CN116988184A

CN116988184A - Polymer coloring method, spinning color paste, spinning solution and colored fiber

Info

Publication number: CN116988184A
Application number: CN202310900471.7A
Authority: CN
Inventors: 王蒙; 王恒宇; 刘庆备; 张�林; 高欢; 梅李超; 赵润; 张旭; 张鹏飞; 宋飞虎
Original assignee: Jiangsu New Vision Advanced Functional Fiber Innovation Center Co ltd
Current assignee: Jiangsu New Vision Advanced Functional Fiber Innovation Center Co ltd
Priority date: 2023-07-21
Filing date: 2023-07-21
Publication date: 2023-11-03

Abstract

The invention relates to a high molecular coloring method, spinning solution and colored fibers, belongs to the technical field of textile printing and dyeing, and solves the problems of low relative strength and elongation at break of dyed fiber products caused by high filtering pressure and high breakage rate of a spinning nozzle in the existing dyeing method. The polymer coloring method comprises the following steps: polymerizing a color reaction monomer, an m-phenylenediamine monomer and m-phthaloyl chloride to prepare poly m-phthaloyl m-phenylenediamine color paste; mixing the prepared poly m-phenylene isophthalamide color paste with a poly m-phenylene isophthalamide solution to prepare a colored spinning solution, and carrying out pre-spinning slurry pretreatment; spinning the pretreated spinning solution to obtain nascent fibers; and (3) carrying out post-treatment on the nascent fiber to obtain the poly (m-phenylene isophthalamide) coloring yarn. The invention improves the filtering performance and spinnability of the spinning solution, and the fiber product has good physical properties and low dyeing cost.

Description

Polymer coloring method, spinning color paste, spinning solution and colored fiber

Technical Field

The invention relates to the technical field of textile printing and dyeing, in particular to a polymer coloring method, spinning color paste, spinning solution and colored fibers.

Background

Poly (m-phenylene isophthalamide), PMIA for short, has excellent heat resistance, fiber decomposition temperature up to 500 ℃, long-term use temperature higher than 230 ℃, limiting oxygen index higher than 29, excellent high-temperature acid-base resistance, electrical insulation and good textile processing performance, is widely applied to the fields of protective clothing, high-temperature filter materials, electrical industry and composite materials, and is an indispensable strategic important material in national economic development. However, because the PMIA fiber has a regular molecular structure and high crystallinity and lacks active functional groups on a molecular chain, dye or pigment molecules are difficult to permeate into the structure, and the polymerized PMIA fiber molecules are difficult to combine with the dye or pigment molecules, so that the PMIA fiber and the prepared fabric are difficult to dye, and the PMIA fiber is used as a 'short board' in the field of high-temperature protection.

The existing coloring and dyeing method is to blend pigment or dye with natural color slurry (poly (m-phenylene isophthalamide) solution) of fiber. Pigments are generally inorganic or insoluble organic, exist in the form of particles in the dope fiber, are liable to clog micropores of a spinneret, have large filtration pressure and high breakage rate, and result in low relative strength and elongation at break of the colored fiber product. The dye is generally small organic molecules, cannot resist temperature, and is easy to change color, fade and the like in the high-temperature treatment and use process of fiber products.

In addition, during wet spinning, as the polar solvent and water can be mutually dissolved with dye molecules, the dye is easily dissolved and taken away by the solvent and water, the exhaustion rate is low, and even dyeing cannot be implemented; in addition, small organic molecule dyes are typically dyed in fibers, yarns or fabrics in special solutions containing the dye and specific chemical materials. Dye molecules are immobilized on the fibers by physical bonding, such as absorption, diffusion or adhesion, at a certain temperature and pressure. The bond between the dye molecules and the fibers depends on the physical bond between the dye molecules and the fibers used, for example, PMIA fibers tend to fade or change color due to the weak physical bond between themselves and the dye molecules. In addition, dyeing needs to be performed in a solvent, is energy-consuming, and generates a large amount of wastewater and waste residues.

Disclosure of Invention

In view of the above analysis, the present invention aims to provide a polymer coloring method, a spinning color paste, a spinning solution and a colored fiber, which are used for solving the problems of high filtration pressure, high breakage rate, low relative strength and elongation at break and poor light resistance of dyed fiber products, and the problems of large amount of waste water and waste residue generated by printing and dyeing and environmental pollution of the existing coloring method spinneret.

The aim of the invention is mainly realized by the following technical scheme:

a method of coloring a polymer comprising the steps of:

step 1: reacting the color reaction monomer, the first monomer and the second monomer to obtain poly m-phenylene isophthalamide color paste; wherein, the chromogenic reaction monomer, the first monomer and the second monomer generate an amide bond and are connected with the second monomer through the amide bond;

step 2: mixing the prepared poly m-phenylene isophthalamide color paste with poly m-phenylene isophthalamide unbleached pulp to prepare colored spinning solution, and carrying out pre-spinning slurry pretreatment;

step 3: carrying out wet spinning and precipitation on the poly (m-phenylene isophthalamide) colored spinning solution treated in the step 2 to obtain nascent fibers;

step 4: and (3) carrying out post-treatment on the nascent fiber obtained in the step (3) to obtain the corresponding coloring yarn of the poly (m-phenylene isophthalamide).

Preferably, the preparation of the poly m-phenylene isophthalamide color paste in the step 1 comprises the following steps:

s101: dissolving a color reaction monomer and a first monomer in a polar organic solvent and uniformly mixing;

s102: and gradually adding a second monomer, and polymerizing to obtain the poly m-phenylene isophthalamide color paste.

Preferably, the ratio of the amount of the substances of the color reaction monomer to the first monomer in step 1 is in the range of: 0.1 to 100:0 to 99.9; the mass ratio of the PMIA color paste to the PMIA unbleached paste is 1:1-30.

Preferably, the chromogenic reaction monomer is a compound containing two primary amino groups; preferably, the chromogenic reaction monomer is an aromatic compound containing two primary amino groups; preferably, the color reaction monomer is diaminoanthraquinone or azo-based aromatic diamine.

Preferably, the diaminoanthraquinone is one or more of 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 2, 6-diaminoanthraquinone, 1, 5-diamino-4, 8-dihydroxyanthraquinone, 1, 2-diaminoanthraquinone, 1, 8-diaminoanthraquinone, 1, 4-diamino-2, 3-diphenoxyanthraquinone, 1, 4-diamino-2, 3-dichloroanthraquinone, 1, 4-diamino-2-methoxy-9, 10-anthraquinone, 1, 5-dihydroxy-4, 8-diamino-2-chloroanthraquinone, and/or the azo aromatic diamine is 4- [ (4-nitrophenyl) azo ] benzene-1, 3-diamine.

The spinning color paste for the colored fibers is prepared by the polymer coloring method, and comprises colored polymers and polar organic solvents, wherein the colored polymers and the polar organic solvents are used for preparing spinning solution;

the colored polymer includes: the two structural units (I) and (II) are randomly distributed, and Aq contains anthraquinone functional groups or aromatic azo groups.

Preferably, the number ratio of the two structural units (I) and (II) is as follows: 0 to 99.9:0.1 to 100.

The spinning solution for coloring fibers is prepared by the polymer coloring method and comprises coloring polymers and polar organic solvents;

Preferably, the viscosity [ η ] of the dope is: 1.60 to 2.50, preferably 2.00 to 2.30.

