Functionalized lactam oligomer, preparation method and application thereof, functional polymer and preparation method thereof

Abstract

The invention relates to a polymer preparation technology, and discloses a functionalized lactam oligomer, a preparation method and application thereof, a functional polymer and a preparation method thereof. The functionalized lactam oligomer contains a lactam oligomerization unit and a functional unit bonded with the lactam oligomerization unit, and the melting point of the functionalized lactam oligomer is 180-220 DEG C; the preparation method comprises the following steps: reacting a functional agent with lactam under a ring-opening polymerization reaction condition; the functional agent has a functional group capable of bonding with an oligomeric unit of the lactam. The functional polymer contains the functional lactam oligomer, and the functional lactam oligomer is bonded with the chain segment of the polymer. According to the functionalized lactam oligomer, functional groups can be efficiently introduced into polymer chain segments, preparation of the functionalized polymer is achieved, particularly, the dyeing function is uniform in effect and high in stability, the excellent performance of polymer products can be kept, the process is simple, and the cost is low.

Description

TECHNICAL FIELD

[0001] The present application relates to polymer preparation technology, in particular, to a functionalized lactam oligomer, a preparation method of the functionalized lactam oligomer, an application of the functionalized lactam oligomer, and a functional polymer and a preparation method of the functional polymer. BACKGROUND

[0002] Nylon fiber has become the second largest chemical fiber next to polyester. With the development of science and technology and the improvement of people's living standards, people have higher requirements for the color of clothing. Although the price of nylon spinning products is higher than that of polyester, due to its excellent performance, it has been more and more favored in the high-end clothing industry. The preparation of nylon fiber with bright and rich color and stable coloring has gradually become a research hotspot in product development.

[0003] The existing preparation method of dyed nylon fiber is to dye nylon and dye molecules in an acid solution. The dye molecules are combined by hydrogen bond, coulomb force and van der waals force, etc. to achieve the purpose of dyeing, which belongs to the category of physical dyeing. However, physical dyeing has the disadvantages of serious pollution, poor stability, easy color loss, etc., and it is difficult to meet the requirements of textile products for end use. Due to the increasing emphasis on environmental ecology, the requirements for dyeing rate, color fixing rate and environmental protection of dyeing waste liquid are becoming higher and higher. The traditional physical dyeing method cannot meet the dyeing needs of nylon. At present, there is an urgent need for a dyeing nylon preparation method with low raw material cost, bright color and excellent performance, which can reduce environmental pollution.

[0004] Chemical dyeing refers to introducing dye molecules into the main chain or side chain of nylon by copolymerization or grafting, so as to dye nylon. This method has the advantages of strong dyeing stability, uniform dyeing and controllable dyeing process, and thus has important significance for preparing nylon fabric with uniform color, stability and multi-tone effect. However, due to the large amount of hydrogen bonds in nylon products, the solubility in conventional solvents is very poor, so it is difficult to perform chemical dyeing, which seriously restricts the development of chemically dyed nylon products.

[0005] CN112961341A discloses a preparation method of a photosensitive color-changing azobenzene polyamide, which comprises synthesizing an azobenzene dye containing amino and carboxyl groups, and then adding the dye to the polymerization process of nylon-6 to prepare a nylon copolymer containing azobenzene groups, thereby successfully performing chemical dyeing on nylon-6; the addition of a small amount of azobenzene monomer enables the prepared nylon copolymer to have sensitive ultraviolet light-induced color-changing function and maximum retention of excellent mechanical properties of nylon-6. However, the preparation process of the color-changing group designed by the technology involves diazotization of nitrite, reduction of phenolic hydroxyl group, halogenation and nitro reduction, and the preparation route is complex, the industrial production cost is high, and the operability is low. CN110343242A discloses a photochromic hyperbranched azopolyamide and a preparation method thereof, which uses 4,4'-diaminoazobenzene and trimesic acid as raw materials, and low-temperature solution polycondensation to obtain a hyperbranched azopolyamide with photochromic function, but the spinning processability of the hyperbranched polymer is greatly different from that of the mature nylon products on the market.

[0006] Therefore, it is of great significance to provide a dyeing method with simple process, low cost and excellent performance of nylon products for the industrial production and development of colored nylon products. SUMMARY

[0007] The present application aims to overcome the above-mentioned problems existing in the prior art, and provides a functionalized lactam oligomer, a preparation method and application thereof, and a functional polymer and a preparation method thereof, which can efficiently introduce functional groups into polymer segments to realize the preparation of functional polymers, especially in terms of uniform and stable dyeing function, and can maintain excellent performance of polymer products, with simple process and low cost.

[0008] To achieve the above-mentioned purpose, the first aspect of the present application provides a functionalized lactam oligomer, which contains a lactam oligomer unit represented by formula (I) and a functional unit bonded to the lactam oligomer unit, wherein the functional unit is a functional agent residue;

[0009]

[0010] wherein R1 is an alkylene group, and m is an integer of 1-100.

[0011] The melting point of the functionalized lactam oligomer is 180-220℃.

[0012] The second aspect of the present application provides a preparation method of a functionalized lactam oligomer, which comprises: reacting a functional agent with a lactam under ring-opening polymerization conditions; the functional agent has a functional group capable of bonding with the oligomer unit of the lactam.

[0013] The third aspect of the present application provides the functionalized lactam oligomer prepared by the above preparation method.

[0014] The fourth aspect of the present application provides the use of the above functionalized lactam oligomer in the preparation of functional polymers, preferably in the preparation of colored polymers.

[0015] The fifth aspect of the present application provides a functional polymer, which contains the above functionalized lactam oligomer, and the functionalized lactam oligomer is bonded to the chain segment of the polymer.

[0016] The sixth aspect of the present application provides a preparation method of a functional polymer, which comprises: mixing a polymer monomer and / or a polymer matrix with the above functionalized lactam oligomer to perform a polycondensation reaction; and the polymer monomer and the polymer matrix both have a functional group capable of being bonded to the functionalized lactam oligomer.

[0017] Through the above technical solution, the functionalized lactam oligomer provided by the present application bonds a conventional polymer functional agent to a lactam oligomer unit, uses the terminal carboxyl group or the terminal amino group of the lactam oligomer unit to cooperate with the functional group on the polymer monomer and / or the polymer matrix which is capable of being bonded to the terminal carboxyl group or the terminal amino group, combines the melting point of the functionalized lactam oligomer within a specific range, efficiently introduces the functional group into the chain segment of the polymer, realizes the preparation of the functional polymer, especially has uniform effect and high stability in the dyeing function of the colored polymer, and can maintain the excellent performance of the polymer matrix itself. In addition, the preparation process of the functionalized lactam oligomer provided by the present application is simple, the reaction product of the functional agent and the lactam is directly used for subsequent processing after cooling, the full use of the functional agent can be realized, the formation of high-pollution wastewater is effectively avoided, and then the energy consumption, water consumption and chemical consumption are reduced, the environmental protection performance is high, the cost is low, and the operability is strong. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 is the nuclear magnetic resonance spectrum of the functionalized lactam oligomer A in Example 1;

[0019] Figure 2 is the infrared spectrum of the functionalized lactam oligomer A in Example 1;

[0020] Figure 3 is the nuclear magnetic resonance spectrum of the functionalized lactam oligomer E in Example 5;

[0021] Figure 4 is the infrared spectrum of the functionalized lactam oligomer E in Example 5.

