Self-coloring polyamide product as well as preparation method and application thereof

Abstract

The invention relates to a polyamide synthesis technology, and discloses a self-coloring polyamide product as well as a preparation method and application thereof. The polyamide product contains a chromogenic structural unit, the chromogenic structural unit contains a dye chromogenic group, and the dye chromogenic group is selected from at least one of a solvent black group, an acid black group, an acid blue group and an acid yellow group; the polyamide product does not have a decoloration phenomenon after being cooked by an organic solvent, and the color depth difference value of the polyamide product does not exceed 0.2. The preparation method of the polyamide product comprises the following steps: carrying out a reaction I on a polyamide monomer, a dye condensate and an auxiliary agent under an anaerobic condition; the polyamide product provided by the invention not only is uniform in dyeing, good in stability and high in color fastness, but also omits a physical dyeing process in the preparation process, and is low in energy consumption, small in pollution, high in environmental protection property and good in economic benefit and social benefit.

Description

Technical Field

[0001] The present invention relates to polyamide synthesis technology, and specifically, to a self-coloring polyamide product, a preparation method and an application of the self-coloring polyamide product. Background Art

[0002] Polyamide is a general term for thermoplastic resins containing repeating amide groups in the main molecular chain, including aliphatic polyamides, aliphatic-aromatic polyamides and aromatic polyamides. Among them, aliphatic polyamides have excellent toughness, self-lubricity, wear resistance, chemical resistance, gas permeability and oil resistance, etc., and are widely used in the textile industry, industrial fibers, daily engineering materials and other fields; aromatic polyamides have good mechanical properties, insulation properties, chemical stability and ultra-high thermal properties due to the aryl groups in the molecular chain. Currently, fully aromatic polyamides are mainly used in aerospace, atomic energy industry and electronics and electrical industries.

[0003] Polyamide base materials need to be dyed into different colors according to the requirements of the application scenario to meet different product needs. Traditional dyeing methods mainly include dip dyeing and mass coloring. Among them, dip dyeing generally uses a process of mixing polyamide base materials with acid dyes for high-temperature dyeing; mass coloring is to add an appropriate colorant to the spinning solution, and after sufficient mixing, dissolution and filtration, the colorant or colored stock solution can also be injected before entering the spinneret. However, the dyeing effects of dip dyeing and mass coloring are mainly achieved through physical forces such as hydrogen bonds, Coulomb forces and van der Waals forces between the dye and the polyamide base material. The uniformity of dyeing is difficult to control, and the stability is poor. Especially in organic solvents, color change and color fading are extremely likely to occur.

[0004] In the prior art, there has been a method of introducing dye groups into polyamide in the form of chemical bonds. For example, DE2404460A1 mixes diamine dyes with aromatic diamines and aromatic dicarboxylic acid dihalides for condensation to achieve the dyeing of aromatic polyamides. However, the process of directly adding dyes to the polyamide system for copolymerization has obvious problems such as incomplete reaction, poor water resistance after dyeing, and uneven dyeing. If halides are used as substrates, the subsequent treatment process will be more complex and the environmental pollution will be large. Summary of the Invention

[0005] The purpose of the present invention is to overcome the above problems existing in the prior art, and provide a self-coloring polyamide product, a preparation method and an application thereof. The polyamide product not only has uniform dyeing, good stability and high color fastness, but also omits the physical dyeing process in the preparation process, has high environmental protection, good economic benefits and social benefits.

[0006] To achieve the above object, a first aspect of the present invention provides a self-coloring polyamide product, the polyamide product containing a chromogenic structural unit, the chromogenic structural unit containing a dye chromophore group, the dye chromophore group being selected from at least one of a solvent black group, an acid black group, an acid blue group, and an acid yellow group; the polyamide product does not show decolorization after being steamed with an organic solvent, and the color depth difference value of the polyamide product does not exceed 0.2.

[0007] A second aspect of the present invention provides a method for preparing a self-coloring polyamide product, the method comprising the following steps: under an anaerobic condition, reacting a polyamide monomer, a dye condensate represented by formula (IV), and an auxiliary agent in reaction I;

[0008]

[0009] wherein, R1 is an aliphatic alkylene group or an aromatic alkylene group, Q' is a dye chromophore group, and the dye chromophore group is selected from at least one of a solvent black group, an acid black group, an acid blue group, and an acid yellow group.

[0010] A third aspect of the present invention provides a self-coloring polyamide product prepared by the foregoing preparation method.

[0011] A fourth aspect of the present invention provides an application of the foregoing polyamide product in at least one of textiles, industrial fibers, and engineering materials.

[0012] Through the above technical solutions, the self-coloring polyamide product provided by the present invention has a high dyeing uniformity for an aliphatic polyamide matrix, no mottling, no deep and shallow edges, and no streaks, and does not show decolorization after being steamed with an organic solvent, has good dyeing stability and high color fastness, and thus has good water resistance.

[0013] The method for preparing the polyamide product provided by the present invention adds a dye condensate connecting a dye chromophore group through a specific amide bond structure to a polymerization system of an aliphatic polyamide, and directly introduces dye molecules into the aliphatic polyamide chain segment as a capping agent through a polymerization method, aiming to prepare a colored polyamide with uniform dyeing, good stability, and high color fastness on the basis of retaining the excellent mechanical properties of the polyamide product; at the same time, obtaining a colored polyamide product by allowing a dye condensate containing a dye chromophore group to participate in the polymerization system of the polyamide can omit the process of physical dyeing of the dye, effectively reduce the energy consumption, water consumption, chemical consumption, and COD emission in the dyeing process, has high environmental protection, a shorter process flow, and effectively improves the economic and social benefits of the production of the colored polyamide. Description of the Drawings

[0014] Figure 1 is the infrared spectrum of the dye monomer, dibasic acid, and dye condensate 1-1 in Preparation Example 1;

[0015] Figure 2 are the infrared spectra of the dye condensate 1-1, caprolactam, and the colored polyamide in Example 1. Detailed implementation mode

[0016] The endpoints and any values within the ranges disclosed herein are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be considered to be specifically disclosed herein.

[0017] The first aspect of the present invention provides a self-coloring polyamide product, the polyamide product contains a color-developing structural unit, the color-developing structural unit contains a dye color-developing group, and the dye color-developing group is selected from at least one of a solvent black group, an acid black group, an acid blue group, and an acid yellow group; after being cooked with an organic solvent, there is no decolorization phenomenon in the polyamide product, and the color depth difference value of the polyamide product does not exceed 0.2.

[0018] The polyamide product provided by the present invention has stable color fastness after being cooked in an organic solvent (such as ethyl acetate, ethanol, methanol, acetone, etc.), and there is no decolorization phenomenon. After detecting the solution obtained by cooking with an organic solvent by ultraviolet absorption spectroscopy, there is no new absorption peak, which verifies that the polyamide product provided by the present invention has significantly excellent dyeing stability and color fastness. At the same time, the color depth difference value of the polyamide product does not exceed 0.2, making the polyamide product have excellent dyeing uniformity and good water resistance.

[0019] In order to solve the problems existing in the prior art, the inventors of the present invention have conducted extensive and in-depth research and found that by contacting the dye color-developing group in the form of a condensate with the polyamide substrate and participating in the polymerization system of the polyamide, through the oligomer, a high competitive cohesion effect between the dye color-developing group and the polyamide monomer is achieved, and the dye color-developing group is efficiently and uniformly introduced into the polyamide chain segment. Aiming to retain the excellent mechanical properties of the polyamide product, the prepared polyamide product has high dyeing uniformity, good stability, and high color fastness, can withstand cooking with an organic solvent without decolorization, and further enables the polyamide product to obtain excellent water resistance and dyeing uniformity.

[0020] The test process of cooking the polyamide product by mixing it with an organic solvent is as follows: After mixing the polyamide product with ethyl acetate at a weight ratio of 1:1, reflux and cook at 77°C for 24 hours, filter to remove the solid polyamide product, and then measure the ultraviolet absorption spectrum of ethyl acetate after cooking. If there is no new absorption peak compared with before cooking, it indicates no decolorization phenomenon, that is, the polyamide product has solvent cooking resistance.

