl group polyamine and the alkyl group polyacid, into the reaction system, raising the temperature of the polymerization system to 260-270 ℃, adjusting the stirring rotation speed to 250-300 r/min, closing the nitrogen, vacuumizing the reaction container, and carrying out reduced pressure polycondensation for 10-30 min to obtain the azobenzene polyamide.
As a further improvement of the invention, the lactam is butyrolactam or caprolactam, the alkane polyamine is a straight chain alkane diamine with 5-10 carbon atoms, and the alkane polyacid is a straight chain alkane diacid with 6-12 carbon atoms.
As a further improvement of the present invention, in step S1, the nitrite is sodium nitrite.
In a further improvement of the present invention, in step S2, the alkyl bromide is an alkyl group having 2 to 10 carbon atoms.
In a further improvement of the present invention, in step S2, the volume ratio of ethanol to water in the mixed solvent is 1:3 to 2: 1.
The photochromic nylon fiber is obtained by melt spinning the photochromic azobenzene polyamide or the photochromic azobenzene polyamide prepared by the preparation method.
The invention has the beneficial effects that:
1. the photochromic azobenzene polyamide structure provided by the invention is different from a side chain type or main chain type azobenzene polymer in the prior art, one benzene ring in azobenzene is embedded into a polyamide main chain through polymerization, the high temperature resistance of polyamide can be improved under the condition of not influencing the photochromic function of azobenzene, and the defects of no high temperature resistance, poor durability, poor wear resistance, inconvenience for industrial production, complex operation and the like of photochromic fibers prepared by blending are overcome.
2. According to the invention, parameters such as molecular weight of azobenzene polyamide and content of azobenzene are regulated and controlled, so that the polymer has a color changing function, high temperature resistance and excellent polyamide performance, and the polymer can be directly used for melt spinning, thus the high-performance polyamide fiber with photochromic performance is prepared, and the color changing sensitivity is high. The azobenzene polyamide fiber can be applied to various fields, and has important significance for improving the high temperature resistance and the durability of the color changing function of the photosensitive color changing nylon fiber.
3. The method takes 3-amino-5-nitrobenzoic acid as a raw material, the raw material reacts with nitrite to obtain diazonium salt, and then the diazonium salt reacts with phenol to obtain azobenzene containing carboxyl; then the phenolic hydroxyl and halogenated alkane are subjected to substitution reaction, and then the nitro is reduced into amino to obtain azobenzene with the amino and the carboxyl on the same benzene ring. The azobenzene has high thermal stability, and is used as a reaction monomer to be subjected to melt polycondensation with a polyamide reaction monomer to obtain the azobenzene polyamide with one benzene ring at the main chain and the other benzene ring at the side chain. The invention has the advantages of simple and reasonable preparation method, mild reaction conditions, high yield, low energy consumption, less pollutants and suitability for large-scale production.
Drawings
FIG. 1 shows the intermediate product of example 1, carboxyazobenzene (R) containing an alkyl group and a nitro group2Pentanyl) is used.
FIG. 2 shows a carboxyazobenzene (R) containing an alkyl group and an amino group in example 12Pentyl) is used as a light source.
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.
The invention provides photochromic azobenzene polyamide, which comprises a polyamide chain segment and an azobenzene derivative chain segment, wherein one benzene ring in the azobenzene derivative chain segment is on the main chain of the photochromic azobenzene polyamide, and the other benzene ring is on the side chain; the structural formula of the photochromic azobenzene polyamide is shown as a formula I or a formula II:
wherein R is1Is an alkyl group having 4 to 12 carbon atoms, R2Is an alkyl group with 2-10 carbon atoms, R3Is an alkyl group having 5 to 10 carbon atoms, R4Is an alkyl group having 6 to 12 carbon atoms, m is 50 to 1500, and n is a positive integer of 10 to 50.
The mass content of the azobenzene chain segment in the photochromic azobenzene polyamide is 1-20%.
The R is1Is an alkyl group having 4 to 8 carbon atoms, R3Is an alkyl group having 5 to 8 carbon atoms, R4Is an alkyl group having 6 to 8 carbon atoms.