[0022] Figure 5 is the nuclear magnetic resonance spectrum of the functionalized lactam oligomer G in Example 7;

[0023] Figure 6 is an infrared spectrum of the functionalized lactam oligomer G in Example 7;

[0024] Figure 7 is a DSC spectrum of the functionalized lactam oligomer G in Example 7. DETAILED DESCRIPTION

[0025] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not, and should not be, to be construed as being critical to the scope of the invention. Any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10, that is, all subranges beginning with a minimum value equal to or greater than 1 and ending with a maximum value equal to or less than 10, as well as all subranges that neither begin nor end with one of the specified values. Any maximum numerical limitation recited is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited is intended to include all higher numerical limitations subsumed therein. In this disclosure, the use of "or" means "and / or" unless clearly indicated otherwise. In addition, the combinations of features described herein are not limited to only combinations of the features described herein.

[0026] The first aspect of the present application provides a functionalized lactam oligomer, which contains a lactam oligomer unit represented by formula (I) and a functional unit bonded to the lactam oligomer unit, the functional unit being a functional agent residue;

[0027]

[0028] wherein R1 is an alkylene group, and m is an integer from 1 to 100.

[0029] The functionalized lactam oligomer has a melting point of 180-220℃.

[0030] The inventors of the present application found in the research on colored nylon that, by bonding a conventional amine functional agent or an organic acid functional agent to a lactam oligomer unit to form a functionalized lactam oligomer having a melting point within a specific range, the terminal carboxyl group or the terminal amino group of the lactam oligomer unit can be used to cooperate with the functional groups on the polymer monomer and / or the polymer matrix that can be bonded to the terminal carboxyl group or the terminal amino group to perform a highly efficient reaction, so as to stably introduce the functional groups into the chain segments of the polymer, to obtain a functionalized polymer having corresponding functions, and to maintain the excellent performance of the polymer itself. The functionalized lactam oligomer is particularly suitable for participating in the polymerization system of the polymer monomer (such as nylon monomer) to perform a highly efficient reaction, to directly synthesize a functionalized polymer having corresponding functions, which not only has a good effect on the functional modification of the polymer, but also simplifies the process, and is conducive to improving the economic benefits.

[0031] In the present application, the lactam oligomer unit, the functional unit, and the bonding mode of the two can be determined by nuclear magnetic resonance and infrared spectrum detection. For example, the functional agent residue is a 1,4-diaminoanthraquinone residue, and the absorption peak appearing near the wave number 3072 cm -1 in the infrared spectrum corresponds to =C-H- on the anthraquinone ring, and the absorption peak appearing near the wave number 2936-2868 cm -1There are two absorption peaks, corresponding to the -CH2- stretching vibration peak on the aliphatic chain in the lactam oligomer unit; in the infrared spectrum of the 1,4-diaminoanthraquinone dye, in the wavenumber range of 3400–3250 cm⁻¹ -1 There are two absorption peaks, corresponding to the stretching vibration peaks of its amino group (primary amine). These two peaks were not observed in the infrared spectra of the corresponding functionalized lactam oligomers, but they were observed at a wavenumber of 3294 cm⁻¹. -1 The appearance of a strong absorption peak corresponds to the NH stretching vibration on the amide bond, indicating that the lactam oligomer unit and the functional unit are connected by amide bonds.

[0032] The functionalized lactam oligomers provided by the present invention have a melting point of 180°C, 190°C, 200°C, 210°C, 220°C, or any value between the above two values, and are more preferably 205.5-210.5°C.

[0033] To improve the effect of functionalized lactam oligomers bonding with polymer monomers or polymer matrices for functional modification, preferably, the number average molecular weight of the functionalized lactam oligomers is 500-5000 g / mol; more preferably, it is 500-3000 g / mol.

[0034] In this invention, the melting point is tested using differential scanning calorimetry (DSC) with a DSC-Q20 thermogravimetric analyzer. The testing conditions are a high-purity N2 atmosphere, a heating rate of 10℃ / min, a cooling rate of 20℃ / min, and a gas flow rate of 50 mL / min. The DSC testing range is 30-280℃. The number-average molecular weight is determined using gel permeation chromatography (GPC). Specifically, a 2 mg / mL solution of functionalized lactam oligomers is obtained by dissolving functionalized lactam oligomers in hexafluoroisopropanol solvent. Calibration with polystyrene standards is performed before testing.

[0035] In this invention, R1 can be any alkylene group, preferably a C2-C20 alkylene group, which can be a straight-chain alkylene group, a branched alkylene group, or an alkylene group with a cyclic group. For example, it can be ethylene, propyleneene, methylene ethyl, butylene, methylene propylene, pentylene, methylene butylene, hexylene, methylene pentylene, heptylene, methylene hexylene, octylene, nonylene, octylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecanylene, octadecylene, nonadecanylene, eicosylene, etc., more preferably at least one of propyleneene, butylene, pentylene, hexylene, heptylene, nonylene, octylene, and undecylene; further preferably pentylene. m can be 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, or any integer between the above two values, preferably an integer from 2 to 20.

[0036] According to the present invention, the functional unit can be any residue of an amine (linked to the carbonyl end of the lactam oligomer) or an organic acid (linked to the amino end of the lactam oligomer) functional agent used for functionalizing polymers. For example, the functional agent can be a dye, a softener, or a plasticizer. Preferably, the functional unit is selected from at least one of amine dye residues, organic acid dye residues, amine softener residues, and organic acid softener residues, wherein the amine dye residue is a primary amine dye residue, and the amine softener residue is a primary amine softener residue. When the functional unit is an amine softener residue or an organic acid softener residue, the corresponding functionalized lactam oligomer, after bonding with the polymer chain segment, can achieve a slipping and softening effect on the polymer. When the functional unit is an amine dye residue or an organic acid dye residue, the corresponding functionalized lactam oligomer, after bonding with the polymer chain segment, can achieve a dyeing effect on the polymer. The functional unit is further preferably an amine dye residue.

[0037] According to the present invention, preferably, the amine dye residue is selected from at least one of amine anthraquinone dye residue, amine solvent black dye residue, amine acid black dye residue, amine acid blue dye residue, and amine acid yellow dye residue.

[0038] More preferably, the amine dye residue is selected from at least one of the groups shown in formula (II), formula (III), unsubstituted or substituted groups shown in formula (IV), unsubstituted or substituted groups shown in formula (V), and unsubstituted or substituted groups shown in formula (VI).

[0039]

[0040]

[0041] Among them, R I R II R III and R IV Each is independently hydrogen and / or a water-soluble group, and p is an integer from 1 to 10;

[0042] The substituents of the groups shown in formula (IV), (V), and (VI) are selected from -NO2, -Cl, -Br, -OH, -OCH3, -CH3, -OCH3, -SO3H, -CN, -SO3Na, -NH-CH3,

[0043]

[0044] and At least one of them. The inventors have found that, under this preferred embodiment, the reaction efficiency of block condensation polymerization between the functionalized lactam oligomer and the polymer matrix is ​​higher, and the functionalization effect on the polymer is more uniform and stable.

[0045] In this 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 Each is independently selected from at least one of hydrogen and C1-C5 alkyl groups (e.g., 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, and more preferably Li. + Na + or K + m' is an integer between 0 and 4.

[0046] A second aspect of the present invention provides a method for preparing a functionalized lactam oligomer, the method comprising: reacting a functional agent with a lactam under ring-opening polymerization conditions; wherein the functional agent has functional groups capable of bonding with the oligomer units of the lactam.

[0047] The functionalized lactam oligomer preparation process provided by this invention is simple. The reaction product of the functional agent and lactam is cooled and directly used for subsequent processing, which can realize the full utilization of the functional agent, effectively avoid the formation of highly polluting wastewater, and thus reduce energy consumption, water consumption, chemical consumption and COD emissions. It is environmentally friendly, low in cost and highly operable.

[0048] According to the present invention, preferably, the molar ratio of the functional agent to the lactam is 1:1-100, more preferably 1:2-20; under this preferred embodiment, it is beneficial to improve the preparation efficiency and stability of functionalized lactam oligomers.