The colored fiber is prepared by the polymer coloring method, and comprises two structural units (I) and (II) which are randomly distributed:

wherein Aq represents an anthraquinone functional group or an aromatic azo group;

the dynamic viscosity of the colored fiber is 20000 to 50000/centipoise, preferably 29000 to 45000/centipoise.

Compared with the prior art, the invention has at least one of the following beneficial effects:

(1) The coloring method of the invention introduces dye molecules into the main chain of the polymer to copolymerize to form the colored polymer through a certain chemical reaction, which is different from the mechanism of blending coloring and graft copolymerization coloring. The color reaction monomer is taken as one of reactants, is copolymerized with other monomers of the fiber to form a polymer main chain, is dissolved in a solvent system to form an in-phase solution, and compared with the existing fiber coloring method using the particle pigment, the color reaction monomer has the advantages of small filtering pressure, low breakage rate, high relative strength and high elongation at break of the dyed fiber, and greatly improves the physical properties of the colored fiber product; the defects of the prior art that micropores of a spinneret are easy to be blocked, the filtration pressure is high, the breakage rate is high, and the relative strength and the breaking elongation of the dyed fiber product are low are overcome; compared with the method of dyeing the fiber after spinning, the dyeing unit structure of the invention is more stable, is not easy to leach out and run off or age, and has obviously improved dyeing durability and light aging resistance.

(2) The PMIA color paste containing the high-concentration color development units is prepared from the color development reaction monomers and the PMIA raw materials, and the PMIA color paste and the PMIA unbleached paste are mixed according to different proportions to prepare the spinning solution, so that the influence on the whole spinnability of the spinning solution when the color development reaction monomers are more is improved, PMIA colored fibers with different concentrations can be flexibly prepared, and the applicability is improved; meanwhile, by synthesizing PMIA color paste, the synthesis reaction scale and the synthesis amount of the colored spinning solution can be reduced, and the PMIA dyeing cost is further reduced.

(3) The invention obtains rich color system by selecting the color reaction monomers with different reactivities to copolymerize with other monomers of the polymer to be dyed to form a high molecular chain; in the prior art, the blending coloring method needs to consider pigment dispersibility, uniformity and pigment and polymer compatibility, so that the pigment selection range is limited.

(4) The invention forms a high molecular chain through the polymerization of the chromogenic reaction monomer, and the high molecular chain is dispersed in a resin matrix at a molecular level, so that the dispersion is uniform, the tinting strength is strong, the dosage of the monomer is small, and the dyeing cost can be saved; the existing blending coloring adjusts the color and shade of the coloring through the addition amount of the pigment, the pigment exists in the polymer in the form of particles, the coloring power is poor, and the required addition amount is large.

(5) The polar solvent used in the spinning process can be recovered by means of reduced pressure distillation and the like, so that the dyeing waste residue and waste water generated in the dyeing process in the prior art are completely avoided, and compared with the existing spinning method, the energy conservation and consumption reduction are realized, and the environmental pollution is reduced.

In the invention, the technical schemes can be mutually combined to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.

Drawings

The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, like reference numerals being used to refer to like parts throughout the several views.

FIG. 1 is a process flow diagram of a one-step mill base process in one embodiment of the invention.

Detailed Description

The following detailed description of preferred embodiments of the invention is made in connection with the accompanying drawings, which form a part hereof, and together with the description of the embodiments of the invention, are used to explain the principles of the invention and are not intended to limit the scope of the invention.

Aiming at the defects that pigment exists in a particle form in spinning solution fiber, micropores of a spinneret are easy to be blocked, the filtering pressure is high, the breakage rate is high, the relative strength and the breakage elongation of a dyed fiber product are low, an organic small-molecule dye cannot resist temperature, the color is easy to change and fade in the high-temperature treatment and use process of the fiber product, and the printing and dyeing wastewater is large and difficult to treat, a color reaction monomer with reactivity is selected as one of reactants, and is copolymerized with other monomers of the fiber to form a high-molecular main chain, and the polymer main chain is dissolved in a solvent system to form an in-phase solution, so that the defects that in the prior art, the filtering pressure of pigment dyeing on PMIA dyeing is low, the breakage rate is low, and the relative strength and the breakage elongation of the dyed fiber are low are overcome; on the other hand, the color reaction monomer participates in macromolecular chain formation and is dispersed in the resin matrix at a molecular level, so that PMIA is dyed by the organic micromolecule dye, and the color reaction monomer is more uniform in dispersion, stronger in tinting strength, more stable in effect and longer in tinting time.

The invention discloses a high polymer coloring method, which comprises the following steps:

step 1: reacting the color reaction monomer with the first monomer and the second monomer to obtain poly m-phenylene isophthalamide (PMIA) color paste; wherein, the chromogenic reaction monomer, the first monomer and the second monomer generate an amide bond and are connected with the second monomer through the amide bond;

step 2: mixing the PMIA color paste with PMIA natural color paste to prepare colored spinning solution, and carrying out pre-spinning slurry pretreatment;

step 3: carrying out wet spinning and precipitation on the PMIA colored spinning solution treated in the step 2 to obtain nascent fibers;

step 4: and (3) carrying out post-treatment on the nascent fiber obtained in the step (3) to obtain the corresponding PMIA colored silk.

In the invention, dye molecules are introduced into a main chain of a polymer to be copolymerized into a colored polymer through chemical reaction, and the mechanism is different from the mechanism of blending coloring and graft copolymerization coloring: the chromogenic reaction monomer is taken as one of reactants, is copolymerized with other monomers (such as a first monomer or a second monomer) of the synthetic fiber to form a high molecular main chain, and is dissolved in a solvent system to form an in-phase solution.

Compared with the fiber coloring method in the prior art using the particle pigment, the coloring method has the characteristics of small filtering pressure, low breakage rate and high relative strength and elongation at break of the dyed fiber, and greatly improves the physical properties of colored fiber products; the defects of high filtering pressure and high breakage rate, which cause low relative strength and elongation at break of dyed fiber products, of micropores which are easy to block a spinneret in the prior art are overcome; meanwhile, the coloring unit directly participates in forming the coloring polymer, so that the structure of the coloring unit is more stable compared with the dye for dyeing, the leaching loss or aging is not easy, and the dyeing durability and the light aging resistance are obviously improved.

It can be understood that the invention prepares spinning color paste by connecting a color reaction monomer as a reaction monomer of the colored PMIA fiber to a PMIA polymer main chain in the reaction, thereby realizing the direct preparation of the colored fiber by the PMIA spinning process, and the fibers can be conveniently processed into colored yarns in the subsequent process to further prepare colored fabrics; or directly preparing non-woven fabrics, and dyeing is not needed in the subsequent use process of the fiber. In contrast, if the fibers are spun from the PMIA natural color pulp, and then dyed after spinning or weaving, a dyeing process is added, and the bath used in the dyeing process is also treated and then discharged. Compared with the prior art, the invention has no dyeing wastewater, and reduces wastewater discharge after water treatment.

It can be understood that the PMIA color paste containing the high-concentration color development unit is prepared, and the PMIA color paste and the PMIA natural color paste are mixed according to the design proportion when in use, so that the PMIA fibers with different chromaticity are obtained after spinning, and the applicability is improved; meanwhile, the synthesis reaction scale and the synthesis amount of the colored spinning solution can be reduced, so that the PMIA dyeing cost is reduced.