The photosensitive color-changing azobenzene polyamide structure is different from side-chain or main-chain azobenzene polymers in the prior art, only one benzene ring in azobenzene is in the main chain, and the high-temperature resistance of polyamide can be improved under the condition of not influencing the photosensitive color-changing function of azobenzene. By regulating and controlling the molecular weight and the content of azobenzene, the polymer has the color changing function, high temperature resistance and excellent performance of polyamide, and the polymer chip meeting the requirement of melt spinning under the high temperature condition is obtained and can be directly used for melt spinning, so that the polyamide fiber with the photochromic performance is prepared, and the color changing sensitivity is high.
The preparation method of the photochromic azobenzene polyamide comprises the following steps:
s1, preparing azobenzene containing carboxyl: placing the 3-amino-5-nitrobenzoic acid suspension in a hydrochloric acid solution, cooling the solution in a water-ice bath at 0-5 ℃, adding a nitrite aqueous solution under the stirring condition, and stirring to obtain a diazonium salt suspension;
wherein the nitrite is preferably sodium nitrite.
Then adding a solution consisting of sodium acetate and phenol, and stirring and reacting for 20-40 min at 5 ℃; then adding the red orange azo compound into an acidic aqueous solution to obtain a red orange azo compound precipitate;
then filtering and taking a precipitate, washing the precipitate by using a sodium bicarbonate aqueous solution, then drying the precipitate, and recrystallizing the dried precipitate in boiling n-octane to obtain red-orange azobenzene containing carboxyl;
s2, preparing carboxyazobenzene containing alkyl groups: the azobenzene and K containing carboxyl obtained in the step S12CO3Adding KI, acetonitrile and bromoalkane into a round-bottom flask, refluxing for 3-10 h, pouring the reaction liquid into water, performing suction filtration, and recrystallizing in a mixed solvent consisting of ethanol and water to obtain yellow carboxyl azobenzene containing alkane groups;
the brominated alkane is preferably an alkane group with 5-10 carbon atoms.
The volume ratio of ethanol to water in the mixed solvent is 1: 3-2: 1.
S3, preparing carboxyl azobenzene containing alkyl and amino: amination is carried out on the carboxyazo benzene containing the alkyl group obtained in the step S2 under the condition of a catalyst Pd/C and hydrogen to obtain carboxyazo benzene containing the alkyl group and amino; for example, the structural formula can be represented by the following formula:
one synthetic route of steps S1-S3 is shown as follows:
s4, preparing azobenzene polyamide: and (4) performing melt polycondensation by using the carboxyazobenzene containing the alkyl group and the amino group obtained in the step (S3) and lactam or alkyl polyamine and alkyl polyacid as polymerization monomers to obtain the azobenzene polyamide.
In step S4, the melt polycondensation includes: introducing nitrogen into a condensation reaction container to remove air, then adding 1-3% of lactam or alkyl polyamine and alkyl polyacid, water and concentrated phosphoric acid into the reaction container according to the mass percent of 100%, continuously introducing nitrogen, and stirring and reacting for 3-4 hours at 230-250 ℃;
and then adding the carboxyazobenzene containing the alkane group and the amino group, which accounts for 0.05-1.0% of the lactam or the sum of the alkane group polyamine and the alkane group polyacid, into the reaction system, raising the temperature of the polymerization system to 260-270 ℃, adjusting the stirring rotation speed to 250-300 r/min, closing the nitrogen, vacuumizing the reaction container, and carrying out reduced pressure polycondensation for 10-30 min to obtain the azobenzene polyamide.
The lactam is butyrolactam, caprolactam and the like, the alkane-based polyamine is straight-chain alkane-based diamine with 5-10 carbon atoms, and the alkane-based polyacid is straight-chain alkane-based diacid with 6-12 carbon atoms.
One synthetic route of step S4 is shown below:
the photochromic nylon fiber is obtained by melt spinning the photochromic azobenzene polyamide or the photochromic azobenzene polyamide prepared by the preparation method.