[0049] According to the present invention, preferably, the functional agent is selected from at least one of amine dyes, organic acid dyes, amine softeners and organic acid softeners; for example, the amine softener is γ-aminoethylaminopropyltrimethoxysilane, and the amine dye is anthraquinone dye having one or two terminal amino groups. More preferably, the functional agent is an amine dye, specifically a primary amine dye; even more preferably, the amine dye is selected from 1-amino-2,4-dibromoanthraquinone, 1-amino-2-bromo-4-hydroxyanthraquinone, 2-amino-3-hydroxyanthraquinone, 2-amino-1-chloroanthraquinone, 1-amino-2-(4-bromophenoxy)-4-hydroxyanthraquinone, 1-amino-4-phenylamino-2-bromoanthraquinone, 1-amino-5-hydroxy-4-[(1-methylpropyl)amino]-8-nitro-9,10-anthraquinone, Acid Blue 129, Acid Blue 25, CI Disperse Red 60, Disperse Blue 359, 1-amino-4-nitroanthraquinone-2-carboxylic acid cyclohexyl ester, and Disperse... Violet 4, 1-Amino-5-benzamidoanthraquinone, 1-Aminoanthraquinone, 2-Aminoanthraquinone, 1-Amino-4-hydroxyanthraquinone, Acid Blue 40, 2-Chloro-4-hydroxy-1-aminoanthraquinone, 1-Bromo-3-chloro-2-aminoanthraquinone, 1-Amino-4-bromo-2-methylanthraquinone, Disperse Violet 15, 1-Amino-4-hydroxy-2-(phenylthio)anthraquinone, 1-Amino-9,10-dihydro-4-[[(4-tolyl)sulfonyl]amino]anthraquinone-2-sulfonic acid, CI Reactive Blue 19, 1-Amino-4-[(2-methoxyphenyl)amino]anthraquinone, 1-Amino-5-hydroxy-4-[(4-methoxyphenyl)amino]-8- Nitroanthraquinone, 1-amino-4-bromoanthraquinone-2-sulfonate sodium, 1-amino-4-bromoanthraquinone-2-sulfonic acid, 1-amino-2-bromo-4-[[3-(dimethylamino)propyl]amino]anthraquinone, 1-amino-4-hydroxy-2-[2-[4-(2-hydroxyethyl)phenyl]ethoxy]anthraquinone, 1-amino-4-bromoanthraquinone, 1-amino-4-hydroxy-2-(4-methoxyphenoxy)anthraquinone, Disperse Red 86, Disperse Red 53, 2-amino-3-hydroxyanthraquinone, Disperse Orange 11, 1-amino-5-[(2,4-dibromophenyl)amino]-4,8-dihydroxyanthraquinone, 1-amino-4,5-dihydroxy-8-(methylamino)anthraquinone Anthraquinone, Reactive Blue 4, 1-Amino-4-hydroxy-2-[(2-hydroethyl)thio]anthraquinone, 1-Amino-5-chloroanthraquinone, 1-Amino-2-bromo-4-(3-chloroaniline)anthraquinone, Disperse Red E-4B, 2-Amino-3-chloroanthraquinone, Alcohol-soluble Aniline Black, Water-soluble Aniline Black, Acid Black, 1,4-Diaminoanthraquinone, 2,6-Diaminoanthraquinone, 1,2-Diaminoanthraquinone, 1,5-Diaminoanthraquinone, 1,8-Diaminoanthraquinone, 1,4-Diamino-2,3-dichloroanthraquinone, 1,4-Diamino-2,3-dihydroxyanthraquinone, Disperse Red 11, Solvent Violet 59, 1,5-Diamino-4,8-dihydroxyanthraquinone, CIDisperse Blue 56, Disperse Blue 56, 4,8-diamino-1,5-dihydroxy-2-(4-hydroxyphenyl)anthraquinone, 1,5-diamino-4,8-dihydroxy(4-methoxyphenyl)anthraquinone, 4,4-diamino-1,1-iminodianthraquinone, 1,1-iminobis(5-aminoanthraquinone), 4,8-diamino-2-bromo-1,5-dihydroxyanthraquinone, 1,4-diaminoanthraquinone-2,3-disulfonic acid, Disperse Violet 8, Disperse Blue 81, 1,5-diamino-2-bromo-4,8-dihydroxy At least one of 1,5-diamino-4,8-dihydroxy(4-hydroxyphenyl)anthraquinone, 1,8-diamino-4,5-dihydroxyanthraquinone, and 1,2-diamino-3,4-dicyanoanthraquinone; more preferably, any one of 1,4-diaminoanthraquinone, 2,6-diaminoanthraquinone, 1,2-diaminoanthraquinone, 1,5-diaminoanthraquinone, alcohol-soluble aniline black, water-soluble aniline black, and acid black; in this case, the structural formula of the formed functional unit is as shown in formulas (II) to (VI) above.

[0050] In this invention, the lactam can be any cyclic lactam substance. Preferably, the lactam is a lactam having 3-21 carbon atoms, more preferably at least one selected from butyrolactam, valproic acid lactam, caprolactam, heptalactam, octyllactam, decalactam, undecalactam, and dodecalactam, and even more preferably caprolactam.

[0051] In this invention, the functional agent and the lactam can be commercially available or prepared by conventional methods.

[0052] According to the present invention, preferably, the ring-opening polymerization reaction conditions include: a temperature of 200-300°C in the presence of an initiator, specifically 200°C, 220°C, 240°C, 260°C, 280°C, 300°C, or any value between the above two values, more preferably 220-240°C; a pressure of 0.08-3 MPa, specifically 0.08 MPa, 0.5 MPa, 1 MPa, 1.5 MPa, 2 MPa, 2.5 MPa, 3 MPa, or any value between the above two values; and a time of 1-20 h, specifically 1 h, 5 h, 10 h, 15 h, 20 h, or any value between the above two values, more preferably 8-12 h. The inventors have found that under this preferred embodiment, it is beneficial to promote the ring-opening polymerization reaction and improve the production efficiency of functionalized lactam oligomers.

[0053] In this invention, the initiator can be any substance capable of catalyzing the ring-opening of a lactam. Preferably, the initiator is water. More preferably, the weight ratio of the initiator to the lactam is 0.001-1:1.

[0054] For example, when the functional agent is alcohol-soluble aniline black and the lactam is caprolactam, the synthetic route for forming the functionalized lactam oligomer is as follows:

[0055]

[0056] The third aspect of the present invention provides functionalized lactam oligomers prepared by the above-described preparation method.

[0057] The fourth aspect of the present invention provides the application of the above-described functionalized lactam oligomers in the preparation of functional polymers.

[0058] In this invention, the polymer matrix of the functional polymer has functional groups that can bond to the carbonyl or amino ends of the lactam oligomer units, so that the functionalized lactam oligomers can efficiently and uniformly introduce functional agent residues into the polymer chain segments to form block copolymers with functional residues. The aim is to achieve functionalization of the polymer matrix while retaining the properties of the polymer matrix itself, with high efficiency, uniform effect and good stability. It is especially suitable for introducing dye residues into the polymer chain segments to color the polymer matrix and prepare colored polymers.

[0059] A fifth aspect of the present invention provides a functional polymer containing the aforementioned functionalized lactam oligomers, wherein the functionalized lactam oligomers are segmentally bonded to the polymer. This functional polymer utilizes the bonding between the functionalized lactam oligomers and polymer segments to endow the polymer with corresponding functions, exhibiting uniform effects, high stability, and maintaining the excellent properties of the polymer itself.

[0060] In this invention, the functionalized lactam oligomer can be embedded in the polymer chain segment or located at the end of the polymer chain segment.

[0061] According to the present invention, preferably, the functional polymer is a colored polymer, and the colored polymer does not show any decolorization when boiled in water and ethanol for 24 hours respectively.