[0021] In order to comparatively analyze the difference in dyeing uniformity between the polyamide products provided by the present invention and those in the prior art, the standard deviation △K / S (i.e., the color depth difference Sr) of the ratio K / S of the colorant absorption coefficient K to the colorant scattering coefficient S at multiple test points of the polyamide products is used to characterize the dyeing uniformity effect of the polyamide products. The specific test process is as follows: Measure the K / S values at different positions of the polyamide chips on a Datacolor 850 colorimeter (8 measurement points are selected along the two diagonals and two long sides for each chip position), and calculate the standard deviation of the obtained K / S values as the sample data to obtain the color depth difference, which is represented by Sr.

[0022] In the present invention, the perspiration fastness of the polyamide products is determined according to the international standard ISO 105-E04, the soaping fastness is determined according to the international standard ISO 105-C10, and the water immersion fastness is determined according to the international standard ISO 105-E01. The perspiration fastness of the self-coloring polyamide products provided by the present invention is 4-5 grades, the soaping fastness is 4-5 grades, and the water immersion fastness is 4-5 grades. It can be seen that on the basis of improving the dyeing uniformity, the polyamide products provided by the present invention also have excellent perspiration resistance, soaping resistance and water resistance.

[0023] According to the present invention, preferably, the structural formula of the chromogenic structural unit is as shown in formula (I);

[0024]

[0025] Among them, R1 is an aliphatic alkylene or an aromatic alkylene, and Q’ is a dye chromogenic group. The inventors have found that in this preferred embodiment, the dye chromogenic group is connected to the dibasic acid through an amide bond, and then the carboxyl group of the dibasic acid is used to effectively introduce the dye chromogenic group into the chain segment of the aliphatic polyamide, further improving the uniformity of the self-coloring of the polyamide.

[0026] In the present invention, R1 can be any aliphatic alkylene, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, octylene, undecylene, dodecylene; it can also be any aromatic alkylene, for example, terephthalylene, phthalylene, isophthalylene, 1,3-naphthalenediyl, 1,4-naphthalenediyl, 1,5-naphthalenediyl, 1,7-naphthalenediyl, 2,6-naphthalenediyl and 2,7-naphthalenediyl, etc.; preferably, R1 is a C2-C16 aliphatic alkylene or a C8-C14 aromatic alkylene. The inventors have found that in this preferred embodiment, the polyamide products have higher dyeing uniformity and better dyeing stability.

[0027] In the present invention, the dye chromophore groups contained in the self-coloring polyamide product can all be determined by nuclear magnetic resonance and infrared spectroscopy. For example, when the dye chromophore group is Acid Black, characteristic peaks of carbon-nitrogen double bonds appear at around 1588 cm -1 in the infrared spectrum of the polyamide product, and characteristic peaks of cyclohexadienyl appear at around 1487 - 1460 cm -1 .

[0028] According to the present invention, further preferably, the structural formula of the dye chromophore group is as shown in formula (II) and / or formula (III), wherein, R I , R II , R III , R IV are each independently hydrogen and / or water-soluble groups, and p is an integer from 1 to 10. The inventors have found that in this preferred embodiment, the polyamide product has higher dyeing uniformity and better product stability.

[0029] In the present invention, the water-soluble group can be any hydrophilic or water-soluble substituent; preferably, the water-soluble group is -(CR V R VI ) m -SO3M, R V , R VI are each independently selected from at least one of hydrogen and C1-C5 alkyl groups (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl); M is a monovalent metal ion and / or ammonium ion, preferably an alkali metal ion, more preferably Li + , Na + or K + ; m is an integer from 0 to 4. The inventors have found that in this preferred embodiment, the dyeing uniformity and stability of the polyamide product can be further improved.

[0030] In the second aspect of the present invention, a method for preparing a self-coloring polyamide product is provided, and the method includes the following steps: under anaerobic conditions, reacting a polyamide monomer, a dye condensate represented by formula (IV) with an auxiliary agent in reaction I;

[0031]

[0032] wherein, R1 is an aliphatic alkylene group or an aromatic alkylene group, Q' is a dye chromophore group, and the dye chromophore group is selected from at least one of a solvent black group, an acid black group, an acid blue group, and an acid yellow group.

[0033] The preparation method of the polyamide product provided by the present invention adds the dye condensate shown in formula (IV) to the polymerization system of polyamide, and directly introduces the dye chromogenic molecule into the polyamide chain segment in the form of a covalent bond as a capping agent during polymerization. The aim is to obtain a colored polyamide product with uniform dyeing, good stability and high color fastness while retaining the excellent mechanical properties of the polyamide product; this preparation process can omit the physical dyeing process, avoid the energy consumption, water consumption, chemical consumption and COD emissions during the dyeing process, has a shorter process flow, and effectively improves the economic and social benefits of the production of colored polyamide products.

[0034] According to the present invention, preferably, the preparation process of the dye condensate includes: reacting the dye monomer containing the dye chromogenic group with a dibasic acid in reaction II, so that the end of the dye condensate contains a carboxyl group, and then embedding it into the polyamide polymer in the form of an amide bond, realizing the introduction of the dye chromogenic group into the polyamide chain segment to self-color the polyamide product, further improving the dyeing uniformity, stability and color fastness of the polyamide, and effectively retaining the excellent mechanical properties of the polyamide product.

[0035] More preferably, the structural formula of the dye monomer is as shown in formula (V) and / or formula (VI), wherein, R I , R II , R III , R IV are each independently hydrogen and / or a water-soluble group, and p is an integer from 1 to 10. More preferably, the water-soluble group is -(CR V R VI ) m -SO3M, R V , R VI are each independently selected from at least one of hydrogen and C1-C5 alkyl, M is a monovalent metal ion and / or an ammonium ion, and m is an integer from 0 to 4. In this preferred case, the dye condensate is a colored amide condensate with a carboxyl group at the end, and its terminal carboxyl group can be effectively connected to the polyamide chain segment through an amide covalent bond to prepare a colored polyamide product with rich colors and stable properties.

[0036] Exemplarily, when the dye monomer is solvent black, its structural formula is (abbreviated as alcohol-soluble aniline black, solvent black 5);

[0037] When the dye monomer is acid black, its structural formula is (abbreviated as water-soluble aniline black, acid black 2);

[0038] When the dye monomer is acid blue, its structural formula is (abbreviated as acid blue 260).

[0039] According to the present invention, the dibasic acid can be any aliphatic dibasic acid or aromatic dibasic acid, preferably an aliphatic C2-C16 dibasic acid and / or an aromatic C8-C14 dibasic acid, and more preferably at least one selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, terephthalic acid, phthalic acid, isophthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. In this preferred case, the synthesis efficiency of the dye condensate can be further improved.

[0040] In the present invention, the dye monomer and the dibasic acid can be obtained commercially or prepared by conventional preparation methods.

[0041] According to the present invention, the molar ratio of the amount of the dye monomer to the dibasic acid can be set according to factors such as the type of the dye monomer and the type of the dibasic acid. Preferably, the molar ratio of the dye monomer to the dibasic acid is 1:2-50, and more preferably 1:15-50.

[0042] According to the present invention, preferably, the process of Reaction II includes: under an anaerobic condition, mixing the dye monomer and the dibasic acid and sequentially performing the first-stage Reaction I and the second-stage Reaction I. In this preferred case, the condensate is prepared by melt condensation, and the process is simple and easy to operate.

[0043] In the present invention, the anaerobic condition can be obtained by a conventional method in the art, for example, by introducing nitrogen and / or evacuating.

[0044] According to the present invention, preferably, the conditions of the first-stage Reaction I include at least: a temperature of 215-250 °C, a pressure of 0.08-0.12 MPa, and a time of 3-5 h.

[0045] According to the present invention, preferably, the conditions of the second-stage Reaction I include at least: a temperature of 215-250 °C, a pressure of -0.03 to -0.06 MPa, and a time of 4-10 h.

[0046] In the present invention, after the reaction solution obtained by the second-stage Reaction I is cooled, the dye condensate containing the group shown in formula (I) can be obtained by extraction I and drying; the extractant I used in extraction I can be water or a conventional organic solvent, such as: water, methanol, ethanol, or acetone. In a preferred case, the weight ratio of the dye monomer to the extractant I is 1:5-30.