Specifically, the polymerization reaction temperature of the polymerization reaction in the step 1 is-20 ℃ to 50 ℃; for example, it may be-20 ℃, -15 ℃, -10 ℃, -5 ℃, 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ and 50 ℃.

The polymerization reaction temperature is lower than-20 ℃, the reaction speed is low, the efficiency of the whole process can be reduced, and the reaction time can be prolonged; the polymerization temperature is higher than 50 ℃, the side reaction is increased, the linearity of PMIA molecules is destroyed, the molecular weight is lower, the viscosity is lower, the spinnability is reduced, and the fiber strength and the elongation at break are reduced.

Specifically, the preparation of the PMIA color paste in the step 1 can adopt a one-step color paste method, as shown in fig. 1:

s102: and gradually adding a second monomer, and polymerizing to obtain PMIA color paste.

The second monomer (such as isophthaloyl dichloride) is added into the solution of the chromogenic reaction monomer and the first monomer to form a local large excess of the chromogenic reaction monomer and the first monomer, which is favorable for the main reaction, inhibits the reaction of a small amount of impurities such as water and the like in the system with the second monomer, and generates side reaction to influence the chain extension growth of the PMIA prepolymer.

Under the condition that the second monomer is sufficient or excessive, the first monomer and the chromogenic reaction monomer can react with the second monomer in competition, and the prepared coloring macromolecule long chain simultaneously has a structural unit containing the first monomer and the second monomer and a structural unit containing the chromogenic reaction monomer and the second monomer.

Specifically, the first monomer comprises an amino group and the second monomer comprises a formyl group.

Preferably, the first monomer is m-phenylenediamine and the second monomer is m-phthaloyl chloride.

Specifically, the chromogenic reaction monomer is a compound containing two primary amino groups.

Preferably, the chromogenic reactive monomer is an aromatic compound containing two primary amino groups.

Preferably, the chromogenic reactive monomer is a diaminoanthraquinone or an azo-based aromatic diamine. Preferably, the color-forming reaction monomer may be selected from one or more of 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 2, 6-diaminoanthraquinone, 1, 5-diamino-4, 8-dihydroxyanthraquinone, 1, 2-diaminoanthraquinone, 1, 8-diaminoanthraquinone, 1, 4-diamino-2, 3-diphenoxyanthraquinone, 1, 4-diamino-2, 3-dichloroanthraquinone, 1, 4-diamino-2-methoxy-9, 10-anthraquinone, 1, 5-dihydroxy-4, 8-diamino-2-chloroanthraquinone.

Specifically, the structural formula of 1, 4-diamino-2, 3-diphenoxyanthraquinone is as follows:

the structural formula of the 1, 4-diamino-2, 3-dichloro anthraquinone is as follows:

1, 4-diamino-2-methoxy-9, 10-anthraquinone structural formula satisfies:

the structural formula of the 1, 5-dihydroxy-4, 8-diamino-2-chloroanthraquinone is as follows:

preferably, the chromogenic reaction monomer may be chosen to be 4- [ (4-nitrophenyl) azo ] benzene-1, 3-diamine.

Specifically, the structural formula of 4- [ (4-nitrophenyl) azo ] benzene-1, 3-diamine is as follows:

illustratively, taking m-phenylenediamine as a first monomer and isophthaloyl chloride as a second monomer and the second monomer being in sufficient or excess, the first monomer and the second monomer react as follows:

wherein n represents the number of polymer constituent units;represents a polymer constituent unit formed by the reaction of a first monomer and a second monomer.

Illustratively, a diaminoanthraquinone (of the formula NH ₂ -Aq-NH ₂ ) As the color reaction monomer and isophthaloyl dichloride as the second monomer and a sufficient amount or an excessive amount of the second monomer are exemplified, the color reaction monomerThe first monomer reacts with the second monomer as follows:

wherein, the liquid crystal display device comprises a liquid crystal display device,a represents the number of polymer structural units formed by reaction of a chromogenic reaction monomer and a second monomer, n-a represents the number of polymer structural units formed by reaction of diaminoanthraquinone, and Aq contains anthraquinone functional groups or aromatic azo groups; in the color paste, two structural units (I) and (II) are randomly distributed:

Specifically, the number ratio of the two structural units (I) to (II) in the color paste is as follows: 0 to 99.9:0.1 to 100.

Specifically, in step S102, the polymerization reaction for preparing the polymelia color paste includes a plurality of different reaction stages, and the polymerization reaction temperatures of the reaction stages are different:

the first stage: the preparation method mainly comprises the steps of reacting a first monomer, a chromogenic reaction monomer and a second monomer to generate a micromolecule prepolymer and randomly copolymerizing the micromolecule prepolymer to generate a long-chain prepolymer;

and a second stage: as the second monomer continues to be added, the second monomer reacts with the first monomer or the end groups of the chromophoric reaction monomer of the prepolymer molecule to achieve long chain prepolymer ligation and long chain propagation.

Specifically, taking the second monomer as isophthaloyl dichloride as an example, the primary reaction equation in the first stage satisfies:

wherein R represents a first monomer or a reactive chromonic unit other than an amino group; NH (NH) ₂ -R-NH ₂ Represents a first monomer or reactive chromonic unit; m represents the number of polymetaphthaloyl structures in the long chain prepolymer or the consumption of the second monomer in the first stageNumber of volumes.

Specifically, taking the second monomer as isophthaloyl dichloride as an example, the main reaction equation in the second stage satisfies the following conditions:

wherein n represents the number of high molecular structural units in the poly (m-phenylene isophthalamide); p represents the consumption of a second monomer amount in the second stage for the preparation of PMIA molecules having a number of structural units n; r is R _p+1 Representing the p+1th long chain prepolymer, the number of polymetaphthaloyl structures of different long chain prepolymers may be the same or different.

Preferably, the polymerization reaction temperature in the first stage is-20 ℃ to 20 ℃, and PMIA molecules have larger viscosity average molecular weight and better mechanical strength in the range; the reaction time is 0.05 h-1 h.

Further preferably, the first stage polymerization temperature is from-5℃to 20 ℃.

Preferably, the polymerization reaction temperature of the second stage is 20-50 ℃ and the reaction time is 0.05-2 h.

The second monomer (such as isophthaloyl dichloride) is gradually added into the solution of the chromogenic reaction monomer and the first monomer to form a large local excess of the chromogenic reaction monomer and the first monomer, which is favorable for the main reaction, inhibits the reaction of a small amount of impurities such as water and the like in the system with the second monomer, reduces the occurrence of side reaction, is favorable for the chain extension and growth of the prepolymer in the spinning solution, and obtains the colored polymer with larger molecular weight and polymerization degree.

It will be appreciated that the gradual addition of the second monomer allows the reaction temperature to be readily maintained stable, preventing the reaction from running away due to severe exotherms, while the lower temperature helps to reduce side reactions.

Specifically, the gradual addition of the second monomer is achieved by:

The total amount of the second monomer may be divided into equal or unequal portions, and a certain portion of the second monomer is added at each time interval, or the feeding rate may be changed between 0 and any value satisfying instantaneous feeding by using a continuous feeding device.

Specifically, the feeding time of the second monomer is 0.1-4 h, and the polymerization reaction time is 0.1-6 h; the polymerization reaction time is less than 0.1h, and the reaction is insufficient; the polymerization reaction time exceeds 6 hours, side reactions are increased, the molecular weight of the polymer is affected, and the efficiency is low.

Preferably, the polymerization temperature is monitored, and the feed rate is adjusted according to the polymerization temperature to ensure that the polymerization temperature does not exceed the set temperature range.