[0062] In this invention, the test process of boiling the colored polymer in water or ethanol is as follows: the colored polymer is mixed with water or ethanol at a weight ratio of 1:3, then refluxed and boiled for 24 hours, the solid colored polymer is removed by filtration, and then the color of the water or ethanol supernatant is observed to see if there is any change.

[0063] The sixth aspect of the present invention provides a method for preparing a functional polymer, the method comprising: mixing a polymer monomer and / or a polymer matrix with the above-mentioned functionalized lactam oligomer to carry out a polycondensation reaction; wherein both the polymer monomer and the polymer matrix have functional groups capable of bonding with the functionalized lactam oligomer.

[0064] In this invention, the polymer monomer can be any monomer that polymerizes into a polymer. For example, the polymer monomer of nylon can be at least one of the following: lactam, nylon 66 salt (a salt formed by neutralizing adipic acid and hexamethylenediamine), nylon 610 salt (a salt formed by neutralizing adipic acid and decanediamine), nylon 612 salt, nylon 56 salt, nylon 512 salt, nylon 1212 salt (a salt formed by neutralizing dodecanoic acid and dodecylamine), nylon 1313 salt, nylon 1012 salt (a salt formed by neutralizing sebacic acid and dodecylamine), and nylon 1010 salt (a salt formed by neutralizing sebacic acid and decanediamine). When the functionalized lactam oligomer has a terminal amino group, the polymer monomer and the polymer matrix have a terminal carboxyl group; when the functionalized lactam oligomer has a terminal carboxyl group, the polymer monomer and the polymer matrix have a terminal amino group.

[0065] According to the present invention, preferably, the method includes: mixing the polymer monomer with the functionalized lactam oligomer to carry out a polycondensation reaction, wherein the weight ratio of the functionalized lactam oligomer to the polymer monomer is 1:1-10000, more preferably 2000-10000, and even more preferably 1:4500-8500.

[0066] According to the present invention, preferably, the polycondensation reaction process includes a first-stage reaction, a second-stage reaction, and a third-stage reaction carried out sequentially.

[0067] According to the present invention, preferably, the conditions for the first stage reaction include at least: an anaerobic condition (achieved by purging nitrogen gas), a temperature of 210-240°C, specifically 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, or any value between the above two values; and a pressure of 0.1-1.8 MPa, specifically 0.1 MPa, 0.4 MPa, 0.6 MPa, 0.8 MPa, 1 MPa, 1.2 MPa, 1.4 MPa, 1... 0.6 MPa, 1.8 MPa, or any value between the two above; stirring speed is 400-500 rpm, specifically 400 rpm, 420 rpm, 440 rpm, 460 rpm, 480 rpm, 500 rpm, or any value between the two above; time is 25-35 min, specifically 25 min, 27 min, 29 min, 31 min, 33 min, 35 min, or any value between the two above.

[0068] The conditions for the second stage reaction include at least the following: a temperature of 220-270℃, specifically 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, or any value between the two above; a pressure of 0.1-1.8MPa, specifically 0.1MPa, 0.4MPa, 0.6MPa, 0.8MPa, 1MPa, 1.2MPa, 1.4MPa, 1.6MPa, 1.8MPa, or any value between the two above; a stirring rate of 600-800rpm, specifically 600rpm, 650rpm, 700rpm, 750rpm, 800rpm, or any value between the two above; and a time of 0.5-1.5h, specifically 0.5h, 0.7h, 0.9h, 1.1h, 1.3h, 1.5h, or any value between the two above. The inventors have discovered that, under this preferred embodiment, it is advantageous to further enhance the degree of polycondensation reaction between the functionalized lactam oligomer and the polymer matrix.

[0069] The conditions for the third-stage reaction include at least the following: a temperature of 220-270℃, specifically 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, or any value between the two above; a pressure of -0.05 to -0.09 MPa, specifically -0.05 MPa, -0.06 MPa, -0.07 MPa, -0.08 MPa, -0.09 MPa, or any value between the two above; and a time of 1-3 hours, specifically 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, or any value between the two above.

[0070] Exemplary, exemplary, the functional agent is alcohol-soluble aniline black, and the lactam is a functionalized lactam oligomer formed from caprolactam. The reaction route for further using it to form colored nylon 6 with nylon 6 monomer (caprolactam) is as follows:

[0071] m and p are each an integer greater than or equal to 1;

[0072] For example, the functional agent is alcohol-soluble aniline black, and the lactam is a functionalized lactam oligomer formed from caprolactam. The reaction route for further using it to form colored nylon 6 with the nylon 6 matrix is ​​as follows:

[0073]

[0074] m and p' are each an integer greater than or equal to 1, and R is a hydroxyl group or other group that can bond with a carbonyl group.

[0075] The present invention will be described in detail below through embodiments.

[0076] In the following examples and comparative examples, the test process for nylon products to be boiled in water or ethanol is as follows: the nylon product is mixed with water or ethanol at a weight ratio of 1:3, then refluxed at 100°C for 24 hours, the solid substances are removed by filtration, and then the color of the supernatant of water or ethanol is observed against a white paper background to see if there is any change.

[0077] Number average molecular weight was determined by gel permeation chromatography (GPC). Specifically, a functionalized lactam oligomer solution with a concentration of 2 mg / mL was obtained by dissolving the functionalized lactam oligomer in hexafluoroisopropanol solvent. The solution was calibrated with polystyrene standards before testing. The melting point was determined by differential scanning calorimetry (DSC) using a DSC-Q20 thermogravimetric analyzer. The test conditions were a high-purity N2 atmosphere, a heating rate of 10 °C / min, a cooling rate of 20 °C / min, and a gas flow rate of 50 mL / min. The DSC test range was 30–280 °C.

[0078] Unless otherwise specified, all raw materials and reagents used are conventional commercial products.

[0079] Unless otherwise specified, atmospheric pressure refers to 1 atmosphere, which is approximately 0.1 MPa.

[0080] Example 1

[0081] 7.2 g (30 mmol) of 1,4-diaminoanthraquinone, 30.55 g (270 mmol) of caprolactam and 2 g of initiator water were added sequentially to the reactor. The mixture was then heated to 80 °C and stirred until fully dissolved. The mixture was then heated to 230 °C and reacted for 10 h. The reaction was stopped, the product was discharged, and cooled to room temperature to obtain amino-terminated brown functionalized lactam oligomer A (ZN9).

[0082] The structural formula of the functionalized lactam oligomer A is shown in Table 1, and its NMR spectrum is shown in Table 1. Figure 1 Infrared spectrum Figure 2 Infrared spectral data: wavenumber 3072 cm⁻¹ -1 The absorption peaks that appear correspond to the stretching vibration peak of =CH- on the anthraquinone ring; in the wavenumber range of 2936–2868 cm⁻¹ -1 There are two absorption peaks, corresponding to the -CH2- stretching vibration peak on the aliphatic chain; in the infrared spectrum of the starting material 1,4-diaminoanthraquinone, the peaks are in the wavenumber range of 3400–3250 cm⁻¹. -1 There are two absorption peaks, corresponding to the stretching vibration peaks of its amino group (primary amine). These two peaks were not observed in the infrared spectrum of functionalized lactam oligomer A, but they were observed at a wavenumber of 3294 cm⁻¹. -1A strong absorption peak was observed, corresponding to the NH stretching vibration on the amide bond. The melting point of functionalized lactam oligomer A was determined to be 207.2℃.

[0083] Example 2

[0084] 50 g (210 mmol) of 1,5-diaminoanthraquinone, 71.29 g (630 mmol) of caprolactam and 2 g of initiator water were added sequentially to the reactor. The mixture was then heated to 80 °C and stirred until fully dissolved. The mixture was then heated to 240 °C and reacted for 8 h. The reaction was stopped, the product was discharged, and cooled to room temperature to obtain amino-terminated purple functionalized lactam oligomer B.