[0047] As a particularly preferred method for preparing the dye condensate in the present invention, it includes: mixing a dye monomer containing the dye chromophore group with a dibasic acid in a molar ratio of 1:2 - 50, introducing nitrogen for protection, and reacting under the conditions of a temperature of 215 - 250 °C, a pressure of 0.08 - 0.12 MPa, and stirring for 3 - 5 h; then evacuating to a pressure of -0.03 to -0.06 MPa and continuing to react at a temperature of 215 - 250 °C for 4 - 10 h, ending the reaction and cooling the reaction solution to room temperature to obtain a crude condensate; adding an extractant to the crude condensate (the weight ratio of the dye monomer to the extractant I is 1:5 - 30), heating and stirring, performing solid-liquid separation, and drying to obtain a dye condensate containing the group shown in formula (I).

[0048] In the present invention, solid-liquid separation can adopt conventional separation methods, such as filtration, centrifugation, etc., and drying can adopt conventional separation methods, such as vacuum drying, hot air drying, etc.

[0049] Exemplarily, when the dye monomer is alcohol-soluble aniline black, the synthetic route for forming a dye condensate with a dibasic acid is as follows:

[0050]

[0051] When the dye monomer is water-soluble aniline black, the synthetic route for forming a dye condensate with a dibasic acid is as follows:

[0052]

[0053] Among them, R2 is -(CH2) a -, or a is an integer from 0 to 14.

[0054] According to the present invention, the dosage ratio of the dye condensate to the polyamide monomer can be set according to factors such as the type of polyamide monomer, the type of dye chromophore group, and the requirement for the depth of dyeing. Exemplarily, the weight ratio of the dye condensate to the polyamide monomer is 1:50 - 3000, more preferably 1:50 - 500, and further preferably 1:100 - 200.

[0055] According to the present invention, the molar ratio of the polyamide monomer to the acid can be set according to factors such as the type of polyamide monomer and the molecular weight of the colored polyamide polymer formed. Preferably, the molar ratio of the polyamide monomer to the acid is 30 - 350:1, more preferably 50 - 320:1, and further preferably 100 - 250:1. In this preferred case, the reaction efficiency of the polyamide polymerization system and the dye condensate can be effectively improved.

[0056] According to the present invention, the polyamide monomer may be any monomer substance for synthesizing polyamide, or may be formed by copolymerizing a monomer substance for synthesizing polyamide with an auxiliary tool (at least one of ω-aminocarboxylic acid, ω-aminocarboxylate, and polyamine-polyacid mixture) to form the corresponding polyamide.

[0057] As a preferred embodiment of the polyamide monomer, the polyamide monomer is lactam, preferably C2-C20 lactam, more preferably at least one selected from caprolactam, undecanolactam, and dodecanolactam. At this time, the polyamide monomer may further contain at least one of ω-aminocarboxylic acid, ω-aminocarboxylate, and polyamine-polyacid mixture, wherein the ω-aminocarboxylic acid is selected from at least one of aminohexanoic acid, aminoundecanoic acid, and aminododecanoic acid, the ω-aminocarboxylate is selected from at least one of nylon 66 salt, nylon 610 salt, nylon 612 salt, nylon 56 salt, nylon 512 salt, nylon 1212 salt, nylon 1313 salt, nylon 1012 salt, and nylon 1010 salt, and the polyamine in the polyamine-polyacid mixture is selected from at least one of ethylenediamine, hexamethylenediamine, decanediamine, and p-phenylenediamine, and the polyacid is selected from at least one of oxalic acid, adipic acid, sebacic acid, and dodecanedioic acid.

[0058] As another preferred embodiment of the polyamide monomer, the polyamide monomer is an aliphatic nylon salt, preferably at least one selected from nylon 66 salt, nylon 610 salt, nylon 612 salt, nylon 56 salt, nylon 512 salt, nylon 1212 salt, nylon 1313 salt, nylon 1012 salt, and nylon 1010 salt.

[0059] In the present invention, the polyamide monomer can be commercially available or can be prepared by conventional preparation methods.

[0060] In the present invention, the dye condensate, polyamide monomer, and auxiliary agent are subjected to Reaction I in a reaction solvent, and the reaction solvent can be deionized water. The weight ratio of the reaction solvent to the polyamide monomer is preferably 1:5-100.

[0061] According to the present invention, when the polyamide monomer is lactam, the auxiliary agent is an organic monocarboxylic acid. Preferably, the polyamide monomer is at least one selected from caprolactam, undecanolactam, and dodecanolactam, the acid is an aliphatic monocarboxylic acid and / or an aromatic monocarboxylic acid, more preferably an aromatic monocarboxylic acid, and further preferably benzoic acid.

[0062] Based on the lactam as the polyamide monomer, the reaction I system may further contain at least one of ω-aminocarboxylic acid, ω-aminocarboxylate, and polyamine-polyacid mixture. Among them, the ω-aminocarboxylic acid is selected from at least one of caproic acid, undecanoic acid, and dodecanoic acid; the ω-aminocarboxylate is selected from at least one of nylon 66 salt, nylon 610 salt, nylon 612 salt, nylon 56 salt, nylon 512 salt, nylon 1212 salt, nylon 1313 salt, nylon 1012 salt, and nylon 1010 salt; in the polyamine-polyacid mixture, the polyamine is selected from at least one of ethylenediamine, hexamethylenediamine, decanediamine, and p-phenylenediamine, and the polyacid is selected from at least one of oxalic acid, adipic acid, sebacic acid, and dodecanedioic acid.

[0063] According to the present invention, preferably, the molar ratio of the terminal amino group of the polyamine to the carboxyl group of the polyacid is 1:0.9 - 1.1.

[0064] At this time, further preferably, the reaction I includes a ring-opening reaction, a first-stage reaction II, a second-stage reaction II, and a third-stage reaction I carried out in sequence.

[0065] According to the present invention, preferably, the conditions of the ring-opening reaction at least include: temperature is 200 - 230 °C, pressure is 0.08 - 0.12 MPa, and time is 0.5 - 1 h.

[0066] According to the present invention, preferably, the conditions of the first-stage reaction II at least include: temperature is 240 - 270 °C, pressure is 0.6 - 1.5 MPa, and time is 2 - 4 h.

[0067] According to the present invention, preferably, the conditions of the second-stage reaction II at least include: temperature is 235 - 250 °C, pressure is 0.08 - 0.12 MPa, and time is 0.5 - 1.5 h.

[0068] According to the present invention, preferably, the conditions of the third-stage reaction I at least include: temperature is 235 - 250 °C, pressure is -0.05 to -0.09 MPa, and time is 1 - 3 h.

[0069] Exemplarily, as the first particularly preferred preparation method of the polyamide product in the present invention, it includes: mixing a dye condensate with a structural formula as shown in formula (IV), a lactam, benzoic acid and deionized water (the weight ratio of the dye condensate to the lactam is 1:50 - 2000, preferably 1:50 - 200, the weight ratio of deionized water to the lactam is 1:20 - 100, and the molar ratio of benzoic acid to the lactam is 1:50 - 300), performing vacuum pumping - nitrogen purging, cycling three times to displace the air in the system; reacting at a temperature of 200 - 230 °C and a pressure of 0.08 - 0.12 MPa for 0.5 - 1 h to carry out the ring-opening reaction of the lactam, then continuing to heat up to 240 - 270 °C, controlling the system at 0.6 - 1.5 MPa and reacting for 2 - 4 h, then cooling down to 235 - 250 °C, releasing the system pressure, and after pressure relief, continuing to react at a pressure of 0.08 - 0.12 MPa for 0.5 - 1.5 h, and finally performing vacuum pumping, controlling the system pressure to be -0.05 to -0.09 MPa and reacting for 1 - 3 h to obtain a reaction solution, and cooling the reaction melt.

[0070] According to the present invention, when the polyamide monomer is an aliphatic nylon salt, the auxiliary agent is an organic dibasic acid. Preferably, the polyamide monomer is selected from at least one of nylon 66 salt (hexamethylenediamine adipate), nylon 610 salt (hexamethylenediamine sebacate), nylon 612 salt (hexamethylenediamine dodecanedioate), nylon 56 salt (pentamethylenediamine adipate), nylon 512 salt (pentamethylenediamine dodecanedioate), nylon 1212 salt (dodecanedioic acid dodecamethylenediamine salt), nylon 1313 salt (tridecanedioic acid tridecamethylenediamine salt), nylon 1012 salt (dodecanedioic acid decamethylenediamine salt) and nylon 1010 salt (decamethylenediamine sebacate), and the acid is an organic dibasic acid, preferably an aliphatic dibasic acid and / or an aromatic dibasic acid, more preferably an aliphatic dibasic acid, and further preferably adipic acid.