Further preferably, in the polymerization reaction temperature monitoring, a temperature control feedback mechanism for the continuous feeding device is arranged, so that the automatic feeding of the polymerization reaction temperature in a controllable range is realized by automatically adjusting the feeding rate according to the temperature.

Specifically, the temperature is higher than a preset target temperature, the feeding is reduced or stopped, and the heat dissipation rate of a heat dissipation device on the reactor is increased (such as the cooling water temperature is reduced and the water flow speed is increased); the temperature is lower than the preset target temperature, the feeding speed is improved, the heat dissipation rate of a heat dissipation device on the reactor is reduced, and a heating device is opened for heating if necessary, so that the feeding quantity is adjusted by utilizing temperature feedback.

Specifically, the mass ratio range of the color reaction monomer in the color paste to the substances in the color reaction monomer and the first monomer is as follows: 0.1 to 100 percent.

Preferably, the mass ratio range of the chromogenic reaction monomer in the color paste to the substances in the chromogenic reaction monomer and the first monomer is: 0.1 to 20 percent.

When the mass ratio of the color reaction monomer to the substances in the first monomer exceeds 20%, the colored high molecular weight and the polymerization degree in the color paste are reduced, and the spinnability is reduced; the invention improves the influence on the integral spinnability of the spinning solution when more color reaction monomers are used by adopting the process of preparing the spinning solution by mixing the PMIA unbleached pulp and the colored color pulp.

Specifically, the polar organic solvent in step S101 may be selected from any one of N-dimethylacetamide, dimethylformamide (DMF), and N-methylpyrrolidone, which has good solubility to the raw material monomer in the range of-20 ℃ to 60 ℃ and does not react with any raw material monomer.

Specifically, in the step S101, the mass concentration of the colored polymer in the PMIA color paste is 16-22%.

Regarding color paste, spinning solution and color development effect after spinning, it is to be noted that, on one hand, the color reaction monomers participating in the reaction make PMIA colored spinning solution and spun PMIA colored fiber present the corresponding color reaction monomer colors; on the other hand, after the compounding of a plurality of different color chromophoric reaction monomers, the mixed color different from any single chromophoric reaction monomer can be generated after spinning.

Specifically, the reactor for obtaining PMIA color paste can use various types of reactors which have strong material mixing functions, such as a vertical or horizontal kettle type reactor, a screw reactor, and a kneader; the aspect ratio of the reactor is more than 1:1 with a jacket or other form of heat sink or heating means to which a cooling or heating liquid is fed.

Specifically, the stirring power of the vertical or horizontal kettle type reactor is 3KW/m ³ ～50KW/m ³ The stirring speed is 100 rpm-3000 rpm, and various stirring paddles can be used, such as anchor type, paddle type, frame type, multi-layer paddle type, cross type or composite structure type stirring paddles.

Specifically, the screw reactor and various mixing and mixing structural units are used in a combined mode, the rapid rolling state of the solution in the reaction process is maintained, good heat exchange between the inside and the outside is achieved, and rapid polymerization is achieved under the safety condition.

On the one hand, when the radial flow brought by stirring is required to meet the requirement of feeding of the second monomer, substances in different radial areas inside the reaction vessel are uniformly mixed, namely radial mass transfer is realized; on the other hand, when the axial flow brought by stirring can meet the requirement of feeding the second monomer, substances in axially different areas inside the reaction vessel are uniformly mixed, namely, the axial mass transfer is realized; in addition, the heat in the internal region of the reaction vessel is transferred to the region exchanging external heat while the mixing of the regions is realized, and the heat is exchanged with external heat, so that the heat transfer and stable temperature control of the regions in the reactor are realized.

Specifically, in order to ensure the spinnability of the spinning solution and the mechanical property of the dyed fiber after the PMIA color paste and the PMIA natural color paste are mixed; the mass ratio range of the substances of the color reaction monomer and the first monomer in the step 1 is as follows: 0.1 to 100:0 to 99.9; in the step 2, the mass ratio of the PMIA color paste to the PMIA unbleached paste is 1:1-300.

Specifically, the pre-spinning slurry pretreatment in step 2 comprises: neutralization, filtration and deaeration.

Specifically, the neutralizing agent is selected from: inorganic base, or organic amine.

Preferably, the inorganic base is one or more of calcium hydroxide, sodium hydroxide, lithium hydroxide and ammonia water.

Specifically, the organic amine is one or more of diethylamine and triethylamine.

Specifically, the filtration pressure is 0.4Mpa to 0.5Mpa.

Specifically, the filtration adopts a closed filter such as a plate-and-frame filter press, a candle filter element filter, a disc filter, a van filter and other precision pressure-resistant filters.

It can be understood that the filtration pressure is related to the density of the spinning solution, the filtration speed and the content of insoluble impurities in the solution, and the inorganic dye in the prior art is insoluble in the spinning solution, so that agglomeration is easy to generate during filtration, and the filtration pressure and the energy consumption of a filtration pump are increased during filtration.

Specifically, vacuum defoaming is adopted for defoaming, and the vacuum degree is 0.1 Kpa-20 Kpa.

Specifically, the spinning pressure of the wet spinning in the step 3 is set to 0.2 to 2MPa, for example, 0.2MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.8MPa, 1.0MPa, 1.2MPa, 1.4MPa, 1.5MPa, 1.6MPa, 1.8MPa, 2.0MPa; the spinning temperature is 5-40 ℃, such as 5 ℃, 6 ℃, 8 ℃, 10 ℃, 12 ℃, 14 ℃, 15 ℃, 18 ℃, 20 ℃, 22 ℃, 24 ℃, 25 ℃, 28 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃; the spin feed rate is 1 m/min to 30 m/min, for example 1 m/min, 2 m/min, 5 m/min, 8 m/min, 10 m/min, 12 m/min, 15 m/min, 18 m/min, 20 m/min, 22 m/min, 25 m/min, 28 m/min, 30 m/min.

Specifically, the aperture of the wet spinning spinneret is 0.04 mm-0.10 mm. For example, the thickness of the material may be 0.04mm, 0.06mm, 0.08mm, or 0.10mm.

Specifically, the precipitation solution used in the precipitation in the step 3 is a mixed solution of the above-mentioned polar organic solvent and an aqueous solution of an alcohol and/or calcium chloride.

The addition of alcohol or calcium chloride to the solution of PMIA fibers and polar organic solvent helps to reduce the solubility of PMIA fibers in the mixed solution.

Specifically, the mass ratio of the polar organic solvent to the alcohol and/or the aqueous solution of calcium chloride is in the range of 0.2-0.7: from 0.3 to 0.8, in which the spinning precipitate has the highest yield.

Specifically, the post-processing in step 4 includes: plasticizing and stretching, washing, drying and high-temperature heat treatment.

Specifically, the specific method and process conditions for plasticizing and stretching are as follows: the fibers are passed through a plurality of rollers of varying speeds in sequence so that the speed of the fibers as they leave the stretcher is greater than the speed of the fibers as they enter the stretcher, thereby achieving the stretching effect.

In particular, the fibers are immersed in the plasticizing liquid or rinsed by the plasticizing liquid when in two multi-roll machines of different speeds.

Specifically, the plasticizing liquid is a mixed liquid of a polar solvent, inorganic salt and water.