[0085] The structural formula of the functionalized lactam oligomer B is shown in Table 1. Infrared spectral data: wavenumber 3075 cm⁻¹ -1 The absorption peaks that appear correspond to the stretching vibration peak of =CH- on the anthraquinone ring; in the wavenumber range of 2940–2865 cm⁻¹. -1 There are two absorption peaks, corresponding to the -CH2- stretching vibration peak on the aliphatic chain; in the infrared spectrum of the starting material 1,5-diaminoanthraquinone, the peaks are in the wavenumber range of 3400–3260 cm⁻¹. -1 There are two absorption peaks, corresponding to the stretching vibration peaks of its amino group (primary amine). These two peaks were not observed in the infrared spectrum of functionalized lactam oligomer B, but they were observed at a wavenumber of 3298 cm⁻¹. -1 A strong absorption peak was observed, corresponding to the NH stretching vibration on the amide bond. The melting point of the functionalized lactam oligomer B was determined to be 209.3℃.

[0086] Example 3

[0087] 22 g (105 mmol) of 2,6-diaminoanthraquinone, 71.29 g (630 mmol) of caprolactam and 2 g of initiator water were added sequentially to the reactor. The mixture was then heated to 80 °C and stirred until fully dissolved. The mixture was then heated to 220 °C and reacted for 12 h. The reaction was stopped, the product was discharged, and cooled to room temperature to obtain amino-terminated yellow functionalized lactam oligomer C.

[0088] The structural formula of the functionalized lactam oligomer C is shown in Table 1. Infrared spectral data: wavenumber 3070 cm⁻¹ -1 The absorption peaks that appear correspond to the stretching vibration peak of the =CH- group on the anthraquinone ring; in the wavenumber range of 2930–2860 cm⁻¹ -1 There are two absorption peaks, corresponding to the -CH2- stretching vibration peak on the aliphatic chain; in the infrared spectrum of the starting material 2,6-diaminoanthraquinone, the peaks are in the wavenumber range of 3398–3255 cm⁻¹. -1 There are two absorption peaks, corresponding to the stretching vibration peaks of its amino group (primary amine). These two peaks were not observed in the infrared spectrum of functionalized lactam oligomer C, but they were observed at a wavenumber of 3290 cm⁻¹.-1 A strong absorption peak was observed, corresponding to the NH stretching vibration on the amide bond. The melting point of the functionalized lactam oligomer C was determined to be 210.1℃.

[0089] Example 4

[0090] 31.5 g (132.4 mmol) of 1,2-diaminoanthraquinone, 74.91 g (662 mmol) of caprolactam and 2 g of initiator water were added sequentially to the reactor. The mixture was then heated to 80 °C and stirred until fully dissolved. The mixture was then heated to 200 °C and reacted for 20 h. The reaction was stopped, the product was discharged, and cooled to room temperature to obtain amino-terminated purple functionalized lactam oligomer D.

[0091] The structural formula of the functionalized lactam oligomer D is shown in Table 1. Infrared spectral data: wavenumber 3069 cm⁻¹ -1 The absorption peaks that appear correspond to the stretching vibration peak of =CH- on the anthraquinone ring; in the wavenumber range of 2945–2870 cm⁻¹ -1 There are two absorption peaks, corresponding to the -CH2- stretching vibration peak on the aliphatic chain; in the infrared spectrum of the starting material 1,2-diaminoanthraquinone, the peaks are in the wavenumber range of 3395–3264 cm⁻¹. -1 There are two absorption peaks, corresponding to the stretching vibration peaks of its amino group (primary amine). These two peaks were not observed in the infrared spectrum of functionalized lactam oligomer D, but they were observed at a wavenumber of 3288 cm⁻¹. -1 A strong absorption peak was observed, corresponding to the NH stretching vibration on the amide bond. The melting point of the functionalized lactam oligomer D was determined to be 205.3℃.

[0092] Example 5

[0093] 100g (254.4mmol) of alcohol-soluble aniline black (structural formula: [insert structural formula here]) was added sequentially to the reactor. The reaction mixture consisted of 144 g (1272 mmol) of caprolactam and 9.9 g of initiator water. The mixture was then heated to 180 °C and stirred until fully dissolved. The mixture was then heated to 230 °C and reacted for 2 h. The reaction was stopped, the product was discharged, and cooled to room temperature to obtain an amino-terminated black functionalized caprolactam oligomer E (BN5).

[0094] The structural formula of the functionalized lactam oligomer E is shown in Table 1, and its NMR spectrum is shown in Table 1. Figure 3 Infrared spectrum Figure 4 Infrared spectral data: wavenumber 3062 cm⁻¹ -1 The absorption peaks that appear correspond to the stretching vibration peak of the =CH- group on the benzene ring of alcohol-soluble aniline black; the wavenumbers are between 2936 and 2872 cm⁻¹. -1 There are two absorption peaks, corresponding to the -CH2- stretching vibration peaks on the lactam fatty chain; wavenumber 1645 cm⁻¹. -1It is a -C=O stretching vibration with a wave number of 3294 cm⁻¹. -1 A strong absorption peak appeared, corresponding to the NH stretching vibration on the amide bond; the melting point of the functionalized lactam oligomer E was found to be 212.5℃.

[0095] Example 6

[0096] Functionalized lactam oligomers were prepared according to the method in Example 5, except that caprolactam was replaced with 402 g (2035.2 mmol) of dodecyl lactam; amino-terminated black functionalized lactam oligomer F was obtained.

[0097] The structural formula of the functionalized lactam oligomer F is shown in Table 1. Infrared spectral data: wavenumber 3060cm⁻¹ -1 The absorption peaks that appear correspond to the stretching vibration peak of the =CH- group on the benzene ring of alcohol-soluble aniline black; the wavenumbers are between 2940 and 2865 cm⁻¹. -1 There are two absorption peaks, corresponding to the -CH2- stretching vibration peaks on the lactam fatty chain; wavenumber 1642 cm⁻¹. -1 It is a -C=O stretching vibration; wave number 3290cm -1 A strong absorption peak was observed, corresponding to the NH stretching vibration on the amide bond. The melting point of the functionalized lactam oligomer F was determined to be 180.5℃.

[0098] Example 7

[0099] 100g (162.3mmol) of water-soluble aniline black (structural formula: ...) was added sequentially to the reactor. p = 1), 367 g (3246.8 mmol) of caprolactam and 9.9 g of initiator water were added, then heated to 180 °C, stirred until fully dissolved, and then heated to 230 °C for 2 h. The reaction was stopped, the product was discharged, and cooled to room temperature to obtain amino-terminated black functionalized lactam oligomer G (SN20). The structural formula of this functionalized lactam oligomer G is shown in Table 1, and the NMR spectrum is shown in [Table 1]. Figure 5 Infrared spectrum Figure 6 The melting point of the functionalized lactam oligomer G was determined to be 210.5℃ (DSC analysis chromatogram shown). Figure 7 ).

[0100] Example 8

[0101] Functionalized lactam oligomers were prepared according to the method of Example 1, except that 1,4-diaminoanthraquinone was replaced with an equimolar amount of Acid Black (structural formula: ); an amino-terminated black functionalized lactam oligomer H was obtained.

[0102] The structural formula of the functionalized lactam oligomer H is shown in Table 1. The melting point of the functionalized lactam oligomer H was found to be 209.3℃.

[0103] Example 9

[0104] Functionalized lactam oligomers were prepared according to the method of Example 1, except that 1,4-diaminoanthraquinone was replaced with an equimolar amount of dye. p = 1; amino-terminated black functionalized lactam oligomer I was obtained.