[0071] At this time, further preferably, the reaction I includes a first-stage reaction III and a second-stage reaction III carried out in sequence.

[0072] According to the present invention, preferably, the conditions of the first-stage reaction III at least include: a temperature of 200 - 230 °C, a pressure of 1 - 1.8 MPa, and a time of 2 - 4 h.

[0073] According to the present invention, preferably, the conditions of the second-stage reaction III at least include: a temperature of 240 - 270 °C, a pressure of -0.05 to -0.09 MPa, and a time of 1 - 3 h.

[0074] According to the present invention, preferably, the pressure relief time of the first-stage reaction III is 1 - 1.5 h.

[0075] Exemplarily, as the second particularly preferred method for preparing the polyamide product in the present invention, it includes: mixing a dye condensate having a structural formula as shown in formula (VII), a nylon monomer with a ring-opening structure, adipic acid and deionized water (the weight ratio of the dye condensate to the nylon monomer is 1:50 - 3000, the weight ratio of deionized water to the nylon monomer is 1:5 - 50, and the molar ratio of adipic acid to the nylon monomer is 1:30 - 200), performing vacuum evacuation - nitrogen introduction, cycling three times to displace the air in the system; reacting at a temperature of 200 - 230 °C and a pressure of 1 - 1.8 MPa for 2 - 4 h, then relieving the system pressure to atmospheric pressure, controlling the pressure relief time within 1 - 1.5 h, continuously heating to 240 - 270 °C, evacuating to a pressure of -0.05 to -0.09 MPa, reacting for 1 - 3 h to obtain a reaction solution, and cooling the reaction melt.

[0076] In the third aspect of the present invention, a self - colored polyamide product prepared by the aforementioned preparation method is provided. In the present invention, the polyamide product obtained according to the aforementioned preparation method can be processed into products such as nylon and fibers through processes such as slicing, spinning, or winding according to requirements.

[0077] Based on this, in the fourth aspect of the present invention, the application of the aforementioned polyamide product in at least one of textiles, industrial fibers, and engineering materials is provided.

[0078] The present invention will be described in detail below through examples.

[0079] In the following examples and comparative examples, the test process of cooking the colored nylon by mixing it with an organic solvent is as follows: after mixing the colored nylon and ethyl acetate alcohol at a weight ratio of 1:1, cooking at 77 °C for 24 h, observing whether there is a change in the colorimetry of the ethyl acetate solution before and after cooking, and measuring the ultraviolet absorption spectrum of the supernatant before and after cooking to observe whether there is a new ultraviolet absorption peak;

[0080] The perspiration color fastness is measured according to the international standard ISO 105 - E04, the soaping color fastness is measured according to the international standard ISO 105 - C10, and the water immersion color fastness is measured according to the international standard ISO 105 - E01;

[0081] The dyeing uniformity effect is characterized by the levelness Sr, and its test process is as follows: the levelness of dyeing is represented by the standard deviation △K / S of the K / S values measured multiple times; measure the K / S values at different positions of a polyamide slice with a size of 10 cm * 10 cm and a thickness of 3 mm on a Datacolor 850 type colorimeter (8 measurement points are selected along two diagonals and two long sides at each slice position for measurement), calculate the standard deviation △K / S from the obtained K / S values as sample data, and represent it with Sr.

[0082] Unless otherwise specified, the raw materials and reagents used are all conventional commercially available products.

[0083] Unless otherwise specified, normal pressure refers to 1 atmospheric pressure, approximately 0.1 MPa.

[0084] Preparation Example 1

[0085] 10.0 g of alcohol-soluble aniline black (structural formula where p is 1), 125 g of succinic acid were successively added into the reactor. Under a nitrogen atmosphere, it was heated to 220 °C and reacted for 3 h; the vacuum was pumped to -0.04 MPa, and the reaction was continued at 220 °C for 7 h. The stirring was stopped, and the reaction solution was poured into a 250 ml beaker. After cooling to room temperature, 100 ml of water was added to the beaker. After heating, stirring and extraction, filtration and drying were carried out to obtain a carboxyl-containing dye condensate 1-1; the structural formula of the dye condensate 1-1 is shown in Table 1, and the infrared spectrum data: 3100 - 3000 cm -1 corresponding to the stretching vibration peak of =CH- on the benzene ring of aniline black; there are two absorption peaks between the wavenumbers 2939 - 2859 cm -1 corresponding to the stretching vibration peak of -CH2- on the aliphatic chain; the absorption peak at the wavenumber 3303 cm -1 corresponds to the N-H stretching vibration of the amide bond; the absorption peak at the wavenumber 1643 cm -1 corresponds to the absorption peak of the carboxyl group at 1588 cm -1 a characteristic peak of the carbon-nitrogen double bond appears near 1487 - 1460 cm -1 a characteristic peak of cyclohexadienyl appears near 1487 - 1460 cm; the infrared spectra of the dye monomer alcohol-soluble aniline black, succinic acid and the dye condensate 1-1 in Preparation Example 1 are shown in Figure 1 .

[0086] Preparation Example 2

[0087] 10 g of water-soluble aniline black (structural formula where p is 1), 87.5 g of adipic acid were successively added into the reactor. Under a nitrogen atmosphere, it was heated to 230 °C and reacted for 3 h; the vacuum was pumped to -0.06 MPa, and the reaction was continued at 230 °C for 5.5 h. The stirring was stopped, and the reaction solution was poured into a 250 ml beaker. After cooling to room temperature, 100 ml of methanol was added to the beaker. After heating, stirring and extraction, filtration and drying were carried out to obtain a carboxyl-containing dye condensate 1-2; the structural formula of the dye condensate 1-2 is shown in Table 1, and the infrared spectrum data: 3150 - 3010 cm -1 corresponding to the stretching vibration peak of =CH- on the benzene ring of aniline black; there are two absorption peaks between the wavenumbers 2945 - 2850 cm -1 corresponding to the stretching vibration peak of -CH2- on the aliphatic chain; the absorption peak at the wavenumber 3310 cm -1The absorption peak corresponds to the N-H stretching vibration of the amide bond; the wavenumber 1650 cm -1 corresponds to the absorption peak of the carboxyl group; 1590 cm -1 The characteristic peak of the carbon-nitrogen double bond appears near; 1492 - 1450 cm -1 The characteristic peak of the cyclohexadienyl group appears near.

[0088] Preparation Example 3

[0089] 10 g of water-soluble aniline black (structural formula where p is 2), 58.5 g of sebacic acid were successively added into the reactor. Under a nitrogen atmosphere, it was heated to 235 °C and reacted for 3 h; the vacuum was pumped to -0.04 MPa, and the reaction was continued at 235 °C for 7 h. The stirring was stopped, and the reaction solution was poured into a 250 ml beaker. After cooling to room temperature, 100 ml of ethanol was added to the beaker. After heating and stirring for extraction, filtration and drying were carried out to obtain the carboxyl-containing dye condensate 1-3; the structural formula of the dye condensate 1-3 is shown in Table 1, and the infrared spectrum data: 3200 - 3020 cm -1 corresponds to the stretching vibration peak of =CH- on the benzene ring of aniline black; at the wavenumber 2905 - 2810 cm -1 There are two absorption peaks between, corresponding to the stretching vibration peak of -CH2- on the aliphatic chain; the wavenumber 3302 cm -1 The absorption peak corresponds to the N-H stretching vibration of the amide bond; the wavenumber 1652 cm -1 corresponds to the absorption peak of the carboxyl group; 1591 cm -1 The characteristic peak of the carbon-nitrogen double bond appears near; 1496 - 1457 cm -1 The characteristic peak of the cyclohexadienyl group appears near.

[0090] Preparation Example 4

[0091] 10 g of dye monomer (structural formula where p is 2), 58.5 g of sebacic acid were successively added into the reactor. Under a nitrogen atmosphere, it was heated to 235 °C and reacted for 3 h; the vacuum was pumped to -0.04 MPa, and the reaction was continued at 235 °C for 7 h. The stirring was stopped, and the reaction solution was poured into a 250 ml beaker. After cooling to room temperature, 100 ml of ethanol was added to the beaker. After heating and stirring for extraction, filtration and drying were carried out to obtain the carboxyl-containing dye condensate 1-4; the structural formula of the dye condensate 1-4 is shown in Table 1, and the infrared spectrum data: 3210 - 3010 cm -1 corresponds to the stretching vibration peak of =CH- on the benzene ring of aniline black; at the wavenumber 2950 - 2840 cm -1 There are two absorption peaks between, corresponding to the stretching vibration peak of -CH2- on the aliphatic chain; the wavenumber 3315 cm -1 The absorption peak corresponds to the N-H stretching vibration of the amide bond; the wavenumber 1658 cm-1 The absorption peak corresponding to the carboxyl group; 1595 cm -1 The characteristic peak of the carbon-nitrogen double bond appears near; 1495 - 1445 cm -1 The characteristic peak of the cyclohexadienyl group appears near.

[0092] Preparation Example 5

[0093] 10 g of Acid Blue 260 (structural formula is ) and 32.0 g of succinic acid were successively added into the reactor. Under a nitrogen atmosphere, it was heated to 220 °C and reacted for 3 h; the vacuum was pumped to -0.04 MPa, and the reaction was continued at 220 °C for 7 h. The stirring was stopped, and the reaction solution was poured into a 250 ml beaker. After cooling to room temperature, 100 ml of water was added to the beaker. After heating extraction, filtration and drying, the dye condensate 1-5 containing carboxyl groups was obtained; the structural formula of the dye condensate 1-5 is shown in Table 1, and the infrared spectrum data: wave numbers 3100 - 3000 cm -1 The small absorption peak that appears corresponds to the stretching vibration peak of =CH- on the anthraquinone ring; wave numbers 2900 - 2750 cm -1 The absorption peak between corresponds to the stretching vibration peak of -CH2- on the aliphatic chain; wave number 3260 cm -1 The absorption peak corresponds to the N-H stretching vibration on the amide bond.

[0094] Preparation Example 6

[0095] 10 g of Acid Blue 260 (structural formula is ) and 39 g of adipic acid were successively added into the reactor. Under a nitrogen atmosphere, it was heated to 230 °C and reacted for 3.0 h; the vacuum was pumped to -0.04 MPa, and the reaction was continued at 230 °C for 7 h. The stirring was stopped, and the reaction solution was poured into a 250 ml beaker. After cooling to room temperature, 100 ml of methanol was added to the beaker. After heating extraction, filtration and drying, the dye condensate 1-6 containing carboxyl groups was obtained; the structural formula of the dye condensate 1-6 is shown in Table 1, and the infrared spectrum data: wave numbers 3100 - 3000 cm -1 The small absorption peak that appears corresponds to the stretching vibration peak of =CH- on the anthraquinone ring; wave numbers 2920 - 2760 cm -1 The absorption peak between corresponds to the stretching vibration peak of -CH2- on the aliphatic chain; wave number 3250 cm -1 The absorption peak corresponds to the N-H stretching vibration on the amide bond.

[0096] Preparation Example 7

[0097] 10 g of Acid Blue 260 (structural formula is )、54 g of sebacic acid, heated to 235 °C and reacted for 3 h under a nitrogen atmosphere; evacuated to -0.04 MPa, and continued to react at 235 °C for 7 h. Stop stirring, pour the reaction solution into a 250 ml beaker, cool to room temperature, add 100 ml of ethanol to the beaker, heat for extraction, filter and dry to obtain a carboxyl-containing dye condensate 1-7; the structural formula of the dye condensate 1-7 is shown in Table 1, and the infrared spectrum data: wave numbers 3100 - 3000 cm -1 The small absorption peak that appears corresponds to the stretching vibration peak of =CH- on the anthraquinone ring; wave numbers 2930 - 2780 cm -1 The absorption peak between corresponds to the stretching vibration peak of -CH2- on the aliphatic chain; wave number 3270 cm -1 The absorption peak corresponds to the stretching vibration of N-H on the amide bond.

[0098] Preparation Example 8

[0099] Prepare the dye condensate according to the method of Example 1, except that the structural formula of the alcohol-soluble aniline black is replaced with p is 1; obtain a carboxyl-containing dye condensate 1-8; the structural formula of the dye condensate 1-8 is shown in Table 1, and the infrared spectrum data: 3150 - 3010 cm -1 Corresponds to the stretching vibration peak of =CH- on the benzene ring of aniline black; there are two absorption peaks between wave numbers 2945 - 2850 cm -1 Corresponds to the stretching vibration peak of -CH2- on the aliphatic chain; wave number 3315 cm -1 The absorption peak corresponds to the stretching vibration of N-H on the amide bond; wave number 1650 cm -1 The absorption peak corresponding to the carboxyl group is at; 1595 cm -1 The characteristic peak of the carbon-nitrogen double bond appears near; 1495 - 1455 cm -1 The characteristic peak of cyclohexadienyl appears near.

[0100] Preparation Example 9

[0101] Prepare the dye condensate according to the method of Example 2, except that the structural formula of the water-soluble aniline black is replaced with p is 1; obtain a carboxyl-containing dye condensate 1-9; the structural formula of the dye condensate 1-9 is shown in Table 1, and the infrared spectrum data: 3150 - 3010 cm -1 Corresponds to the stretching vibration peak of =CH- on the benzene ring of aniline black; there are two absorption peaks between wave numbers 2945 - 2850 cm -1 Corresponds to the stretching vibration peak of -CH2- on the aliphatic chain; wave number 3310 cm -1 The absorption peak corresponds to the stretching vibration of N-H on the amide bond; wave number 1652 cm -1corresponding to the absorption peak of the carboxyl group; 1593 cm -1 nearby, a characteristic peak of the carbon-nitrogen double bond appears; 1497 - 1452 cm -1 nearby, a characteristic peak of the cyclohexadienyl group appears.

[0102] Preparation Example 10

[0103] The dye condensate was prepared according to the method of Example 5, except that the structural formula of Acid Blue 260 was replaced with to obtain the carboxyl-containing dye condensate 1 - 10; the structural formula of the dye condensate 1 - 10 is shown in Table 1, and the infrared spectrum data: wave numbers 3100 - 3000 cm -1 The small absorption peak that appears corresponds to the stretching vibration peak of =CH- on the anthraquinone ring; wave numbers 2935 - 2765 cm -1 The absorption peak between corresponds to the stretching vibration peak of -CH2- on the aliphatic chain; wave number 3270 cm -1 The absorption peak corresponds to the N-H stretching vibration on the amide bond.

[0104] Preparation Example 11

[0105] The dye condensate 1 - 3 was prepared according to the method of Example 3, except that the reaction process was replaced with: under a nitrogen atmosphere, heated to 215 °C and reacted for 5 h; evacuated to -0.03 MPa, and continued to react at 215 °C for 10 h, stopped stirring, poured the reaction solution into a 250 ml beaker, cooled to room temperature, added 100 ml of ethanol to the beaker, heated and stirred for extraction, filtered and dried to obtain the carboxyl-containing dye condensate 1 - 3.

[0106] Preparation Example 12

[0107] The dye condensate 1 - 3 was prepared according to the method of Example 3, except that the reaction process was replaced with: under a nitrogen atmosphere, heated to 250 °C and reacted for 3 h; evacuated to -0.06 MPa, and continued to react at 250 °C for 4 h, stopped stirring, poured the reaction solution into a 250 ml beaker, cooled to room temperature, added 100 ml of ethanol to the beaker, heated and stirred for extraction, filtered and dried to obtain the carboxyl-containing dye condensate 1 - 3.

[0108] Preparation Example 13

[0109] The dye condensate 1 - 3 was prepared according to the method of Example 3, except that the reaction process was replaced with: under a nitrogen atmosphere, heated to 200 °C and reacted for 3 h; evacuated to -0.06 MPa, and continued to react at 200 °C for 4 h, stopped stirring, poured the reaction solution into a 250 ml beaker, cooled to room temperature, added 100 ml of ethanol to the beaker, heated and stirred for extraction, filtered and dried to obtain the carboxyl-containing dye condensate 1 - 3.

[0110] Preparation Example 14

[0111] The dye condensate was prepared according to the method of Example 1, except that the structural formula of alcohol-soluble aniline black was replaced with (Acid Black) to obtain a carboxyl-containing dye condensate 1-11; the structural formula of the dye condensate 1-11 is shown in Table 1.

[0112] According to the feeding ratio of the reactants fed, the theoretical yield of the dye condensate was calculated, and then the yield of the actually prepared dye condensate was measured, and the yields of the dye condensates in Preparation Examples 1-14 were calculated. The results are shown in Table 1.