Preferably, the plasticizing liquid is an aqueous solution of DMAC (dimethylacetamide) and calcium chloride, and the mass ratio is as follows: DMAC: calcium chloride: water= (5-30): (0-20): (70:50).

It will be appreciated that the effect of plasticising and stretching is: under the action of plasticizing liquid, the polymer is swelled to a certain extent by the action of solvent, and the polymer can slide mutually to a certain extent under the action of external force, so as to achieve the drawing aim of the molecular in the fiber along the axial orientation of the fiber.

Specifically, the fiber absorbs the plasticizing liquid in the plasticizing and stretching process, so that substances such as polar solvent, inorganic salt and the like remain in the plasticizing liquid; the physical and mechanical properties of the fiber are affected by the substances, and the impurity substances are removed by water washing, the solvent is recovered, so that the material consumption is reduced; the specific method for water washing comprises the following steps: the fiber is washed with water in a multistage countercurrent immersion or leaching mode by using multistage water washing.

Specifically, the specific method and process conditions for drying are as follows: drying the fiber bundles by means of a multi-stage hot roller hot plate or a hot cavity and the like, wherein when the fibers pass through the surface of the heat equipment, heat is transferred from machinery to the fibers, the temperature of the fiber bundles rises, and moisture in the fiber bundles is heated and evaporated, so that the drying effect is achieved; the equipment such as the hot roller or the hot plate can be heated by using an electric resistor, a heating medium (such as heat conducting oil) or steam and the like.

It will be appreciated that drying may remove residual moisture and polar organic solvents.

Specifically, the specific method for high-temperature heat treatment in post-treatment comprises the following steps: and heating the dried fiber by a high-temperature hot cavity device and drawing.

It will be appreciated that the effect of the high temperature heat treatment is: the polymer in the fiber is further oriented along the axial direction of the fiber, so that the physical and mechanical properties are further improved, and the heat resistance of the fiber after being colored is also improved.

The invention discloses a spinning color paste of colored fibers, which comprises colored polymers and a polar organic solvent, wherein the colored polymers and the polar organic solvent are used for preparing the colored fibers by spinning;

Specifically, the number ratio of the two structural units (I) to (II) is as follows: 80-99.9:0.1-20.

Specifically, the polar organic solvent may be any one of N-dimethylacetamide, dimethylformamide (DMF), and N-methylpyrrolidone.

The invention discloses a spinning color paste of colored fibers, which comprises colored polymers and a polar organic solvent, wherein the colored polymers and the polar organic solvent are used for preparing spinning solution by spinning;

Specifically, the number ratio of the two structural units (I) to (II) is as follows: 0 to 99.9:0.1 to 100.

The invention discloses a spinning solution of colored fibers, which comprises colored polymers and a polar organic solvent, wherein the colored polymers and the polar organic solvent are used for preparing the colored fibers by spinning;

Preferably, the concentration of PMIA colored polymer mass in the spinning solution is 16 to 22%.

Preferably, the viscosity [ η ] of the dope is: 2.0 to 2.30.

[ eta ] represents the relative viscosity, the dynamic viscosity of spinning solution and the dynamic viscosity ratio of the solvent in the spinning solution.

In one embodiment of the present invention, a colored fiber is disclosed comprising two structural units of (I) and (II) randomly distributed:

wherein Aq comprises an anthraquinone functionality or an aromatic azo group.

Optionally, the colored fibers are prepared by the polymer coloring method.

Specifically, PMIA colored spinning solution is prepared by reacting a colored reaction monomer, a first monomer and a second monomer, and colored spinning solution is further spun to obtain colored fibers.

Preferably, the chromogenic reaction monomer is a diaminoanthraquinone. For example, one or more of 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 2, 6-diaminoanthraquinone, 1, 5-diamino-4, 8-dihydroxyanthraquinone, 1, 2-diaminoanthraquinone, 1, 8-diaminoanthraquinone, 1, 4-diamino-2, 3-diphenoxyanthraquinone, 1, 4-diamino-2, 3-dichloroanthraquinone, 1, 4-diamino-2-methoxy-9, 10-anthraquinone, 1, 5-dihydroxy-4, 8-diamino-2-chloroanthraquinone may be selected.

Specifically, the dynamic viscosity of the fiber is 29000-45000/centipoise; the glass transition temperature of the colored fiber is 260-275 ℃; the relative strength of the fiber is 4.05 to 4.4cN/dtex; the breaking elongation of the fiber is 21% -32%; the light color fastness is 3-5 grade; the washing fastness grade is 4-5 grade.

In order to better illustrate the invention, the following examples and comparative examples are further provided:

example 1

(1) Preparing colored color paste: 1, 5-diaminoanthraquinone and m-phenylenediamine are mixed according to a molar ratio of 10:46, adding the mixture into a proper amount of N-dimethylacetamide solvent, adding isophthaloyl dichloride the same as the total mass of diaminoanthraquinone and m-phenylenediamine into the solution for polymerization for 4 times in 2 hours, neutralizing the solution to pH7.0 by using calcium hydroxide after the reaction is finished, and obtaining color paste with extra-normal concentration (the mass concentration of solute is 16.1%), wherein the polymerization temperature and time are controlled at-5 ℃ for 1 hour in the first stage, and the polymerization temperature is controlled at 20 ℃ for 1 hour in the second stage.

(2) Mixing the obtained color paste with PMIA unbleached pulp with the same mass concentration according to the following weight percentage of 1:30 mass ratio to obtain PMIA colored spinning solution;

(3) Filtering PMIA colored spinning solution, filtering at 0.45Mpa and defoaming, then wet spinning at 20 ℃ and spinning feeding rate of 6 m/min under the spinning pressure or the pressure of each spinning area of 0.55Mpa, and obtaining the nascent fiber. Wherein the aperture of the spinning jet is 0.06mm, and the precipitation solution is a mixed solution of N-dimethylacetamide, calcium chloride and water (the mass ratio is 45:25:30).

(4) And (3) plasticizing and stretching the nascent fiber by 3 times, washing with water, drying at 120 ℃ and performing high-temperature heat treatment at 370 ℃ to directly obtain the corresponding PMIA colored silk.

Example 2

(1) 1, 4-diaminoanthraquinone and m-phenylenediamine are mixed according to a molar ratio of 95:5, adding the mixture into a proper amount of N-dimethylacetamide solvent, adding isophthaloyl dichloride with the same amount of total substances of diaminoanthraquinone and m-phenylenediamine into the solution for polymerization for 6 times in equal amount within 4 hours, neutralizing the solution to PH9.0 by using calcium hydroxide after the reaction is finished, obtaining color paste with extra-normal concentration (the mass concentration of solute is 22%), controlling the polymerization temperature and time at-20 ℃ in the first stage by using temperature feedback to adjust the feeding amount, and controlling the polymerization temperature and time at 50 ℃ in the second stage for 2 hours.

(2) Mixing the obtained color paste with PMIA unbleached pulp with the same mass concentration according to the following weight percentage of 1:5, mixing the materials according to the mass ratio to obtain PMIA colored spinning solution;

(3) Filtering PMIA colored spinning solution, filtering at 0.37Mpa and defoaming, then wet spinning at 26 ℃ and spinning feeding rate of 6.5 m/min under the conditions of spinning pressure or pressure of each spinning area of 0.67Mpa, cooling at 30 ℃ for 2min after wet spinning to solidify into filaments, and obtaining the nascent fiber after smooth and basically no filoplume and precipitation in the spinning process. Wherein the aperture of the spinning nozzle is 0.04mm; wherein the coagulating bath is an N-dimethylacetamide solution, the mass percentage concentration of the coagulating bath is 40 percent, and the temperature is 30 ℃.