[0105] The structural formula of the functionalized lactam oligomer I is shown in Table 1. The melting point of functionalized lactam oligomer I was tested to be 187.5℃.

[0106] Example 10

[0107] Functionalized lactam oligomers were prepared according to the method of Example 1, except that 1,4-diaminoanthraquinone was replaced with an equimolar amount of Acid Blue 260 (structural formula: ); amino-terminated blue functionalized lactam oligomer J was obtained.

[0108] The structural formula of the functionalized lactam oligomer J is shown in Table 1. The melting point of the functionalized lactam oligomer J was found to be 192.4℃.

[0109] Example 11

[0110] Functionalized lactam oligomers were prepared according to the method of Example 1, except that 1,4-diaminoanthraquinone was replaced with an equimolar amount of 1-amino-2,4-dibromoanthraquinone; amino-terminated red functionalized lactam oligomer K was obtained.

[0111] The structural formula of the functionalized lactam oligomer K is shown in Table 1. The melting point of the functionalized lactam oligomer K was found to be 214.6℃.

[0112] Example 12

[0113] 7.2 g (30 mmol) of 1,4-diaminoanthraquinone, 30.55 g (270 mmol) of caprolactam and 2 g of initiator water were added sequentially to the reactor. The mixture was then heated to 80 °C and stirred until fully dissolved. The mixture was then heated to 180 °C and reacted for 10 h. The reaction was stopped, the product was discharged, and cooled to room temperature to obtain amino-terminated brown functionalized lactam oligomer L.

[0114] The structural formula of the functionalized lactam oligomer L is shown in Table 1. The melting point of the functionalized lactam oligomer L was found to be 213.8℃.

[0115] Example 13

[0116] 7.2 g (30 mmol) of 1,4-diaminoanthraquinone, 33.9 g (300 mmol) of caprolactam and 0.22 g of initiator water were added sequentially to the reactor, and the mixture was heated to 230 °C and reacted for 10 h. The reaction was then stopped, the product was discharged, and cooled to room temperature to obtain amino-terminated brown functionalized lactam oligomer N.

[0117] The structural formula of the functionalized lactam oligomer N is shown in Table 1. Infrared spectral data: wavenumber 3070 cm⁻¹ -1 The absorption peaks that appear correspond to the stretching vibration peak of =CH- on the anthraquinone ring; in the wavenumber range of 2936–2868 cm⁻¹ -1 There are two absorption peaks, corresponding to the -CH2- stretching vibration peak on the aliphatic chain; in the infrared spectrum of the starting material 1,4-diaminoanthraquinone, the peaks are in the wavenumber range of 3389–3258 cm⁻¹. -1 There are two absorption peaks, corresponding to the stretching vibration peaks of its amino group (primary amine). These two peaks were not observed in the infrared spectrum of functionalized lactam oligomer A, but they were observed at a wavenumber of 3290 cm⁻¹. -1 A strong absorption peak was observed, corresponding to the NH stretching vibration on the amide bond. The melting point of the functionalized lactam oligomer N was determined to be 204.5℃.

[0118] Comparative Example 1

[0119] A dispersion consisting of 36g of Pigment Blue 15 (CAS No.: 147-14-8), 16g of caprolactam, and 20g of initiator water was sequentially added to the reactor and continuously fed to a multi-stage grinding device for grinding and dispersion. The multi-stage grinding device consisted of three grinding mills connected in series, resulting in a slurry with a Pigment Blue 15 content of 50wt% and an average particle size of 0.28μm. The slurry was then mixed evenly with caprolactam melt and catalyst in a dynamic mixer. After the temperature was adjusted by a heat exchanger, the mixture was fed into a high-pressure hydrolysis reactor for a ring-opening reaction. The catalyst was phosphoric acid, with an addition amount of 90ppm of the caprolactam melt mass. The slurry addition amount was 78% of the caprolactam melt mass. The heat exchanger temperature was 160℃, the ring-opening reaction temperature was 260℃, the reaction pressure was 4.7MPa, and the reaction time was 30min, yielding a blue reactant.

[0120] The infrared spectrum of this reactant did not show an absorption peak corresponding to the NH stretching vibration on the amide bond, indicating that the caprolactam oligomer and Pigment Blue 15 did not form a bond. The melting point of the functionalized caprolactam oligomer N was determined to be 367.3℃.

[0121] Table 1

[0122]

[0123]

[0124]

[0125] Example 14

[0126] 2150g of nylon-6 monomer (caprolactam) with carboxyl groups at the end and 0.43g of amino-terminated brown functionalized lactam oligomer A prepared in Example 1 were added to the reactor. Nitrogen gas was purged into the reactor for 10 min, followed by vacuuming for 10 min. This process was repeated three times to remove all air from the reactor. Finally, the reactor was heated to 220°C under a nitrogen atmosphere and stirred at a speed of 450 rpm for 30 min. The system temperature was then raised to 230°C, and the stirring speed was increased to 700 rpm. After reacting for 1 h, the system was vacuumed and subjected to reduced pressure polymerization at -0.07 MPa. The reaction was stopped after 2 h of reduced pressure reaction, the material was discharged, and after cooling, the brown nylon block polymer was obtained.

[0127] Example 15

[0128] 2485g of carboxyl-terminated nylon-66 monomer (hexamethylenediamine adipic acid salt) and 0.31g of amino-terminated purple functionalized lactam oligomer B prepared in Example 2 were added to the reactor. Nitrogen gas was purged into the reactor for 10 min, followed by vacuuming for 10 min. This process was repeated three times to remove all air from the reactor. Finally, the reactor was heated to 210°C under a nitrogen atmosphere and stirred at 400 rpm for 35 min. The system temperature was then raised to 220°C, and the stirring speed was increased to 600 rpm. After reacting for 1.5 h, the system was vacuumed and subjected to reduced pressure polymerization at -0.05 MPa. The reaction was stopped after 3 h of reduced pressure reaction, and the material was discharged and cooled to obtain the purple nylon block polymer.

[0129] Example 16

[0130] 1895g of carboxyl-terminated nylon-1010 monomer (decanediamine sebacate) and 0.38g of amino-terminated purple functionalized lactam oligomer B prepared in Example 2 were added to the reactor. Nitrogen gas was purged into the reactor for 10 min, followed by vacuuming for 10 min. This process was repeated three times to remove all air from the reactor. Finally, the reactor was heated to 230°C under a nitrogen atmosphere and stirred at 500 rpm for 25 min. The system temperature was then raised to 240°C, and the stirring speed was increased to 800 rpm. After reacting for 0.5 h, the system was vacuumed and subjected to reduced pressure polymerization at -0.09 MPa. The reaction was stopped after 1 h of reduced pressure reaction, and the material was discharged and cooled to obtain the purple nylon block polymer.

[0131] Example 17

[0132] The yellow nylon block polymer was prepared according to the method of Example 16, except that the purple functionalized lactam oligomer B obtained in Example 2 was replaced with the yellow functionalized lactam oligomer C obtained in Example 3.

[0133] Example 18

[0134] Purple nylon block polymers were prepared according to the method of Example 16, except that the purple functionalized lactam oligomer B obtained in Example 2 was replaced with the purple functionalized lactam oligomer D obtained in Example 4.

[0135] Example 19

[0136] The black nylon block polymer was prepared according to the method of Example 16, except that the purple functionalized lactam oligomer B obtained in Example 2 was replaced with the black functionalized lactam oligomer E obtained in Example 5.

[0137] Example 20

[0138] The black nylon block polymer was prepared according to the method of Example 16, except that the purple functionalized lactam oligomer B obtained in Example 2 was replaced with the black functionalized lactam oligomer F obtained in Example 6.

[0139] Example 21

[0140] The black nylon block polymer was prepared according to the method of Example 16, except that the purple functionalized lactam oligomer B obtained in Example 2 was replaced with the black functionalized lactam oligomer G obtained in Example 7.