Example 1
The photochromic azobenzene polyamide has the following structural formula:
where m is about 330 and n is about 15.
Is prepared by the following steps:
(1) synthesis of azobenzene compound:
s1, placing a 5-amino-3-nitro-1-benzoic acid (9.10g) suspension in a hydrochloric acid solution (300mL, 0.5M), and cooling the solution in a water-ice bath at 0-5 ℃. Sodium nitrite (3.80 g) was dissolved in water (solution A) with stirring and added slowly. After the nitrite solution is added, continuously stirring at low temperature for 20min to finally obtain a diazonium salt suspension;
then, preparing a solution (solution B) from sodium acetate (40.8g) and phenol (5.17g), dropwise adding the solution A into the solution B, stirring at 5 ℃, and continuously reacting the system for 20 min; then slowly adding the final solution into an acidic aqueous solution (HCl) to obtain a red-orange azo compound precipitate;
then filtering to obtain a precipitate, washing the precipitate with water containing a small amount of sodium bicarbonate (pH 8), drying the precipitate in vacuum, and recrystallizing the dried precipitate in boiling n-octane (500mL) to obtain red-orange azobenzene containing carboxyl groups, wherein the final yield is between 50 and 60 percent;
s2, azobenzene (5.74g) containing carboxyl and K2CO3Adding (4.14g), potassium iodide (4.98g), acetonitrile (150mL) and bromopentane (4.50g) into a round-bottom flask, refluxing for 7h, pouring the reaction liquid into water, performing suction filtration, and then recrystallizing in a mixed solvent consisting of ethanol (30mL) and water (60mL) to obtain carboxyazobenzene containing alkyl;
and S3, amination is carried out on the carboxyazobenzene containing the alkyl group under the conditions of Pd/C and hydrogen to obtain the carboxyazobenzene containing the alkyl group and the amino group.
(2) Preparing azobenzene-containing discolored nylon 6:
and S4, adding an azobenzene compound serving as a comonomer into a reaction system by adopting a melt copolymerization method to participate in reaction, so that an azobenzene structure is connected into a nylon molecular chain, and preparing the color-changing nylon containing the azobenzene structure. The method comprises the following specific steps:
firstly, building a condensation reaction device, introducing nitrogen into a reaction container to remove air in the device, and exhausting for 10-15 min. Then adding caprolactam, water and concentrated phosphoric acid into a reaction vessel according to the mass percent of 100 percent to 1.5 percent to 2 percent. Continuously introducing nitrogen, starting a stirrer (the rotating speed is 100-150 r/min), stirring, heating to 240 ℃, and starting ring-opening reaction for 3-4 h;
and then adding carboxyl azobenzene (mass ratio is 0.5%) containing alkyl and amino into the reaction system, raising the temperature of the polymerization system to 265 ℃, stirring and rotating at a speed of 250-300 r/min, changing a condensing device into a vacuumizing device, closing nitrogen, vacuumizing the system, and carrying out reduced pressure polycondensation for 10-30 min. And (3) stopping vacuumizing when the melt viscosity in the reactor is obviously increased and obvious rod climbing phenomenon occurs and air bubbles are less, closing the stirrer, pouring out the melt in the three-neck flask, and cooling to obtain the azobenzene structure-containing color-changing nylon 6.
The photochromic nylon 6 obtained in the example was melt-spun at 265 ℃ and the winding speed was 4200m/min, whereby a photochromic nylon fiber having a tensile strength of 4.8cN/dtex was obtained. The intermediate synthesized in this example, carboxyazobenzene (R) containing an alkyl group and a nitro group2Pentyl) as shown in figure 1, and it can be seen that the target product can be successfully synthesized by the method of the present invention. Carboxyazobenzenes (R) containing alkanyl and amino groups2Pentyl) is shown in figure 2, the azobenzene derivative has ultraviolet absorption at 364nm, and the azobenzene structure enables the synthesized polyamide 6 copolymer fiber to have the functions of absorbing ultraviolet light and changing color. The fiber can be discolored within 5s by irradiating the fiber with an ultraviolet lamp with the wavelength of 365nm and the power of 5W.