[0113] Table 1 Structural formula and yield of dye condensates in preparation examples

[0114]

[0115]

[0116]

[0117] Example 1

[0118] 1500 g of caprolactam, 8.1 g of benzoic acid, 10.82 g of the dye condensate 1-1 prepared in Preparation Example 1 and 68.2 ml of deionized water were added to the reaction kettle. After purging with nitrogen for 10 min, the reaction kettle was evacuated for 10 min, and the cycle was repeated three times to exhaust the air in the kettle. The temperature was raised to 230 °C, and the ring-opening reaction was carried out for 0.5 h under stirring at normal pressure and a rotation speed of 400 rpm. Then, the temperature was further raised to 250 °C, and the system pressure was controlled at 1.5 MPa by removing the excess water, and the reaction was carried out for 2.5 h. The temperature was lowered to 240 °C, the system pressure was released, and the reaction was continued at normal pressure for 1.0 h. The system was evacuated to a pressure of -0.09 MPa, and after reacting for 1.5 h, the reaction was stopped, the material was discharged, and after cooling, it was sliced to obtain a black nylon-6 polymer.

[0119] The infrared spectra of the dye condensate 1-1, caprolactam and black nylon-6 in Example 1 are shown in Figure 2 .

[0120] Example 2

[0121] Add 1100 g of nylon-66 salt, 4.82 g of adipic acid, 6.25 g of the dye condensate 1-2 prepared in Preparation Example 2, and 58.9 ml of deionized water to the reaction kettle. After purging with nitrogen for 10 min, evacuate the reaction kettle for 10 min, and repeat the cycle three times to exhaust the air in the kettle. Under a nitrogen atmosphere, heat to 215 °C, start stirring at a speed of 450 rpm, and maintain the system pressure at 1.7 MPa by removing water from the system. React at a constant temperature for 2.5 h. Then, relieve the system pressure to atmospheric pressure (the pressure relief time is about 1.5 h). Finally, continue to heat to 265 °C and evacuate to a system pressure of -0.08 MPa, and continue to react for 2 h. Stop the reaction, turn off the stirrer, pour out the melt in the reaction kettle, cool to room temperature, and slice to obtain a black nylon-66 polymer.

[0122] Example 3

[0123] Add 1700 g of nylon-1010 salt, 6.64 g of adipic acid, 15.7 g of the dye condensate 1-3 prepared in Preparation Example 3, and 250 ml of deionized water to the reaction kettle. After purging with nitrogen for 10 min, evacuate the reaction kettle for 10 min, and repeat the cycle three times to exhaust the air in the kettle. Under a nitrogen atmosphere, heat to 210 °C, start stirring at a speed of 450 rpm, and maintain the system pressure at 1.55 MPa by removing water from the system. React at a constant temperature for 3 h. Then, relieve the system pressure to atmospheric pressure (the pressure relief time is about 1 h). Finally, continue to heat to 260 °C and evacuate to a system pressure of -0.08 MPa, and continue to react for 2 h. Stop the reaction, turn off the stirrer, pour out the melt in the reaction kettle, cool to room temperature, and slice to obtain a black nylon-1010 polymer.

[0124] Example 4

[0125] Add 1530 g of nylon-612 salt, 6.58 g of adipic acid, 12.8 g of the dye condensate 1-1 prepared in Preparation Example 1, and 102.0 ml of deionized water to the reaction kettle. After purging with nitrogen for 10 min, evacuate the reaction kettle for 10 min, and repeat the cycle three times to exhaust the air in the kettle. Under a nitrogen atmosphere, heat to 220 °C, start stirring at a speed of 450 rpm, and maintain the system pressure at 1.80 MPa by removing water from the system. React at a constant temperature for 2 h. Then, relieve the system pressure to atmospheric pressure (the pressure relief time is about 1.5 h). Finally, continue to heat to 270 °C and evacuate to a system pressure of -0.06 MPa, and continue to react for 3 h. Stop the reaction, turn off the stirrer, pour out the melt in the reaction kettle, cool to room temperature, and slice to obtain a black nylon-612 polymer.

[0126] Example 5

[0127] Prepare the black nylon-612 polymer according to the method of Example 4, except that the dye condensate 1-1 prepared in Preparation Example 1 is replaced with the dye condensate 1-4 prepared in Preparation Example 4.

[0128] Example 6

[0129] Prepare the blue nylon-6 polymer according to the method of Example 1, except that the dye condensate 1-1 prepared in Preparation Example 1 is replaced with the dye condensate 1-5 prepared in Preparation Example 5.

[0130] Example 7

[0131] Prepare the blue nylon-66 polymer according to the method of Example 2, except that the dye condensate 1-2 prepared in Preparation Example 2 is replaced with the dye condensate 1-6 prepared in Preparation Example 6.

[0132] Example 8

[0133] Prepare the blue nylon-1010 polymer according to the method of Example 3, except that the dye condensate 1-3 prepared in Preparation Example 3 is replaced with the dye condensate 1-7 prepared in Preparation Example 7.

[0134] Example 9

[0135] Prepare the black nylon-612 polymer according to the method of Example 4, except that the dye condensate 1-1 prepared in Preparation Example 1 is replaced with the dye condensate 1-8 prepared in Preparation Example 8.

[0136] Example 10

[0137] Prepare the black nylon-612 polymer according to the method of Example 4, except that the dye condensate 1-1 prepared in Preparation Example 1 is replaced with the dye condensate 1-9 prepared in Preparation Example 9.

[0138] Example 11

[0139] Prepare the blue nylon-1010 polymer according to the method of Example 2, except that the dye condensate 1-3 prepared in Preparation Example 3 is replaced with the dye condensate 1-10 prepared in Preparation Example 10.

[0140] Example 12

[0141] Prepare the black nylon-612 polymer according to the method of Example 4, except that the dye condensate 1-1 prepared in Preparation Example 1 is replaced with the dye condensate 1-3 prepared in Preparation Example 11.

[0142] Example 13

[0143] The black nylon-612 polymer was prepared according to the method of Example 4, except that the dye condensate 1-1 prepared in Preparation Example 1 was replaced with the dye condensate 1-3 prepared in Preparation Example 12.

[0144] Example 14

[0145] The black nylon-612 polymer was prepared according to the method of Example 4, except that the dye condensate 1-1 prepared in Preparation Example 1 was replaced with the dye condensate 1-3 prepared in Preparation Example 13.

[0146] Example 15

[0147] The black nylon-612 polymer was prepared according to the method of Example 4, except that the dye condensate 1-1 prepared in Preparation Example 1 was replaced with the dye condensate 1-11 prepared in Preparation Example 14.

[0148] Example 16

[0149] The black nylon-6 polymer was prepared according to the method of Example 1, except that the reaction process was replaced as follows: Nitrogen was introduced into the reaction kettle for 10 minutes and then evacuated for 10 minutes, and this cycle was repeated three times to exhaust the air in the kettle; The temperature was raised to 250 °C, and ring-opening reaction was carried out for 0.5 h under the conditions of a rotation speed of 400 rpm and a pressure of 0.15 MPa; Then the temperature was continuously raised to 270 °C, and the system pressure was controlled at 1.5 MPa by removing excess water, and the reaction was carried out for 2 h; The temperature was lowered to 250 °C, the system pressure was released, and the reaction was continued at normal pressure for 0.5 h; The system was evacuated to a pressure of -0.09 MPa, and after reacting for 1 h, the reaction was stopped, the material was discharged, and after cooling, it was sliced to obtain the black nylon-6 polymer.

[0150] Example 17

[0151] The black nylon-6 polymer was prepared according to the method of Example 1, except that the reaction process was replaced as follows: Nitrogen was introduced into the reaction kettle for 10 minutes and then evacuated for 10 minutes, and this cycle was repeated three times to exhaust the air in the kettle; The temperature was raised to 200 °C, and ring-opening reaction was carried out for 0.5 h under the stirring conditions of normal pressure and a rotation speed of 400 rpm; Then the temperature was continuously raised to 220 °C, and the system pressure was controlled at 1.8 MPa by removing excess water, and the reaction was carried out for 2.5 h; The temperature was lowered to 200 °C, the system pressure was released, and the reaction was continued at normal pressure for 1.5 h; The system was evacuated to a pressure of -0.09 MPa, and after reacting for 1.5 h, the reaction was stopped, the material was discharged, and after cooling, it was sliced to obtain the black nylon-6 polymer.

[0152] Example 18

[0153] Prepare the black nylon-6 polymer according to the method of Example 1, except that the reaction process is replaced as follows: After introducing nitrogen into the reaction kettle for 10 min, evacuate the air for 10 min, and circulate three times to exhaust the air in the kettle; heat up to 230 °C, and carry out the ring-opening reaction for 0.5 h under normal pressure and stirring conditions with a rotation speed of 400 rpm; then continue to heat up to 265 °C, control the system pressure to 1.5 MPa by removing the excess water, and react for 2.5 h; cool down to 220 °C, relieve the system pressure, and continue to react under normal pressure for 1.0 h; evacuate to a system pressure of -0.02 MPa, stop the reaction after reacting for 1.5 h, discharge the material, and obtain the black nylon-6 polymer after slicing by cooling.

[0154] Example 19

[0155] Prepare the black nylon-612 polymer according to the method of Example 4, except that the reaction process is replaced as follows: After introducing nitrogen into the reaction kettle for 10 min, evacuate the air for 10 min, and circulate three times to exhaust the air in the kettle; under a nitrogen atmosphere, heat up to 245 °C, start stirring with a stirring speed of 450 rpm, maintain the system pressure at 2.00 MPa by removing the water in the system, and carry out the constant-temperature reaction for 2 h; then, relieve the system pressure to normal pressure (the pressure relief time is about 1.5 h); finally, continue to heat up to 270 °C, and evacuate to a system pressure of -0.06 MPa, continue to react for 3 h, stop the reaction, turn off the stirrer, pour out the melt in the reaction kettle, cool to room temperature, and obtain the black nylon-612 polymer after slicing.

[0156] Example 20

[0157] Prepare the black nylon-612 polymer according to the method of Example 4, except that the reaction process is replaced as follows: After introducing nitrogen into the reaction kettle for 10 min, evacuate the air for 10 min, and circulate three times to exhaust the air in the kettle; under a nitrogen atmosphere, heat up to 220 °C, start stirring with a stirring speed of 450 rpm, maintain the system pressure at 1.80 MPa by removing the water in the system, and carry out the constant-temperature reaction for 2 h; then, relieve the system pressure to normal pressure (the pressure relief time is about 1.5 h); finally, continue to heat up to 230 °C, and evacuate to a system pressure of -0.02 MPa, continue to react for 3 h, stop the reaction, turn off the stirrer, pour out the melt in the reaction kettle, cool to room temperature, and obtain the black nylon-612 polymer after slicing.

[0158] Example 21

[0159] Prepare the black nylon-6 polymer according to the method of Example 1, except that the dosage of benzoic acid is replaced with 5 g.

[0160] Example 22

[0161] The black nylon-6 polymer was prepared according to the method of Example 1, except that the amount of dye condensate 1-1 was replaced with 5 g.

[0162] Example 23

[0163] The black nylon-66 polymer was prepared according to the method of Example 2, except that the amount of nylon-66 salt was replaced with 3000 g and the amount of dye condensate 1-2 was replaced with 2.5 g.

[0164] Example 24

[0165] Add 1530 g of p-phenylenediamine terephthalate (PPTA monomer), 6.58 g of adipic acid, 12.8 g of dye condensate 1-1 prepared in Preparation Example 1 and 102 mL of deionized water to the reaction kettle. After purging with nitrogen for 10 min in the reaction kettle, evacuate for 10 min and cycle three times to exhaust the air in the kettle; under a nitrogen atmosphere, heat to 220 °C, start stirring at a stirring speed of 450 rpm, and maintain the system pressure at 1.80 MPa by removing water from the system, and react at a constant temperature for 2 h; then, release the system pressure to atmospheric pressure (the pressure relief time is about 1.5 h); finally, continue to heat up to 270 °C and evacuate to a system pressure of -0.06 MPa, continue to react for 3 h, stop the reaction, turn off the stirrer, pour out the melt in the reaction kettle, cool to room temperature, and slice to obtain a black aromatic nylon product.

[0166] Comparative Example 1

[0167] Alcohol-soluble aniline black was used as the dye, and nylon-6 was dyed by the dipping method. The specific process was as follows: through processes such as feeding the belt, coloring tank, steaming in a hot steam generator, post-washing, post-drying, and discharging the belt, the dye molecules were fully reacted with the corresponding functional groups in nylon-6; finally, through washing and drying, the unreacted dye molecules were removed and fully decomposed to obtain black nylon-6.

[0168] Comparative Example 2

[0169] Black nylon-66 was prepared according to the method of Comparative Example 1, except that nylon 6 was replaced with nylon-66.

[0170] Comparative Example 3

[0171] Black nylon-1010 was prepared according to the method of Comparative Example 1, except that nylon 6 was replaced with nylon-1010.

[0172] Comparative Example 4

[0173] Black nylon-612 was prepared according to the method of Comparative Example 1, except that nylon 6 was replaced with nylon-612.

[0174] Comparative Example 5

[0175] Dissolve 106 parts by weight of m-phenylenediamine and 4.8 parts by weight of 1,5-diaminoanthraquinone in 950 parts by weight of dimethylacetamide; cool the solution to at least 25 °C, add 203 parts by weight of isophthaloyl chloride solution, raise the temperature to 40 - 45 °C, the solution becomes increasingly viscous, cool it to room temperature with the help of an ice bath, and stir for several hours at this temperature; remove the hydrochloric acid formed during the reaction with 10 parts by weight of calcium carbonate and 104 parts by weight of propylene oxide, and then dry and slice the solution.

[0176] The halogen ion content in the water-boiled solution of the nylon chips prepared in Comparative Example 5 is 154 ppm.

[0177] Comparative Example 6

[0178] Dissolve 106 parts by weight of 1,6-hexanediamine and 4.8 parts by weight of 1,5-diaminoanthraquinone in 950 parts by weight of dimethylacetamide; cool the solution to at least 25 °C, add 203 parts by weight of adipoyl chloride solution, raise the temperature to 40 - 45 °C, the solution becomes increasingly viscous, cool it to room temperature with the help of an ice bath, and stir for several hours at this temperature; remove the hydrochloric acid formed during the reaction with 10 parts by weight of calcium carbonate and 104 parts by weight of propylene oxide, and then dry and slice the solution.

[0179] The halogen ion content in the water-boiled solution of the nylon chips prepared in Comparative Example 6 is 342 ppm.

[0180] Comparative Example 7

[0181] Add 1650 g of caprolactam, 9.9 g of benzoic acid, 1.28 g of 2,6-diaminoanthraquinone and 82.5 mL of deionized water to the reaction kettle, pass nitrogen into the reaction kettle for 10 min and then evacuate for 10 min, circulate three times to exhaust the air in the kettle, raise the temperature to 200 °C, carry out the ring-opening reaction under normal pressure and stirring for 0.5 h, with a rotation speed of 400 r / min; raise the temperature to 270 °C, control the system pressure to 1.2 MPa by removing the excess water, and react for 2.5 h; lower the temperature to 250 °C, release the system pressure, and continue to react under normal pressure for 1.5 h; evacuate to a system pressure of -0.08 MPa, stop the reaction after reacting for 2 h to obtain a molten reaction liquid, cool the reaction liquid and then pelletize by strand cutting, extract with water, dry and slice to obtain yellow nylon-6 polymer chips.

[0182] Comparative Example 8

[0183] Add 2000 g of nylon-66 salt, 11.8 g of adipic acid, 1.78 g of 2,6-diaminoanthraquinone and 152 ml of deionized water into the reaction kettle. After purging with nitrogen for 10 min, evacuate the reaction kettle for 10 min, and repeat the cycle three times to exhaust the air in the kettle. Under a nitrogen atmosphere, heat to 200 °C, stir at a speed of 450 r / min, maintain the system pressure at 1.8 MPa by removing water from the system, and react at a constant temperature for 3.5 h. Then, relieve the system pressure to atmospheric pressure, raise the temperature to 270 °C and evacuate to a system pressure of -0.09 MPa, continue the reaction for 2.5 h and then stop the reaction to obtain a molten reaction solution. Turn off the stirrer, pour out the molten reaction solution in the reaction kettle, cool to room temperature, and slice to obtain yellow nylon-66 polymer slices.

[0184] Comparative Example 9

[0185] Commercially available black nylon-6, black nylon-66, black nylon-1010, black nylon-612, blue nylon 6 and blue nylon 1010 were all purchased from Guangzhou Chemical Industry City.