[0141] Example 22

[0142] The black nylon block polymer was prepared according to the method of Example 16, except that the purple functionalized lactam oligomer B obtained in Example 2 was replaced with the black functionalized lactam oligomer H obtained in Example 8.

[0143] Example 23

[0144] The black nylon block polymer was prepared according to the method of Example 16, except that the purple functionalized lactam oligomer B obtained in Example 2 was replaced with the black functionalized lactam oligomer I obtained in Example 9.

[0145] Example 24

[0146] The blue nylon block polymer was prepared according to the method of Example 16, except that the purple functionalized lactam oligomer B obtained in Example 2 was replaced with the blue functionalized lactam oligomer J obtained in Example 10.

[0147] Example 25

[0148] A red nylon block polymer was prepared according to the method of Example 16, except that the purple functionalized lactam oligomer B obtained in Example 2 was replaced with the red functionalized lactam oligomer K obtained in Example 11.

[0149] Example 26

[0150] Brown nylon block polymers were prepared according to the method of Example 16, except that the purple functionalized lactam oligomer B obtained in Example 2 was replaced with the brown functionalized lactam oligomer L obtained in Example 12.

[0151] Example 27

[0152] Brown nylon block polymers were prepared according to the method of Example 16, except that the purple functionalized lactam oligomer B obtained in Example 2 was replaced with the brown functionalized lactam oligomer M obtained in Example 13.

[0153] Example 28

[0154] Brown nylon block polymers were prepared according to the method of Example 16, except that the purple functionalized lactam oligomer B obtained in Example 2 was replaced with the brown functionalized lactam oligomer N obtained in Example 14.

[0155] Example 29

[0156] 1895g of carboxyl-terminated nylon-1010 monomer (decanediamine sebacate) and 3.8g of amino-terminated purple functionalized lactam oligomer B prepared in Example 2 were added to the reactor. Nitrogen gas was purged into the reactor for 10 min, followed by vacuuming for 10 min. This process was repeated three times to remove all air from the reactor. Finally, the reactor was heated to 240°C under a nitrogen atmosphere and stirred at 500 rpm for 25 min. The system temperature was then raised to 240°C, and the stirring speed was increased to 800 rpm. After reacting for 0.5 h, the system was vacuumed and subjected to reduced pressure polymerization at -0.09 MPa. The reaction was stopped after 1 h of reduced pressure reaction, and the material was discharged and cooled to obtain the purple nylon block polymer.

[0157] Example 30

[0158] 1895g of carboxyl-terminated nylon-1010 monomer (decanediamine sebacate) and 0.38g of amino-terminated purple functionalized lactam oligomer B prepared in Example 2 were added to the reactor. Nitrogen gas was purged into the reactor for 10 min, followed by vacuuming for 10 min. This process was repeated three times to remove all air from the reactor. Finally, the reactor was heated to 200°C under a nitrogen atmosphere and stirred at 500 rpm for 25 min. The system temperature was then raised to 240°C, and the stirring speed was increased to 800 rpm. After reacting for 0.5 h, the system was vacuumed and subjected to reduced pressure polymerization at -0.09 MPa. The reaction was stopped after 1 h of reduced pressure reaction, and the material was discharged and cooled to obtain the purple nylon block polymer.

[0159] Example 31

[0160] 1895g of carboxyl-terminated nylon-1010 monomer (decanediamine sebacate) and 0.38g of amino-terminated purple functionalized lactam oligomer B prepared in Example 2 were added to the reactor. Nitrogen gas was purged into the reactor for 10 min, followed by vacuuming for 10 min. This process was repeated three times to remove all air from the reactor. Finally, the reactor was heated to 230°C under a nitrogen atmosphere and stirred at 500 rpm for 25 min. The system temperature was then raised to 270°C, and the stirring speed was increased to 800 rpm. After reacting for 0.5 h, the system was vacuumed and subjected to reduced pressure polymerization at -0.09 MPa. The reaction was stopped after 1 h of reduced pressure reaction, and the material was discharged and cooled to obtain the purple nylon block polymer.

[0161] Comparative Example 2

[0162] Colored nylon block polymers were prepared according to the method of Example 16, except that the purple functionalized lactam oligomer B obtained in Example 2 was replaced with the blue reactant obtained in Comparative Example 1.

[0163] Comparative Example 3

[0164] 1,4-Diaminoanthraquinone was used as the dye, and nylon-6 was dyed by immersion dyeing. The specific process was as follows: through the steps of belt feeding, dyeing bath, steaming in a hot steamer, washing with water, drying with water and belt unloading, the dye molecules were fully contacted with nylon-6 for coloring; finally, brown nylon-6 was obtained by washing with water and drying.

[0165] Comparative Example 4

[0166] Brown nylon-66 was prepared according to the method of Comparative Example 2, except that nylon 6 was replaced with nylon-66.

[0167] Comparative Example 5

[0168] Brown nylon-1010 was prepared according to the method of Comparative Example 2, except that nylon 6 was replaced with nylon-1010.

[0169] Comparative Example 6

[0170] The commercially available black nylon-6, black nylon-66, and black nylon-1010 were all purchased from Guangzhou Chemical City.

[0171] Test Example 1

[0172] The nylon block polymers prepared in Examples 14-31 and the colored nylons in Comparative Examples 2-6 were subjected to boiling tests with water or ethanol, and the color of the supernatant was observed. The nylon block polymers and colored nylons were injection molded into test strips according to GB or ISO standards and their properties were tested: tensile strength and elongation at break were tested according to ISO 527:2019, and cantilever beam notched impact performance was tested according to ISO 180:2019. The results are shown in Table 2.

[0173] Table 2

[0174]

[0175]

[0176] The supernatant obtained after cooking of the colored nylon in Examples 14-31 showed no color change upon visual inspection and had good mechanical properties; the supernatant obtained after cooking of the colored nylon in Comparative Examples 2-5 and commercially available colored nylon before and after cooking with ethanol showed significant color changes.

[0177] 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 inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A functionalized lactam oligomer, characterized in that, The functionalized lactam oligomer contains a lactam oligomer unit as shown in formula (I) and a functional unit bonded to the lactam oligomer unit, wherein the functional unit is a functional agent residue. Where R1 is an alkylene group, and m is an integer from 1 to 100; The melting point of this functionalized lactam oligomer is 180-220℃.

2. The functionalized lactam oligomer according to claim 1, characterized in that, The number average molecular weight of the functionalized lactam oligomer is 500-5000 g / mol, preferably 500-3000 g / mol.

3. The functionalized lactam oligomer according to claim 1 or 2, characterized in that, The functional unit is selected from at least one of amine dye residues, organic acid dye residues, amine softener residues, and organic acid softener residues; preferably, it is an amine dye residue. Preferably, the amine dye residue is selected from at least one of amine anthraquinone dye residues, amine solvent black dye residues, amine acid black dye residues, amine acid blue dye residues, and amine acid yellow dye residues.

4. The functionalized lactam oligomer according to claim 3, characterized in that, The amine dye residues are selected from at least one of the groups shown in formula (II), formula (III), unsubstituted or substituted groups shown in formula (IV), unsubstituted or substituted groups shown in formula (V), and unsubstituted or substituted groups shown in formula (VI). Among them, R I R II R III and R IV Each is independently hydrogen and / or a water-soluble group, and p is an integer from 1 to 10; The substituents of the groups shown in formula (IV), (V), and (VI) are selected from -NO2, -Cl, -Br, -OH, -OCH3, -CH3, -OCH3, -SO3H, -CN, -SO3Na, -NH-CH3, At least one of them; Preferably, the water-soluble group is —(CR) V R VI ) m’ -SO3M,R V R VI Each is independently selected from at least one of hydrogen and C1-C5 alkyl groups, M is a monovalent metal ion and / or ammonium ion, and m' is an integer from 0 to 4.