(4) And (3) plasticizing and stretching the nascent fiber by 2.5 times, washing, drying at 125 ℃ and performing high-temperature heat treatment at 370 ℃ to directly obtain the corresponding PMIA colored silk.

Example 3

(1) 2, 6-diaminoanthraquinone and m-phenylenediamine are mixed according to the molar ratio of 0.5:99.5, adding the mixture into a proper amount of N-dimethylacetamide solvent, adding isophthaloyl dichloride which has the same amount as the total substances of diaminoanthraquinone and m-phenylenediamine into the solution for polymerization for 5 times in 2 hours, neutralizing the solution to PH8.0 by using calcium hydroxide after the reaction is finished, obtaining color paste with extra-high concentration (the solute mass concentration is 16.1 percent), and controlling the polymerization temperature and time at-5 ℃ in the first stage and 30 ℃ in the second stage by using temperature feedback to adjust the feeding amount.

(2) Mixing the obtained color paste with PMIA (PMIA) unbleached pulp with the same mass concentration according to the mass ratio of 1:1 to obtain PMIA colored spinning solution;

(3) Filtering PMIA colored spinning solution, filtering under the pressure of 0.50Mpa, defoaming, then wet spinning under the pressure of 0.50Mpa, the spinning temperature of 22 ℃ and the feeding rate of 5.6/min, wherein the spinning process is smooth without hairline and precipitation, thus obtaining the nascent fiber. Wherein the aperture of the spinning jet is 0.10mm, and the precipitation solution is a mixed solution of N-dimethylacetamide and water (mass ratio of 60:40).

(4) And (3) plasticizing and stretching the nascent fiber by 2.5 times, washing with water, drying at 120 ℃ and performing high-temperature heat treatment at 370 ℃ to directly obtain the corresponding PMIA colored silk.

Example 4

(1) Preparing a colored spinning solution: 1, 5-diamino-4, 8-dihydroxyanthraquinone and m-phenylenediamine are mixed according to the molar ratio of 10:46, adding the mixture into a proper amount of N-dimethylacetamide solvent, adding isophthaloyl dichloride the same as the total mass of diaminoanthraquinone and m-phenylenediamine into the solution for polymerization for 4 times in 2 hours, neutralizing the solution to pH7.0 by using calcium hydroxide after the reaction is finished, and obtaining color paste with extra-normal concentration (the mass concentration of solute is 16.1%), wherein the polymerization temperature and time are controlled at-5 ℃ for 1 hour in the first stage, and the polymerization temperature is controlled at 20 ℃ for 1 hour in the second stage.

(2) Mixing the obtained color paste with PMIA (PMIA) unbleached pulp with the same mass concentration according to the mass ratio of 1:1.5 to obtain PMIA colored spinning solution;

(3) Filtering PMIA colored spinning solution, filtering at 0.40Mpa and defoaming, then wet spinning at 20 ℃ and spinning feeding rate of 5.3/min under the spinning pressure or the pressure of each spinning area of 0.55Mpa, wherein the spinning process is smooth without filoplume, and the primary fiber is obtained by precipitation. Wherein the aperture of the spinning jet is 0.06mm, and the precipitation solution is a mixed solution of N-dimethylacetamide, calcium chloride and water (the mass ratio is 45:25:30).

(4) And (3) plasticizing and stretching the nascent fiber by 2.5 times, washing with water, drying at 120 ℃ and carrying out 365 ℃ high-temperature heat treatment to directly obtain the corresponding PMIA colored silk.

Example 5

(1) Preparing a colored spinning solution: 1, 5-diaminoanthraquinone and m-phenylenediamine are mixed according to a molar ratio of 100:0, adding the mixture into a proper amount of N-dimethylacetamide solvent, adding isophthaloyl dichloride with the same amount of total substances of diaminoanthraquinone and m-phenylenediamine into the solution for polymerization for 4 times in 2 hours, neutralizing the solution to pH7.0 by using calcium hydroxide after the reaction is finished, obtaining color (the solute mass concentration is 16.1%) slurry with extra-normal concentration, controlling the polymerization temperature and time at-5 ℃ in the first stage, controlling the polymerization time at 1h, and controlling the polymerization temperature at 20 ℃ in the second stage for 1h.

(2) Mixing the obtained color paste with PMIA unbleached pulp with the same mass concentration according to the following weight percentage of 1:50 mass ratio to obtain PMIA colored spinning solution;

(3) Filtering PMIA colored spinning solution, wherein the filtering pressure is 0.40Mpa, defoaming, and then wet spinning is carried out at the spinning pressure or the pressure of each spinning area of 0.55Mpa, the spinning temperature is 25 ℃ and the spinning feeding rate is 5.5/min, and the spinning process is smooth without hairline and precipitation, thus obtaining the nascent fiber. Wherein the aperture of the spinning jet is 0.06mm, and the precipitation solution is a mixed solution of N-dimethylacetamide, calcium chloride and water (the mass ratio is 45:25:30).

(3) And (3) plasticizing and stretching the nascent fiber, washing with water, drying at 120 ℃ and performing 370 mu high-temperature heat treatment to directly obtain the corresponding PMIA colored silk.

Example 6

(1) Preparing a colored spinning solution: 1, 5-diaminoanthraquinone and m-phenylenediamine are mixed according to the molar ratio of 0.1:99.9, adding the mixture into a proper amount of N-dimethylacetamide solvent, adding isophthaloyl dichloride which has the same amount as the total substances of diaminoanthraquinone and m-phenylenediamine into the solution for polymerization for 4 times within 2 hours, neutralizing the solution to pH7.0 by using calcium hydroxide after the reaction is finished, and obtaining color paste with extra-high concentration (the solute mass concentration is 16.1 percent), wherein the polymerization temperature and time are controlled at 0 ℃ in the first stage, the polymerization time is controlled at 1h, and the polymerization temperature is controlled at 20 ℃ in the second stage, and the polymerization time is controlled at 1h.

(3) Filtering PMIA colored spinning solution, filtering at 0.39Mpa and defoaming, and wet spinning at 25 deg.C and 5.5/min at 0.55Mpa in spinning pressure or spinning area to obtain nascent fiber. Wherein the aperture of the spinning jet is 0.06mm, and the precipitation solution is a mixed solution of N-dimethylacetamide and water (the mass ratio of the N-dimethylacetamide is 60%).

(3) Plasticizing and stretching, washing, drying and high-temperature treatment are carried out on the nascent fiber to directly obtain the corresponding PMIA colored silk; wherein the hot stretching temperature is 280 ℃, and the hot stretching multiple is 2.5 times.

Example 7

The preparation of PMIA colored fibers was the same as in example 1, the only difference being that: the 1, 5-diaminoanthraquinone light-emitting colouring monomer in example 1 was replaced by a molar ratio of 1:1, 5-diaminoanthraquinone, 2, 6-diaminoanthraquinone.

Example 8

The preparation of PMIA colored fibers was the same as in example 1, the only difference being that: the molar ratio of 1, 5-diaminoanthraquinone to m-phenylenediamine is set to be 50:50.