Examples 2 to 4 and comparative examples 1 to 2
Examples 2 to 4 and comparative examples 1 to 2 provided photochromic azobenzene polyamides, which were different from example 1 in that m, the mass percentage of caprolactam to carboxyazo benzene having an alkyl group and an amino group in step S41:m2As shown in table 1, the rest was substantially the same as example 1, and will not be described herein.
TABLE 1 preparation conditions and Performance test results of examples 1 to 4 and comparative examples 1 to 2
As can be seen from table 1, as the amount of azobenzene derivative used was increased, the temperature at which the resulting fiber lost 10% weight was gradually increased. However, the introduction of the azobenzene derivative reduces the structural regularity of the polyamide 6 molecular chain, so that the tensile strength of the fiber is gradually reduced along with the increase of the using amount of the azobenzene derivative, and the fiber still has the ultraviolet photosensitive color changing function. When the dosage of the azobenzene derivative is too low, the temperature of 10% of fiber weight loss is also reduced, the heat resistance is too low, the tensile strength is increased, but the azobenzene derivative does not have the ultraviolet photosensitive discoloration function. When the dosage of the azobenzene derivative is too high, the temperature of 10% of fiber weight loss is increased, the heat resistance is improved, and the fiber can change color, but the regularity of a polyamide 6 molecular chain is obviously reduced, the tensile strength is too low, and the application requirement cannot be met.
Example 5
The photochromic azobenzene polyamide has the following structural formula:
the preparation procedure differs from example 1 in that the caprolactam in step S4 is replaced by hexamethylenediamine and hexamethylenediamine. The rest is substantially the same as that of embodiment 1, and will not be described herein.
The photochromic azobenzene polyamide prepared by the embodiment has the advantages that the temperature of 10% weight loss is 300 ℃, the tensile strength is 5.1cN/dtex, the color is obviously changed before and after ultraviolet irradiation, and the photochromic azobenzene polyamide has a sensitive ultraviolet photochromic function.
In summary, the photosensitive azobenzene polyamide with color change provided by the invention takes 3-amino-5-nitrobenzoic acid as a raw material, the raw material reacts with nitrite to obtain diazonium salt, and then the diazonium salt reacts with phenol to obtain azobenzene containing carboxyl; then the phenolic hydroxyl and halogenated alkane are subjected to substitution reaction, and then the nitro is reduced into amino, so that azobenzene with amino and carboxyl on the same benzene ring is obtained. The azobenzene is taken as a reaction monomer, and is subjected to melt polycondensation together with a polyamide reaction monomer, so that the azobenzene polyamide with one benzene ring at the main chain and the other benzene ring at the side chain can be obtained. Under the condition of not influencing the photosensitive color changing function of azobenzene, the high temperature resistance of polyamide can be improved, so that the polymer has the color changing function, the high temperature resistance and the excellent performance of polyamide, and the polymer can be directly used for melt spinning, thereby preparing the high-performance polyamide fiber with photochromic performance and having high color changing sensitivity.
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 without departing from the spirit and scope of the invention.
Claims (10)
1. The photochromic azobenzene polyamide is characterized in that the photochromic azobenzene polyamide comprises a polyamide chain segment and an azobenzene derivative chain segment, wherein one benzene ring structure in the azobenzene derivative chain segment is on the main chain of the photochromic azobenzene polyamide, and the other benzene ring structure is on the side chain; the structural formula of the photochromic azobenzene polyamide is shown as a formula I or a formula II:
wherein R is1Is an alkyl group having 4 to 12 carbon atoms, R2Is an alkyl group having 2 to 10 carbon atoms, R3Is an alkyl group having 5 to 10 carbon atoms, R4Is an alkyl group having 6 to 12 carbon atoms, m is 50 to 1500, and n is a positive integer of 10 to 50.
2. The photochromic azobenzene polyamide according to claim 2, wherein the mass content of the azobenzene derivative segment in the photochromic azobenzene polyamide is 1-20%.
3. The photochromic azobenzene polyamide of claim 1, wherein R is1Is an alkyl group having 4 to 8 carbon atoms, R3Is an alkyl group having 5 to 8 carbon atoms, R4Is an alkyl group having 6 to 8 carbon atoms.
4. A process for the preparation of the photochromic azobenzene polyamide according to any one of claims 1 to 3, characterized in that it comprises the following steps:
s1, preparing azobenzene containing carboxyl: placing the 3-amino-5-nitrobenzoic acid suspension in a hydrochloric acid solution, cooling the solution in a water-ice bath at 0-5 ℃, adding a nitrite aqueous solution under the stirring condition, and stirring to obtain a diazonium salt suspension;
then adding a solution consisting of sodium acetate and phenol, and stirring and reacting for 20-40 min at 5 ℃; then adding the red orange azo compound into an acidic aqueous solution to obtain a red orange azo compound precipitate;
then filtering and taking a precipitate, washing the precipitate by using a sodium bicarbonate aqueous solution, then drying the precipitate, and recrystallizing the dried precipitate in boiling n-octane to obtain red-orange azobenzene containing carboxyl;
s2, preparing carboxyazobenzene containing alkyl groups: the azobenzene and K containing carboxyl obtained in the step S12CO3Adding KI, acetonitrile and bromoalkane into a round-bottom flask, refluxing for 3-10 h, pouring the reaction liquid into water, performing suction filtration, and recrystallizing in a mixed solvent consisting of ethanol and water to obtain yellow carboxyl azobenzene containing alkyl;
s3, preparing carboxyl azobenzene containing alkyl and amino: amination is carried out on the carboxyazobenzene containing the alkyl group obtained in the step S2 under the condition of a catalyst Pd/C and hydrogen to obtain carboxyazobenzene containing the alkyl group and amino;
s4, preparing azobenzene polyamide: and (4) performing melt polycondensation by using the carboxyazobenzene containing the alkyl group and the amino group obtained in the step (S3) and lactam or alkyl polyamine and alkyl polyacid as polymerization monomers to obtain the azobenzene polyamide.
5. The process for preparing a photochromic azobenzene polyamide according to claim 4, wherein, in step S4, said melt polycondensation comprises: introducing nitrogen into a condensation reaction container to remove air, then adding lactam or alkyl polyamine, alkyl polyacid, water and concentrated phosphoric acid into the reaction container according to the mass percent of 100%, 1-2%, 1-3%, continuously introducing nitrogen, and stirring and reacting for 3-4 hours at 230-250 ℃;
and then adding the lactam or the carboxyazobenzene containing the alkyl group and the amino group, which accounts for 0.05-1.0% of the sum of the alkyl group polyamine and the alkyl group polyacid, into the reaction system, raising the temperature of the polymerization system to 260-270 ℃, adjusting the stirring rotation speed to 250-300 r/min, closing the nitrogen, vacuumizing the reaction container, and carrying out reduced pressure polycondensation for 10-30 min to obtain the azobenzene polyamide.
6. The method for producing a photochromic azobenzene polyamide as claimed in claim 5, wherein said lactam is butyrolactam or caprolactam, said alkyl polyamine is a linear alkanediamine having 5 to 10 carbon atoms, and said alkyl polyacid is a linear alkanedioic acid having 6 to 12 carbon atoms.
7. The method for preparing a photochromic azobenzene polyamide according to claim 4, wherein in step S1, said nitrite is sodium nitrite.
8. The method for producing a photochromic azobenzene polyamide as claimed in claim 4, wherein in step S2, the brominated alkane is an alkane group having 2 to 10 carbon atoms.
9. The method for producing a photochromic azobenzene polyamide as claimed in claim 4, wherein in step S2, the volume ratio of ethanol to water in the mixed solvent is 1:3 to 2: 1.
10. A photochromic nylon fiber obtained by melt-spinning the photochromic azobenzene polyamide according to any one of claims 1 to 3 or the photochromic azobenzene polyamide obtained by the production process according to any one of claims 4 to 9.
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