5. The functionalized lactam oligomer according to claim 1 or 2, characterized in that, R1 is a C2-C20 alkylene group, and m is an integer from 2 to 20.

6. A method for preparing a functionalized lactam oligomer, characterized in that, The preparation method includes: reacting a functional agent with a lactam under ring-opening polymerization conditions; The functional agent has functional groups that can bond to the oligomeric units of the lactam.

7. The preparation method according to claim 6, characterized in that, The molar ratio of the functional agent to the lactam is 1:1-100, more preferably 1:2-20; Preferably, the functional agent is selected from at least one of amine dyes, organic acid dyes, amine softeners, and organic acid softeners; more preferably, it is an amine dye. Preferably, the amine dye is selected from 1-amino-2,4-dibromoanthraquinone, 1-amino-2-bromo-4-hydroxyanthraquinone, 2-amino-3-hydroxyanthraquinone, 2-amino-1-chloroanthraquinone, 1-amino-2-(4-bromophenoxy)-4-hydroxyanthraquinone, 1-amino-4-phenylamino-2-bromoanthraquinone, 1-amino-5-hydroxy-4-[(1-methylpropyl)amino]-8-nitro-9,10-anthraquinone, Acid Blue 129, Acid Blue 25, CI Disperse Red 60, Disperse Blue 359, 1-amino-4-nitroanthraquinone-2-carboxylic acid cyclohexyl ester, Disperse Violet 4, 1-amino-5-benzamidoanthraquinone, 1-amino-2,4-dibromoanthraquinone, etc. Anthraquinone, 2-aminoanthraquinone, 1-amino-4-hydroxyanthraquinone, Acid Blue 40, 2-chloro-4-hydroxy-1-aminoanthraquinone, 1-bromo-3-chloro-2-aminoanthraquinone, 1-amino-4-bromo-2-methylanthraquinone, Disperse Violet 15, 1-amino-4-hydroxy-2-(phenylthio)anthraquinone, 1-amino-9,10-dihydro-4-[[(4-tolyl)sulfonyl]amino]anthraquinone-2-sulfonic acid, CI Reactive Blue 19, 1-amino-4-[(2-methoxyphenyl)amino]anthraquinone, 1-amino-5-hydroxy-4-[(4-methoxyphenyl)amino]-8-nitroanthraquinone, 1-amino-4-bromoanthraquinone Sodium 2-sulfonate, 1-amino-4-bromoanthraquinone-2-sulfonic acid, 1-amino-2-bromo-4-[[3-(dimethylamino)propyl]amino]anthraquinone, 1-amino-4-hydroxy-2-[2-[4-(2-hydroxyethyl)phenyl]ethoxy]anthraquinone, 1-amino-4-bromoanthraquinone, 1-amino-4-hydroxy-2-(4-methoxyphenoxy)anthraquinone, Disperse Red 86, Disperse Red 53, 2-amino-3-hydroxyanthraquinone, Disperse Orange 11, 1-amino-5-[(2,4-dibromophenyl)amino]-4,8-dihydroxyanthraquinone, 1-amino-4,5-dihydroxy-8-(methylamino)anthraquinone, Reactive Blue 4 1-Amino-4-hydroxy-2-[(2-hydroethyl)thio]anthraquinone, 1-amino-5-chloroanthraquinone, 1-amino-2-bromo-4-(3-chloroaniline)anthraquinone, Disperse Red E-4B, 2-amino-3-chloroanthraquinone, Alcohol-soluble Aniline Black, Water-soluble Aniline Black, Amino Black, Acid Black, 1,4-Diaminoanthraquinone, 2,6-Diaminoanthraquinone, 1,2-Diaminoanthraquinone, 1,5-Diaminoanthraquinone, 1,8-Diaminoanthraquinone, 1,4-Diamino-2,3-dichloroanthraquinone, 1,4-Diamino-2,3-dihydroxyanthraquinone, Disperse Red 11, Solvent Violet 59, 1,5-Diamino-4,8-dihydroxyanthraquinone, CIDisperse Blue 56, Disperse Blue 56, 4,8-diamino-1,5-dihydroxy-2-(4-hydroxyphenyl)anthraquinone, 1,5-diamino-4,8-dihydroxy(4-methoxyphenyl)anthraquinone, 4,4-diamino-1,1-iminodianthraquinone, 1,1-iminobis(5-aminoanthraquinone), 4,8-diamino-2-bromo-1,5-dihydroxyanthraquinone, 1,4-diaminoanthraquinone-2,3-disulfonic acid, Disperse Violet 8, Disperse Blue 81, 1,5- At least one of diamino-2-bromo-4,8-dihydroxyanthraquinone, 1,5-diamino-4,8-dihydroxy(4-hydroxyphenyl)anthraquinone, 1,8-diamino-4,5-dihydroxyanthraquinone, and 1,2-diamino-3,4-dicyanoanthraquinone; more preferably, any one of 1,4-diaminoanthraquinone, 2,6-diaminoanthraquinone, 1,2-diaminoanthraquinone, 1,5-diaminoanthraquinone, alcohol-soluble aniline black, water-soluble aniline black, amino black, and acid black. The lactam is a lactam having 3-21 carbon atoms, preferably selected from at least one of butyrolactam, valproic acid lactam, caprolactam, heptanolactam, octylolactam, decalactam, undecalactam, and dodecalactam, and more preferably caprolactam.

8. The preparation method according to claim 6 or 7, characterized in that, The ring-opening polymerization reaction conditions include: in the presence of an initiator, a temperature of 200-300℃, a pressure of 0.08-5 MPa, and a time of 1-20 h; Preferably, the initiator is water, and the weight ratio of the initiator to the lactam is 0.001-1:

1.

9. Functionalized lactam oligomers prepared by the method according to any one of claims 6 to 8.

10. The use of the functionalized lactam oligomer according to any one of claims 1 to 5 and 9 in the preparation of functional polymers, preferably in the preparation of colored polymers.

11. A functional polymer, characterized in that, The functional polymer contains the functionalized lactam oligomer as described in any one of claims 1 to 5 and 9, wherein the functionalized lactam oligomer is segmentally bonded to the polymer.

12. The functional polymer according to claim 11, characterized in that, The functional polymer is a colored polymer, and the colored polymer does not show any decolorization when boiled in water and ethanol for 24 hours.

13. A method for preparing a functional polymer, characterized in that, The method includes: mixing a polymer monomer and / or a polymer matrix with a functionalized lactam oligomer according to any one of claims 1 to 5 and 9 to carry out a polycondensation reaction; wherein the polymer monomer and the polymer matrix both have functional groups capable of bonding with the functionalized lactam oligomer.

14. The preparation method according to claim 13, characterized in that, The method includes: mixing the polymer monomer with the functionalized lactam oligomer to carry out a polycondensation reaction, wherein the weight ratio of the functionalized lactam oligomer to the polymer monomer is 1:1-10000, more preferably 2000-10000, and even more preferably 1:4500-8500. Preferably, the polycondensation reaction process includes a first-stage reaction, a second-stage reaction, and a third-stage reaction carried out sequentially; Preferably, the conditions for the first stage reaction include at least: anaerobic conditions, a temperature of 210-240℃, a pressure of 0.1-1.8MPa, a stirring rate of 400-500rpm, and a time of 25-35min; The conditions for the second stage reaction include at least the following: temperature of 220-270℃, pressure of 0.1-1.8MPa, stirring rate of 600-800rpm, and time of 0.5-1.5h; The conditions for the third-stage reaction include at least the following: temperature of 220-270℃, pressure of -0.05 to -0.09 MPa, and time of 1-3 hours.

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