Example 9

(1) Preparing colored color paste: 1, 4-diamino-2, 3-diphenoxyanthraquinone and m-phenylenediamine are mixed according to the mol ratio of 10:46, adding the mixture into a proper amount of N-dimethylacetamide solvent, adding isophthaloyl dichloride the same as the total mass of diaminoanthraquinone and m-phenylenediamine into the solution for polymerization for 4 times in 2 hours, neutralizing the solution to pH7.0 by using calcium hydroxide after the reaction is finished, and obtaining color paste with extra-normal concentration (the mass concentration of solute is 16.1%), wherein the polymerization temperature and time are controlled at-5 ℃ for 1 hour in the first stage, and the polymerization temperature is controlled at 20 ℃ for 1 hour in the second stage.

Example 10

(1) Preparing colored color paste: 1, 4-diamino-2, 3-dichloro anthraquinone and m-phenylenediamine are mixed according to the mol ratio of 10:46, adding the mixture into a proper amount of N-dimethylacetamide solvent, adding isophthaloyl dichloride the same as the total mass of diaminoanthraquinone and m-phenylenediamine into the solution for polymerization for 4 times in 2 hours, neutralizing the solution to pH7.0 by using calcium hydroxide after the reaction is finished, and obtaining color paste with extra-normal concentration (the mass concentration of solute is 16.1%), wherein the polymerization temperature and time are controlled at-5 ℃ for 1 hour in the first stage, and the polymerization temperature is controlled at 20 ℃ for 1 hour in the second stage.

Example 11

(1) Preparing colored color paste: 1, 4-diamino-2-methoxy-9, 10-anthraquinone and m-phenylenediamine are mixed according to the molar ratio of 10:46, adding the mixture into a proper amount of N-dimethylacetamide solvent, adding isophthaloyl dichloride the same as the total mass of diaminoanthraquinone and m-phenylenediamine into the solution for polymerization for 4 times in 2 hours, neutralizing the solution to pH7.0 by using calcium hydroxide after the reaction is finished, and obtaining color paste with extra-normal concentration (the mass concentration of solute is 16.1%), wherein the polymerization temperature and time are controlled at-5 ℃ for 1 hour in the first stage, and the polymerization temperature is controlled at 20 ℃ for 1 hour in the second stage.

Example 12

(1) Preparing colored color paste: 1, 5-dihydroxy-4, 8-diamino-2-chloroanthraquinone and m-phenylenediamine are mixed according to the molar ratio of 10:46, adding the mixture into a proper amount of N-dimethylacetamide solvent, adding isophthaloyl dichloride the same as the total mass of diaminoanthraquinone and m-phenylenediamine into the solution for polymerization for 4 times in 2 hours, neutralizing the solution to pH7.0 by using calcium hydroxide after the reaction is finished, and obtaining color paste with extra-normal concentration (the mass concentration of solute is 16.1%), wherein the polymerization temperature and time are controlled at-5 ℃ for 1 hour in the first stage, and the polymerization temperature is controlled at 20 ℃ for 1 hour in the second stage.

Example 13

(1) Preparing colored color paste: 4- [ (4-nitrophenyl) azo ] benzene-1, 3-diamine and m-phenylenediamine are mixed according to the molar ratio of 10:46, adding the mixture into a proper amount of N-dimethylacetamide solvent, adding isophthaloyl dichloride which has the same amount as the total substances of azo aromatic diamine and m-phenylenediamine into the solution for polymerization for 4 times in 2 hours, neutralizing the mixture with calcium hydroxide to reach pH7.0 after the reaction is finished, and obtaining color paste with extra-normal concentration (the solute mass concentration is 16.1%), wherein the polymerization temperature and time are controlled at-5 ℃ for 1 hour in the first stage, and the polymerization temperature is controlled at 20 ℃ for 1 hour in the second stage.

Comparative example 1

Comparative example 1 discloses a method for preparing PMIA colored fibers, which is different from example 1 in that: when the colored spinning color paste is prepared, the non-dyed PMIA fiber is further prepared without adding a color reaction monomer (namely, the molar ratio of the color reaction monomer to the m-phenylenediamine is 0:100).

Comparative example 2 (inorganic dye dyeing method)

A preparation method of PMIA colored fibers comprises the following steps:

(1) Grinding: adding nano-scale inorganic pigment lead yellow into ball milling and dispersing, wherein the maximum particle diameter after ball milling is lower than 180nm;

(2) Preparing a dyeing solution: 4800ml of dimethylacetamide is put into a ball mill circulation system, the ball mill is started to circulate, 6g of inorganic pigment is added into the ball mill for circulation grinding in three times, and the mass ratio of the inorganic pigment to the N-dimethylacetamide solvent is 1:800, mixing and stirring, adding a dispersing agent, and placing the mixed solution on an ultrasonic oscillator for oscillation to obtain a uniform dyeing solution;

(3) Preparing a spinning solution: 113.50g of m-phenylenediamine is dissolved in 10670ml of N-dimethylacetamide solvent, cooled, 213.10g of m-phthaloyl chloride is added for low-temperature solution polymerization, calcium hydroxide is used for neutralization, and a poly-m-phthaloyl m-phenylenediamine spinning solution is obtained for defoaming, wherein the mass percentage concentration of salt is 8%, and the mass percentage concentration of poly-m-phthaloyl m-phenylenediamine is 20%;

(4) Mixing solution: adding the dyeing solution and the spinning solution into an extruder head for mixing, wherein the mass ratio of the dyeing solution to the spinning solution is 1:650, a step of;

(5) Filtering pressure is 0.80Mpa before spinning, wet spinning, finding out broken filaments and broken finger lines in the spinning process, and then stretching, washing, drying, curling, cutting and packaging to obtain PMIA colored fibers. Wherein wet spinning adopts a coagulating bath to treat into filaments, the coagulating bath is an N-dimethylacetamide solution, the mass percentage concentration of the coagulating bath is 40%, and the temperature is 30 ℃; the stretching temperature was 280℃and the stretching ratio was 2.5 times.

Comparative example 3 (organic dyeing method)

The dye of comparative example 2 was replaced by an equivalent amount of 1, 5-diaminoanthraquinone as compared to the CN202011083100.7 protocol by dyeing PMIA by the method of example 1 of CN202011083100.7, the dyed fiber being a colorless PMIA fiber prepared by comparative example 1, consisting of the following steps:

A. deoiling: adding 8.5g/L sodium hydroxide into PMIA fiber, degreasing for 20min at 95 ℃, washing with water and drying;

B. pretreatment: placing the PMIA fiber treated in the step A in an N-methyl pyrrolidone solvent, wherein the bath ratio is 1:15, soaking for 60min at 60 ℃; then washing for 30min at 80 ℃, and drying in an oven at 80 ℃ for later use;

C. Dyeing: placing the PMIA fibers treated in the step B into a high-temperature dye liquor for dyeing; the formula of the dye liquor comprises the following steps: 3% of 1, 5-diaminoanthraquinone, N-diethyl-3-methylbenzamide with the concentration of 30g/L and sodium chloride with the concentration of 30 g/L; dyeing conditions: ph=3 (acetic acid adjustment), temperature 140 ℃, time 60min, bath ratio 1:15;

D. post-treatment: placing the PMIA fibers treated in the step C in 2g/L soap solution, washing for 30min, dehydrating and drying to obtain dyed PMIA fibers.

Comparative example 4

The PMIA colored fibers were produced by the method disclosed in example 1, wherein the difference from example 1 was that: PMIA colored color paste is produced, and the polymerization temperature in the second stage of the polymerization reaction is controlled at 60 ℃.