[0186] Test Example 1

[0187] Perform nuclear magnetic resonance and infrared detection on the colored polyamide slices prepared in Examples 1-24 and Comparative Examples 1-9 respectively to obtain the content of the chromogenic structural units. The results are shown in Table 2. Among them, the infrared spectra of dye condensate 1-1, caprolactam and colored polyamide in Example 1 are shown in Figure 2 .

[0188] Table 2

[0189]

[0190]

[0191] Test Example 2

[0192] The colored nylon chips prepared in Examples 1 - 24 and the colored nylon provided in Comparative Examples 1 - 9 were respectively subjected to color depth difference tests, perspiration color fastness tests, soaping color fastness tests, water immersion color fastness tests, and organic solvent cooking tests, and the halogen ion content in the cooked solution was measured. The results are shown in Table 3; the solutions of the colored nylon chips prepared in Examples 1 - 24 had no color change after cooking, and there were no new absorption peaks in the ultraviolet absorption spectra of the cooked solutions, and they had good water resistance and dyeing uniformity; obvious new absorption peaks appeared in the ultraviolet absorption spectra of the solutions cooked from the colored nylon in Comparative Examples 1 - 4 and commercially available colored nylon. Although the colored nylon prepared in Comparative Examples 5 and 6 was resistant to organic solvent cooking, it contained a large amount of residual halogens, had poor water resistance and dyeing uniformity. In addition, the reaction process took a long time, had low efficiency, and the product purification process was complex, and a large amount of sewage would be generated. In the same nylon preparation system, directly copolymerizing the dye with nylon monomers had low reaction efficiency, incomplete reaction, and poor dyeing effect on nylon.

[0193] Table 3

[0194]

[0195]

[0196]

[0197] The colored nylon obtained by the preparation method provided by the present invention has uniform dyeing, controllable color, good stability, high color fastness, and excellent properties such as perspiration color fastness, soaping color fastness, and water immersion color fastness. There is no decolorization phenomenon after cooking with organic solvents; the colored nylon preparation process provided by the present invention can avoid the formation of by-products containing halogen ions, reduce the energy consumption, water consumption, chemical consumption, and wastewater discharge during the dyeing process.

[0198] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A self-coloring polyamide product, characterized in that, The polyamide product contains a color-developing structural unit, the color-developing structural unit contains a dye color-developing group, and the dye color-developing group is selected from at least one of a solvent black group, an acid black group, an acid blue group, and an acid yellow group; after being cooked with an organic solvent, the polyamide product has no decolorization phenomenon, and the color depth difference value of the polyamide product does not exceed 0.

2.

2. The polyamide product according to claim 1, characterized in that, The polyamide product has a perspiration color fastness of 4-5 levels, a soaping color fastness of 4-5 levels, and a water immersion color fastness of 4-5 levels.

3. The polyamide product according to claim 1 or 2, characterized in that, The structural formula of the color-developing structural unit is shown in Formula (III); wherein, R1 is an aliphatic alkylene group or an aromatic alkylene group, and Q' is the dye color-developing group; Preferably, R1 is a C2-C16 aliphatic alkylene group or a C8-C14 aromatic alkylene group.

4. The polyamide product according to claim 3, characterized in that, The structural formula of the dye color-developing group is shown in Formula (II) and / or Formula (III), wherein, R I , R II , R III , R IV are each independently hydrogen and / or a water-soluble group, and p is an integer from 1 to 10; Preferably, the water-soluble group is —(CR V R VI ) m -SO3M, where R V , R VI are each independently selected from at least one of hydrogen and C1-C5 alkyl, M is a monovalent metal ion and / or ammonium ion, and m is an integer from 0 to 4.

5. A method for preparing a self-coloring polyamide product, characterized in that, This method includes the following steps: under an anaerobic condition, reacting a polyamide monomer, a dye condensate shown in Formula (IV) with an auxiliary agent in Reaction I; wherein, R1 is an aliphatic alkylene group or an aromatic alkylene group, Q' is a dye color-developing group, and the dye color-developing group is selected from at least one of a solvent black group, an acid black group, an acid blue group, and an acid yellow group.

6. The preparation method according to claim 5, characterized in that, The preparation process of the dye condensate includes: reacting a dye monomer containing the dye color-developing group with a dibasic acid in Reaction II; Preferably, the dye monomer is shown in Structural Formula (V) and / or Structural Formula (VI), Among them, R I , R II , R III , R IV are each independently hydrogen and / or a water-soluble group, and p is an integer from 1 to 10; Preferably, the water-soluble group is —(CR V R VI ) m -SO3M, where R V and R VI are each independently selected from at least one of hydrogen and C1-C5 alkyl, M is a monovalent metal ion and / or ammonium ion, and m is an integer from 0 to 4; Preferably, the dibasic acid is an aliphatic C2-C16 dibasic acid and / or an aromatic C8-C14 dibasic acid, and more preferably is selected from at least one of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, terephthalic acid, phthalic acid, isophthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid; Preferably, the molar ratio of the dye monomer to the dibasic acid is 1:2-50, and more preferably is 1:15-50.

7. The preparation method according to claim 6, wherein, The process of Reaction II includes: under an anaerobic condition, mixing the dye monomer and the dibasic acid and successively carrying out a first-stage Reaction I and a second-stage Reaction I; Preferably, the conditions of the first-stage Reaction I at least include: the temperature is 215-250 °C, the pressure is 0.08-0.12 MPa, and the time is 3-5 h; The conditions of the second-stage Reaction I at least include: the temperature is 215-250 °C, the pressure is -0.03 to -0.06 MPa, and the time is 4-10 h.

8. The preparation method according to any one of claims 5 to 7, characterized in that, The weight ratio of the dye condensate to the polyamide monomer is 1:50-3000, and more preferably is 1:50-500; Preferably, the molar ratio of the polyamide monomer to the auxiliary agent is 30-350:1, more preferably is 50-320:1, and further preferably is 100-250:

1.

9. The preparation method according to any one of claims 5 to 7, characterized in that, The polyamide monomer is lactam, preferably C2-C20 lactam, more preferably at least one selected from caprolactam, undecanolactam, and dodecanolactam; The auxiliary agent is organic monobasic acid, preferably aliphatic monobasic acid and / or aromatic monobasic acid, more preferably aromatic monobasic acid, and further preferably benzoic acid; Preferably, the reaction I includes a ring-opening reaction, a first-stage reaction II, a second-stage reaction II, and a third-stage reaction I that are carried out in sequence; Preferably, the conditions of the ring-opening reaction at least include: temperature is 200-230 °C, pressure is 0.08-0.12 MPa, and time is 0.5-1 h; Preferably, the conditions of the first-stage reaction II at least include: temperature is 240-270 °C, pressure is 0.6-1.5 MPa, and time is 2-4 h; The conditions of the second-stage reaction II at least include: temperature is 235-250 °C, pressure is 0.08-0.12 MPa, and time is 0.5-1.5 h; The conditions of the third-stage reaction I at least include: temperature is 235-250 °C, pressure is -0.05 to -0.09 MPa, and time is 1-3 h.

10. The preparation method according to any one of claims 5 to 7, characterized in that, The polyamide monomer is aliphatic nylon salt, preferably at least one selected from nylon 66 salt, nylon 610 salt, nylon 612 salt, nylon 56 salt, nylon 512 salt, nylon 1212 salt, nylon 1313 salt, nylon 1012 salt, and nylon 1010 salt; The auxiliary agent is organic dibasic acid, preferably aliphatic dibasic acid and / or aromatic dibasic acid, more preferably aliphatic dibasic acid, and further preferably adipic acid; Preferably, the reaction I includes a first-stage reaction III and a second-stage reaction III that are carried out in sequence; Preferably, the conditions of the first-stage reaction III at least include: temperature is 200-230 °C, pressure is 1-1.8 MPa, and time is 2-4 h; The conditions of the second-stage reaction III at least include: temperature is 240-270 °C, pressure is -0.05 to -0.09 MPa, and time is 1-3 h; Preferably, the pressure relief time of the first-stage reaction III is 1-1.5 h.

11. A self-coloring polyamide product prepared by the preparation method according to any one of claims 5 to 10.

12. Application of the polyamide product according to any one of claims 1 to 4 and 11 in at least one of textile, industrial fiber, and engineering material.

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