Comparative example 5

The PMIA colored fibers were produced by the method disclosed in example 1, wherein the difference from example 1 was that: PMIA colored color paste is produced, and the polymerization temperature in the first stage of the polymerization reaction is controlled at-30 ℃.

Comparative example 6

The PMIA colored fibers were produced by the method disclosed in example 1, wherein the difference from example 1 was that: the PMIA colored spinning solution is produced, and the temperature is controlled at 30 ℃ in the whole polymerization process.

PMIA spinning solutions and PMIA fibers prepared in examples 1 to 8 and comparative examples 1 to 6 were tested, wherein the light fastness grade was the standard of light fastness-sunlight for the GB/T8426-1998 textile color fastness test; the viscosity of the dope was the ratio of the dynamic viscosity of the dope to the dynamic viscosity of the pure solvent at the same temperature, and the results are shown in Table 1:

TABLE 1 data relating to dope and fiber properties

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Conclusion of the test:

as can be seen from table 1, the mass ratio of the color reaction monomer to the first monomer in examples 1 to 13 is in the range of: 0.1 to 100: when the mass ratio of PMIA color paste to PMIA unbleached pulp is in the range of 0 to 99.9 and 1:1 to 30, preparing the viscosity [ eta ] of the spinning solution: 2.00-2.30, the spinning solution has good spinnability, the color of the fiber can be regulated based on different color reaction monomers, and the spinning process has no broken filaments and broken finger lines, compared with the existing inorganic dye dyeing method, the invention obviously improves the phenomena of broken filaments and broken finger lines, and the relative strength and elongation at break performance indexes of the colored fiber prepared by the method of the invention in the embodiment 1 are obviously improved compared with the conventional pigment coloring of the comparative example 2 and the comparative example 3.

As can be seen from table 1, the mass ratio of the color reaction monomer to the first monomer in examples 1 to 13 is in the range of: 0.1 to 100:0 to 99.9, and the mass ratio of PMIA color paste to PMIA unbleached paste is 1:1 to 30, the glass transition temperature of the prepared colored fiber is 260 ℃ to 275 ℃; the dynamic viscosity of the fiber is 29000-45000 centipoise; the relative strength of the fiber is in the range of 4.05cN/dtex to 4.4 cN/dtex; the breaking elongation of the fiber is in the range of 21-32%; the light fastness is 3-5 grade; the washing fastness grade is 4-5. Wherein, different color forming effect is provided by different color forming reaction monomers, and the combination of different color forming reaction monomers can prepare a new color forming effect different from any color forming reaction monomers.

The structures of the 1, 2-diaminoanthraquinone and the 1, 8-diaminoanthraquinone are similar to those of the 1, 4-diaminoanthraquinone, the 1, 5-diaminoanthraquinone and the 2, 6-diaminoanthraquinone, and the experimental data of the monomer used as the color reaction are similar to those of the latter three, so that the experimental data are limited in space and are not described one by one.

As can be seen from comparative examples 1 and 2, the dyeing scheme of the invention has a remarkable improvement in the relative strength and light fastness of the fiber compared with the conventional dyeing with inorganic dye, wherein the relative strength of the fiber is increased from 3.3cN/dtex to 4.18cN/dtex, the elongation at break of the fiber is increased to 21%, and the filtration pressure is reduced from 0.80Mpa to 0.55Mpa before spinning, thereby greatly reducing the filtration energy consumption.

As can be seen from comparative examples 1 and 3, the dyeing scheme of the present invention is significantly improved in both the relative strength and the light fastness grade of the fiber compared with the conventional organic dye dyeing, wherein the relative strength of the fiber is increased from 3.5cN/dtex to 4.18cN/dtex, the light fastness grade is increased from 2-3 to 4, and the washing fastness grade is increased from 3 to 4.

As is clear from comparative examples 1 and 4, the second stage polymerization temperature is higher than 50 ℃, and the molecular weight of the colored fiber is reduced due to the increase of side reactions and the reduction of polymerization degree, so that the spinnability is reduced, the broken fingerline phenomenon occurs, and the relative strength of the fiber and the elongation at break of the fiber are obviously reduced; meanwhile, as is clear from comparative examples 1 and 5, too low a polymerization reaction temperature also affects the final polymerization degree, the relative strength of the fiber is lowered, the polymerization reaction temperature is in the range of-20 to 50 ℃, and the relative strength of the prepared colored fiber and the elongation at break of the fiber are in a good range. Comparative examples 1 and 6 show that the relative strength and elongation at break of the colored fibers prepared in comparative example 6, which was not subjected to the low-temperature polymerization stage at 20℃or less, were significantly deteriorated.

The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.

Claims

1. A method of coloring a polymer, comprising the steps of:

step 1: mixing a color reaction monomer and a first monomer, and then carrying out polymerization reaction on the mixture and a second monomer to prepare poly m-phenylene isophthalamide color paste; wherein, the chromogenic reaction monomer, the first monomer and the second monomer generate an amide bond and are connected with the second monomer through the amide bond;

step 2: mixing the poly m-phenylene isophthalamide color paste prepared in the step 1 with poly m-phenylene isophthalamide unbleached paste to prepare colored spinning solution, and carrying out pre-spinning slurry pretreatment;

2. The method for coloring polymer according to claim 1, wherein the preparation of the polyisophthaloyl metaphenylene diamine color paste in the step 1 comprises the following steps:

3. The method of coloring polymers according to claim 2, wherein the mass ratio of the color-forming reactive monomer to the first monomer in the step 1 is in the range of: 0.1 to 100:0 to 99.9; the mass ratio of the poly m-phenylene isophthalamide color paste to the poly m-phenylene isophthalamide unbleached paste is 1:1-30.

4. The method of coloring a polymer according to claim 2, wherein the color-forming reactive monomer is a compound containing two primary amino groups; preferably, the chromogenic reaction monomer is an aromatic compound containing two primary amino groups; preferably, the color reaction monomer is diaminoanthraquinone or azo-based aromatic diamine.

5. The method according to claim 4, wherein the diaminoanthraquinone is one or more of 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 2, 6-diaminoanthraquinone, 1, 5-diamino-4, 8-dihydroxyanthraquinone, 1, 2-diaminoanthraquinone, 1, 8-diaminoanthraquinone, 1, 4-diamino-2, 3-diphenoxyanthraquinone, 1, 4-diamino-2, 3-dichloroanthraquinone, 1, 4-diamino-2-methoxy-9, 10-anthraquinone, 1, 5-dihydroxy-4, 8-diamino-2-chloroanthraquinone, and/or the azo aromatic diamine is 4- [ (4-nitrophenyl) azo ] benzene-1, 3-diamine.

6. A spin color paste for coloring fibers, characterized in that it is prepared by the method according to any one of claims 1 to 5, comprising a coloring polymer and a polar organic solvent for preparing a spinning solution;

7. The spinning mill base of claim 6, wherein the ratio of the number of structural units of (i) to (ii) is: 0 to 99.9:0.1 to 100.

8. A dope for colored fibers, characterized by being prepared by the method according to any one of claims 1 to 5, comprising a colored polymer and a polar organic solvent;

9. The dope of claim 8, wherein the dope has a viscosity [ η ]:1.60 to 2.50, preferably 2.00 to 2.30.

10. A colored fiber prepared by the polymer coloring method according to any one of claims 1 to 5, said colored fiber comprising two structural units (i) and (ii) randomly distributed: