A polymer coloring method, spinning color paste, spinning liquid and colored fiber

Abstract

The present invention relates to a polymer coloring method, spinning paste, spinning solution and colored fiber, belonging to the field of textile printing and dyeing technology, including: adding a second monomer and a chromogenic reaction monomer and a first monomer twice or multiple times to obtain a paste, when the second monomer addition reaches 50-95%, an acid binding agent is added to remove by-products in the product, and then the second monomer is added to continue the reaction, and when the system completes the reaction, an acid binding agent is also needed to be added to remove the reaction by-products not removed in the system, and a paste is prepared, and the spinning solution is prepared by mixing the paste with the colorless paste to prepare PMIA. The present invention solves the problem that the filtration pressure of the existing dyeing method spinneret is large, the breakage rate is high, the relative strength and elongation at break of the fiber product after dyeing are low, the filtration performance and spinnability of the spinning solution are improved, and the prepared fiber product has good physical properties and low dyeing cost.

Description

Technical Field

[0001] The invention relates to the technical field of textile printing and dyeing, and in particular to a polymer coloring method, spinning color paste, spinning liquid and colored fiber. Background Art

[0002] Poly(m-phenylene isophthalamide), hereinafter referred to as PMIA, has excellent heat resistance. The decomposition temperature of the fiber made from it reaches 500°C, the long-term use temperature is greater than 230°C, the limiting oxygen index is >29, and it has excellent high temperature acid and alkali resistance, electrical insulation and good textile processing performance. It is widely used in protective clothing, high temperature filter materials, electrical industry and composite materials. It is an important strategic material that cannot be lacking in the country's economic development. However, due to the regular molecular structure, high crystallinity and lack of active functional groups on the molecular chain of PMIA fiber, it is difficult for dye or pigment molecules to penetrate into its structure. The polymerized PMIA fiber molecules are difficult to combine with dye or pigment molecules, which makes it difficult to dye itself and the prepared fabrics, making the application of PMIA fiber in the field of high temperature protection a "short board".

[0003] The existing coloring and dyeing method generally mixes pigments or dyes with fiber natural color slurry (polyisophthalamide solution). Pigments are generally inorganic or insoluble organic matter, which exist in the spinning solution fiber in the form of particles, which are easy to block the micropores of the spinneret, resulting in high filtration pressure and high breakage rate, resulting in low relative strength and elongation at break of the colored fiber products. Dyes are generally small organic molecules that are not heat-resistant and are prone to discoloration and fading during high-temperature treatment and use of fiber products.

[0004] In addition, during wet spinning, since polar solvents and water are miscible with dye molecules, dyes are easily dissolved and carried away by solvents and water washing, resulting in a low exhaustion rate, or even failure to dye. In addition, organic small molecule dyeing usually involves placing fibers, yarns or fabrics in a special solution containing dyes and specific chemical materials. Dye molecules are fixed to fibers by physical bonding, such as absorption, diffusion or bonding, at a certain temperature and pressure. The bonding between dye molecules and fibers depends on the physical bonding force between the dye molecules used and the fibers. For example, PMIA fibers are prone to fading or discoloration due to their weak physical bonding force with dye molecules. In addition, dyeing needs to be carried out in a solvent, which consumes a lot of energy and produces a large amount of wastewater and waste residue. Summary of the invention

[0005] In view of the above analysis, the present invention aims to provide a polymer coloring method, spinning paste, spinning liquid and colored fiber, so as to solve the problems of high filtration pressure of the spinneret, high breakage rate, low relative strength and elongation at break and poor light resistance of the dyed fiber products in the existing coloring method, as well as the problem of large amount of wastewater and waste residue generated by printing and dyeing, polluting the environment.

[0006] The purpose of the present invention is mainly achieved through the following technical solutions:

[0007] The invention discloses a polymer coloring method, comprising the following steps:

[0008] Step 1: After mixing the chromogenic monomer and the first monomer, the second monomer is added twice or more times to react to obtain a poly(m-phenylene isophthalamide) colored spinning solution paste, wherein the by-products generated by the reaction are removed before the second and subsequent additions of the second monomer;

[0009] Step 2: Pre-treating the slurry before spinning by mixing the prepared poly(m-phenylene isophthalamide) color paste with the poly(m-phenylene isophthalamide) original color paste to prepare a colored spinning solution;

[0010] Step 3: wet spinning and precipitation of the pretreated poly(m-phenylene isophthalamide) colored spinning solution to obtain primary fibers;

[0011] Step 4: The primary fibers are post-treated to obtain poly(m-phenylene isophthalamide) colored fibers.

[0012] Preferably, the preparation of poly(m-phenylene isophthalamide) color paste in step 1 comprises:

[0013] S101: dissolving the chromogenic reaction monomer and the first monomer in a polar organic solvent;

[0014] S102: adding the second monomer to the mixed system in S101 multiple times, performing multiple prepolymerizations, adding an acid binder to remove by-products in the product when the amount of the second monomer added reaches 50% to 95%, precipitating and separating the reaction product of the acid binder and the prepolymerization by-products, and then adding the second monomer to continue the reaction, and when the system completes the reaction, it is also necessary to add an acid binder to remove the reaction by-products that have not been removed in the system, so as to obtain poly(m-phenylene isophthalamide) color paste.

[0015] Preferably, in step 1, the mass ratio of the chromogenic monomer to the first monomer is in the range of 0.1-100:0-99.9; the mass ratio of the poly(m-phenylene isophthalamide) color paste to the poly(m-phenylene isophthalamide) base paste is in the range of 1:1-30.

[0016] Preferably, the chromophoric reaction monomer is a compound containing two primary amino groups; preferably, the chromophoric reaction monomer is an aromatic compound containing two primary amino groups; preferably, the chromophoric reaction monomer is diaminoanthraquinone or azo aromatic diamine.

[0017] 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-diphenyloxyanthraquinone, 1,4-diamino-2,3-dichloroanthraquinone, 1,4-diamino-2-methoxy-9,10-anthraquinone, and 1,5-dihydroxy-4,8-diamino-2-chloroanthraquinone, and / or the azo aromatic diamine is 4-[(4-nitrophenyl)azo]benzene-1,3-diamine.

[0018] A spinning paste for colored fibers, comprising a colored polymer and a polar organic solvent, for preparing a spinning solution;

[0019] The colored polymer comprises: The two structural units (Ⅰ) and (Ⅱ) are randomly distributed, and Aq contains an anthraquinone functional group or an aromatic azo group.

[0020] Preferably, the quantitative ratio of the two structural units (I) and (II) is: 0-99.9:0.1-100.

[0021] A spinning solution for colored fibers, comprising a colored polymer and a polar organic solvent;

[0022] The colored polymer comprises: The two structural units (Ⅰ) and (Ⅱ) are randomly distributed, and Aq contains an anthraquinone functional group or an aromatic azo group.

[0023] Preferably, the viscosity [η] of the spinning solution is 2.10 to 2.43, preferably 1.8 to 2.50.

[0024] A colored fiber is prepared by the above-mentioned polymer coloring method, wherein the colored fiber comprises randomly distributed two structural units (I) and (II):

[0025]

[0026]

[0027] Wherein, Aq represents an anthraquinone functional group or an aromatic azo group;

[0028] The dynamic viscosity of the colored silk is 26000-50000 / centipoise.

[0029] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0030] (1) The coloring method of the present invention is to introduce dye molecules into the main chain of polymers through certain chemical reactions to copolymerize to form colored polymers, which is different from the coloring mechanism of blending and grafting copolymerization. The coloring reaction monomer is one of the reactants, copolymerizes with other monomers of the fiber to form a polymer main chain, dissolves in the solvent system, and forms a homogeneous solution. Compared with the existing fiber coloring method using granular pigments, the filtration pressure is small, the breakage rate is low, and the relative strength and elongation at break of the dyed fiber are high, which greatly improves the physical properties of the colored fiber products; improves the defects of the prior art that the micropores of the spinneret are easily blocked, the filtration pressure is large, the breakage rate is high, and the relative strength and elongation at break of the dyed fiber products are low; compared with the method of dyeing the fiber after spinning, the coloring unit structure of the present invention is more stable and not easy to be leached, lost or aged, and the dyeing durability and light aging resistance are significantly improved.

[0031] (2) The present invention uses chromogenic monomers and PMIA raw materials to prepare PMIA color paste containing high-concentration chromogenic units. The PMIA color paste is mixed with PMIA base color paste in different proportions to prepare spinning solution, thereby improving the influence of more chromogenic monomers on the overall spinnability of the spinning solution. PMIA colored fibers of different concentrations can be flexibly prepared, thereby improving applicability. At the same time, by synthesizing PMIA color paste, the scale of synthesis reaction and the amount of colored spinning solution synthesis can be reduced, thereby further reducing the PMIA dyeing cost.

[0032] (3) The present invention obtains a rich color system by selecting chromogenic monomers with different reactivities to copolymerize with other monomers of the polymer to be dyed to form a polymer chain; while the co-blending coloring method in the prior art needs to consider the dispersion and uniformity of the pigment and the compatibility of the pigment with the polymer, which limits the range of pigment selection.

[0033] (4) The present invention adopts a process of adding the second monomer twice or more, and before adding the remaining 5-20% of the second monomer, an acid-binding agent is introduced to combine with the product by-products to promote the reaction to proceed in the forward direction; further, an inorganic acid-binding agent is introduced to react with the reaction by-products, and the reaction by-products are removed by precipitation and filtration, thereby avoiding the introduction of new impurities while removing the reaction by-products.

[0034] (5) The polar solvent used in the spinning process of the present invention can be recovered by vacuum distillation and the like, and there is no printing and dyeing waste residue and waste water generated in the dyeing process of the prior art. Compared with the existing spinning method, energy saving and consumption reduction are achieved, and environmental pollution is reduced.

[0035] In the present invention, the above-mentioned technical solutions can also be combined with each other to achieve more preferred combination solutions. Other features and advantages of the present invention will be described in the subsequent description, and some advantages can be obvious from the description or understood by practicing the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The drawings are only for the purpose of illustrating particular embodiments and are not to be considered limiting of the present invention. Like reference symbols denote like components throughout the drawings.

[0037] Figure 1 The present invention is a two-step color paste process flow chart. DETAILED DESCRIPTION

[0038] The preferred embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings, wherein the accompanying drawings constitute a part of the present invention and are used together with the embodiments of the present invention to illustrate the principles of the present invention, but are not used to limit the scope of the present invention.

[0039] In view of the defects that pigments in the prior art exist in the spinning solution fiber in the form of particles, which are easy to block the micropores of the spinneret, resulting in high filtration pressure and high breakage rate, resulting in low relative strength and elongation at break of the colored fiber products, and organic small molecule dyes are not heat-resistant, are easy to change color and fade during high-temperature treatment and use of fiber products, and the amount of printing and dyeing wastewater is large and difficult to treat, the present invention selects a chromogenic reaction monomer with reaction activity as one of the reactants, copolymerizes with other monomers of the fiber to form a polymer main chain, dissolves in a solvent system, and forms a homogeneous solution. On the one hand, it improves the defects of low filtration pressure, low breakage rate, and low relative strength and elongation at break of the dyed fiber in the prior art of pigment dyeing for PMIA dyeing; on the other hand, because the chromogenic reaction monomer participates in polymer chain formation and is dispersed in the resin matrix at the molecular level, compared with organic small molecule dyes for PMIA dyeing, the dispersion is more uniform, the tinting power is stronger, the effect is more stable, and the coloring time is longer.

[0040] A specific embodiment of the present invention discloses a polymer coloring method, comprising the following steps:

[0041] Step 1: After mixing the chromogenic monomer and the first monomer, the second monomer is added twice or more times to react to obtain a poly(m-phenylene isophthalamide) colored spinning solution paste, wherein when the amount of the second monomer added reaches 80-95%, an acid binder is added to remove byproducts in the product, and the reaction product of the acid binder and the prepolymerized byproduct is separated by precipitation, and then the second monomer is added to continue the reaction. When the system completes the reaction, an acid binder is also needed to remove the reaction byproducts that have not been removed in the system;

[0042] Step 2: The PMIA color paste prepared is mixed with the PMIA natural color paste to prepare a colored spinning solution, and the spinning solution is pretreated;

[0043] Step 3: The pretreated PMIA colored spinning solution is wet-spun and precipitated to obtain primary fibers;

[0044] Step 4: The spun fibers are post-treated to obtain PMIA colored fibers.

[0045] It should be noted that the present invention introduces dye molecules into the main chain of the polymer through chemical reaction to copolymerize to form a colored polymer, which is different from the coloring mechanism of blending and grafting copolymerization: the chromogenic reaction monomer is one of the reactants, copolymerizes with other monomers of the synthetic fiber (such as the first monomer or the second monomer) to form a polymer main chain, and is dissolved in the solvent system to form a homogeneous solution.

[0046] Compared with the fiber coloring method in the prior art using granular pigments, the coloring method of the present invention has the characteristics of low filtration pressure, low breakage rate, high relative strength and elongation at break of the dyed fiber, which greatly improves the physical properties of the colored fiber products; it improves the defects of the prior art that the micropores of the spinneret are easily blocked, the filtration pressure is large, the breakage rate is high, and the relative strength and elongation at break of the dyed fiber products are low; at the same time, since the coloring unit is directly involved in the formation of the coloring polymer, the coloring unit structure of the present invention is more stable than dyeing, is not easy to leach or age, and the dyeing durability and light aging resistance are significantly improved.

[0047] It is understandable that the present invention uses chromogenic monomers as reactive monomers for coloring PMIA fibers, connects them to the PMIA polymer main chain during the reaction, prepares spinning paste, and then realizes the PMIA spinning process to directly prepare colored fibers. These fibers can be easily processed into colored yarns, and further made into colored fabrics; or directly prepared into non-woven fabrics, and no dyeing is required during the subsequent use of the fibers. In contrast, if PMIA natural color paste is used for spinning to obtain fibers, and then they are colored after spinning or weaving, it is necessary to add another dyeing process, and the bath liquid used in the dyeing process also needs to be treated before it can be discharged. Compared with the prior art, the present invention does not generate dyeing wastewater, and reduces the discharge of wastewater after water treatment.

[0048] Specifically, the preparation of the poly(m-phenylene isophthalamide) (PMIA) colored spinning solution in step 1 can be carried out by a two-step or multi-step color paste method:

[0049] Specifically, Figure 1As shown, illustratively, the two-step color paste method is to polymerize the color-forming reaction monomer with the first monomer and the second monomer to prepare a spinning color paste, and the spinning color paste and the PMIA natural color paste are further mixed to prepare a spinning solution, wherein the spinning color paste preparation includes: a prepolymerization according to the insufficient amount of the second monomer, separating the impurity products after each prepolymerization to promote the forward reaction, and further adding the second monomer according to the complete reaction stoichiometric ratio or close to the complete reaction stoichiometric ratio and then polymerizing to prepare the PMIA colored spinning solution.

[0050] It should be noted that reaction byproducts are generated during the synthesis of PMIA. When the reaction byproducts accumulate to a certain extent in the system, the forward reaction will be inhibited, affecting the PMIA chain growth and the final PMIA fiber performance. The present invention adopts a prepolymerization-postpolymerization process in which the second monomer is added twice or multiple times. After the prepolymerization, an acid binding agent is added to combine with the reaction byproducts, and the combined product is separated from the solution system to achieve the purpose of promoting the forward reaction.

[0051] Specifically, the acid binding agent includes inorganic acid binding agents and organic acid binding agents.

[0052] Preferably, the acid binding agent is an inorganic acid binding agent.

[0053] Specifically, the inorganic acid-binding agent is one or more of ammonia, calcium hydroxide, calcium oxide, ammonium carbonate and ammonium bicarbonate.

[0054] Specifically, the organic acid-binding agent includes any one of diethylamine and triethylamine.

[0055] It should be noted that inorganic acid binders have obvious advantages over organic acid binders: on the one hand, organic acid binders are soluble in the PMIA synthetic solvent system and are relatively difficult to separate; on the other hand, the reaction of organic acid binders with hydrochloric acid is a reversible reaction, which is unstable at high temperatures and will decompose while being heated and polymerized, making it difficult to achieve a good acid binding effect; in addition, since PMIA itself has good crystallinity, the surface of the fiber is regular and dense after PMIA is precipitated into silk, making it difficult to thoroughly clean the inside, resulting in some organic acid binders remaining inside the PMIA fiber, affecting its performance.

[0056] The difference is that the inorganic acid-binding agent contains ammonia or its decomposition product is ammonia. On the one hand, ammonia and the like are insoluble in the solvent system, and the excess raw materials are heated to produce ammonia or carbon dioxide which can be easily separated by heating and reducing pressure, thereby fully reacting with hydrogen chloride while avoiding excess ammonia residue and the introduction of raw material impurities. On the other hand, ammonia is insoluble in the hydrogen chloride product ammonium chloride and the organic polar solvent system, and can be easily removed by precipitation, thereby avoiding the introduction of new impurities.

[0057] In addition, multiple additions of the second monomer can prevent the second monomer with higher activity from decomposing, reacting with impurities and volatilizing. On the other hand, multiple additions facilitate control of the reaction rate and reduce uneven reaction levels of the polymerization reaction caused by uneven mass transfer.

[0058] Specifically, the first monomer includes an amino group, and the second monomer includes a formyl group.

[0059] Preferably, the first monomer is m-phenylenediamine, and the second monomer is isophthaloyl chloride; isophthaloyl chloride participates in the polymerization process to generate hydrogen chloride reaction byproduct.

[0060] Specifically, the chromophoric reaction monomer is a compound containing two primary amino groups.

[0061] Preferably, the chromophoric reactive monomer is an aromatic compound containing two primary amino groups.

[0062] Preferably, the chromogenic reaction monomer is diaminoanthraquinone or azo aromatic diamine. Preferably, the chromogenic reaction monomer can 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-diphenyloxyanthraquinone, 1,4-diamino-2,3-dichloroanthraquinone, 1,4-diamino-2-methoxy-9,10-anthraquinone, 1,5-dihydroxy-4,8-diamino-2-chloroanthraquinone.

[0063] Specifically, the structural formula of 1,4-diamino-2,3-diphenoxyanthraquinone satisfies:

[0064]

[0065] The structural formula of 1,4-diamino-2,3-dichloroanthraquinone satisfies:

[0066]

[0067] The structural formula of 1,4-diamino-2-methoxy-9,10-anthraquinone satisfies:

[0068]

[0069] The structural formula of 1,5-dihydroxy-4,8-diamino-2-chloroanthraquinone satisfies:

[0070]

[0071] Preferably, the chromogenic monomer may be an azodiamine such as 4-[(4-nitrophenyl)azo]benzene-1,3-diamine.

[0072] Specifically, the structural formula of 4-[(4-nitrophenyl)azo]benzene-1,3-diamine satisfies:

[0073]

[0074] For example, taking diaminoanthraquinone (general formula NH2-Aq-NH2) as the chromogenic monomer, m-phenylenediamine as the first monomer and isophthaloyl chloride as the second monomer, the overall reaction is as follows:

[0075]

[0076] Where n represents the number of polymer constituent units; represents a polymer constituent unit formed by the reaction of the first monomer and the second monomer, (II) represents the polymer component unit formed by the reaction of the color-forming reaction monomer and the second monomer, a represents the number of polymer structural units formed by the reaction of diaminoanthraquinone, na represents the number of polymer structural units formed by the reaction of m-phenylenediamine, and Aq contains anthraquinone functional groups or aromatic azo groups; the two structural units (I) and (II) are randomly distributed in the color paste:

[0077] Specifically, the quantitative ratio of the two structural units (Ⅰ) and (Ⅱ) in the color paste is: 0~99.9:0.1~100.

[0078] Specifically, adding the second monomer twice or more in step 1 comprises the following steps:

[0079] S101: dissolving the chromogenic reaction monomer and the first monomer in a polar organic solvent;

[0080] S102: adding the second monomer to the mixed system in S101 multiple times, performing multiple prepolymerizations, adding an acid binder after the prepolymerization, precipitating and separating the reaction product of the acid binder and the prepolymerization byproduct, and then continuing to add the second monomer and perform postpolymerization to obtain a PMIA color paste.

[0081] Specifically, in step 1, the second monomer is added twice or more times, and the amount of the second monomer added each time satisfies: M1%: M2%: M3%: ...: M n %, among which M n The ratio of the second monomer actually added for the nth time to the total amount of the second monomer satisfies: M n-1 >M n The ratio of the amount of the second monomer added for the first time to the amount of the second monomer added for the second time is: 50-95%:5-50%.

[0082] Preferably, the amount ratio of the second monomer added for the first time to the second monomer added for the second time is: 60-95%:5-40%.

[0083] It can be understood that impurities such as water are inevitably present in the reaction system, which will react with the second monomer to generate carboxyl compounds. Such substances are difficult to participate in polymer chain formation, and part of the second monomer added for the first time is used for impurity consumption; adding a smaller amount of the second monomer again is beneficial to controlling the reaction temperature, reducing the occurrence of side reactions, avoiding interference from side reaction products, and obtaining a chain compound with a larger molecular weight.

[0084] Specifically, the prepolymerization in step S102 is mainly the reaction of the first monomer, the chromogenic monomer and the second monomer to generate a small molecule prepolymer and the random copolymerization of the small molecule prepolymer to generate a long chain prepolymer. Taking the second monomer as isophthaloyl chloride as an example, the main reaction equation of the prepolymer satisfies:

[0085]

[0086] Wherein, R represents the first monomer or the part of the reaction chromogenic unit excluding the amino group; NH2-R-NH2 represents the first monomer or the reaction chromogenic unit; m represents the number of polyisophthaloyl structures in the long-chain prepolymer or the number of the second monomer consumed in the first stage.

[0087] Specifically, in step S102, the post-polymerization is mainly that as the second monomer is continuously added, the second monomer reacts with the first monomer or the chromophoric reaction monomer end group of the prepolymer molecule to achieve long-chain prepolymer connection and long-chain growth; taking the second monomer as isophthaloyl chloride as an example, the main reaction equation of the post-polymerization satisfies:

[0088]

[0089] Where n represents the number of polymer structural units in poly(m-phenylene isophthalamide); p represents the number of second monomers consumed in the second stage to prepare PMIA molecules with n structural units; R p+1 represents the p+1th long-chain prepolymer, and the number of polyisophthaloyl structures in different long-chain prepolymers may be the same or different.

[0090] Preferably, the prepolymerization reaction temperature is -20°C to 20°C, for example, -20°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C. In this range, PMIA molecules have a larger viscosity average molecular weight and better mechanical strength; the reaction time is 0.05h to 1h.

[0091] More preferably, the prepolymerization reaction temperature is -5°C to 20°C.

[0092] Preferably, the post-polymerization reaction temperature is 20°C to 50°C, for example, 25°C, 30°C, 35°C, 40°C, 45°C, or 50°C; and the reaction time is 0.05h to 2h.

[0093] It should be noted that when the prepolymerization temperature is lower than -20°C, the reaction rate is low, which will reduce the efficiency of the entire process; when the postpolymerization temperature is higher than 50°C, the side reactions increase, the linearity of PMIA molecules is destroyed, the molecular weight is lower, the viscosity is lower, the spinnability decreases, and the fiber strength and elongation at break decrease; the postpolymerization temperature is 1 higher than the prepolymerization temperature.

[0094] Specifically, the amount ratio of the chromogenic reaction monomer in the chromogenic reaction monomer and the first monomer ranges from 0.1% to 100%.

[0095] Specifically, the polar organic solvent in step S101 can be any one of N-dimethylacetamide, dimethylformamide (DMF), and N-methylpyrrolidone, which has good solubility for the raw material monomers in the range of -20°C to 60°C and does not react with any raw material monomers.

[0096] Specifically, in step S102, the mass concentration of PMIA in the poly(meta-phenylene isophthalamide) spinning solution is 16.1-23%.

[0097] Regarding the color development effects of color paste, spinning solution and after spinning, it should be explained that, on the one hand, based on the chromogenic monomers in the PMIA colored spinning solution polymer, the corresponding chromogenic monomer color will appear after spinning; on the other hand, by selecting a variety of different color chromogenic monomers for compounding, a mixed color different from any single chromogenic monomer can be produced after spinning.

[0098] Specifically, various types of reactors can be used to obtain the colored spinning solution of poly(metaphenylene isophthalamide) (PMIA), all of which have strong material mixing functions, such as vertical or horizontal kettle reactors, screw reactors, and kneaders; the length-to-diameter ratio of the reactor is mostly greater than 1:1, and it is equipped with a jacket for passing cooling liquid or heating liquid or other forms of heat dissipation equipment or heating devices.

[0099] Specifically, the stirring power of the vertical or horizontal kettle reactor is 3KW / cubic to 50KW / cubic, the stirring speed is 100rpm to 3000rpm, and there are many types of stirring paddles available, such as anchor type, paddle type, frame type, multi-layer paddle type, cross type or their composite structure type stirring paddles.

[0100] Specifically, a screw reactor and various mixing and kneading structural units are used in combination to maintain a rapid tumbling state of the solution during the reaction, achieve good internal and external heat exchange, and realize rapid polymerization while ensuring safety conditions.

[0101] It should be noted that, on the one hand, the radial flow rate brought by stirring is required to meet the requirement that when the second monomer is added, the materials in different radial regions inside the reaction vessel are evenly mixed, that is, radial mass transfer is realized; on the other hand, the axial flow rate brought by stirring can meet the requirement that when the second monomer is added, the materials in different axial regions inside the reaction vessel are evenly mixed, that is, axial mass transfer is realized; in addition, while achieving mixing of various regions, the heat in the internal region of the reaction container is transferred to the heat exchange region with the outside world, and heat is exchanged with the outside world, thereby realizing heat transfer in various regions inside the reactor and stable temperature control.

[0102] Specifically, in order to ensure the spinnability of the spinning solution after the PMIA color paste and the PMIA natural color paste are mixed and the mechanical properties of the fiber after coloring; the amount ratio of the color reaction monomer to the first monomer in step 1 is in the range of: 0.1~100:0~99.9; the mass ratio of the PMIA color paste and the PMIA natural color paste in step 2 is 1:1~30.

[0103] Specifically, the pretreatment of the spinning slurry in step 2 includes: neutralization, filtration and degassing.

[0104] Specifically, the neutralizing agent is selected from: any one of inorganic bases and organic amines.

[0105] Preferably, the inorganic base is one or more of calcium hydroxide, sodium hydroxide, lithium hydroxide, and ammonia water.

[0106] Specifically, the organic amine is one or more of diethylamine and triethylamine.

[0107] Specifically, the filtration pressure is 0.4Mpa to 0.5Mpa.

[0108] Specifically, the filtration uses closed filters such as plate and frame filter presses, candle filter element filters, disc filters, chamber filters and other precision pressure-resistant filters.

[0109] It can be understood that the filtration pressure is related to the spinning solution density, filtration speed and the content of insoluble impurities in the solution. In the prior art, inorganic dyes are insoluble in the spinning solution and are prone to agglomeration during filtration, which increases the filtration pressure and energy consumption of the filtration pump.

[0110] Specifically, the degassing adopts vacuum degassing, and the vacuum degree is 0.1Kpa ~ 20Kpa.

[0111] Specifically, the spinning pressure of the wet spinning in step 3 is set to 0.2MPa 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°C to 40°C, for example, 5°C, 6°C, 8°C, 10°C, 12°C, 14°C, 15 ℃, 18℃, 20℃, 22℃, 24℃, 25℃, 28℃, 30℃, 32℃, 35℃, 38℃, 40℃; the spinning 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.

[0112] Specifically, the hole diameter of the wet spinning spinneret is 0.04 mm to 0.10 mm, for example, 0.04 mm, 0.06 mm, 0.08 mm, or 0.10 mm.

[0113] Specifically, the precipitation solution used in step 3 is a mixture of the above-mentioned polar organic solvent and an aqueous solution of alcohol and / or calcium chloride.

[0114] In the solution composed of PMIA fiber and polar organic solvent, the addition of alcohol or calcium chloride helps to reduce the solubility of PMIA fiber in the mixed solution.

[0115] Specifically, the mass ratio of the polar organic solvent to the aqueous solution of alcohol and / or calcium chloride is in the range of 0.2-0.7:0.3-0.8, within which the spinning precipitate has the highest yield.

[0116] Specifically, the post-processing in step 4 includes: plasticizing and stretching, water washing, drying and high-temperature heat treatment.

[0117] Specifically, the specific method and process conditions of plasticizing and stretching are: the fiber passes through a plurality of rollers with different speeds in sequence, so that the speed of the fiber when leaving the stretching machine is greater than the speed when entering the stretching machine, thereby achieving the stretching effect.

[0118] Specifically, the fibers are immersed in the plasticizing liquid or washed by the plasticizing liquid in two multi-roll machines at different speeds.

[0119] Specifically, the plasticizing liquid is a mixture of polar solvent, inorganic salt and water.

[0120] Preferably, the plasticizing liquid is an aqueous solution of DMAC (dimethylacetamide) and calcium chloride, and the mass ratio satisfies: DMAC: calcium chloride: water = (5-30): (0-20): (70:50).

[0121] It can be understood that the effect of plasticization and stretching is: the fiber is affected by the plasticizing liquid, and the polymer is affected by the solvent, so it swells to a certain extent. Under the action of external force, the polymer can slide against each other to a certain extent, so as to achieve the purpose of stretching the molecules in the fiber along the axial orientation of the fiber.

[0122] Specifically, during the plasticization and stretching process, the fibers absorb the plasticizing liquid, and thus polar solvents, inorganic salts and other substances in the plasticizing liquid remain. The presence of these substances affects the physical and mechanical properties of the fibers. Water washing is used to remove impurities, recover solvents, and reduce material consumption. Specific methods of water washing include: using multi-stage water washing, and washing the fibers by multi-stage countercurrent immersion or elution.

[0123] Specifically, the specific method and process conditions of drying are: drying the fiber bundle by means of multi-stage hot rollers, hot plates or hot cavities, etc. When the fibers pass through the surface of the above-mentioned thermal equipment, the heat is transferred from the machine to the fibers, the temperature of the fiber bundle rises, and the moisture in the fiber bundle evaporates due to the heat, thereby achieving a drying effect; equipment such as hot rollers or hot plates can be heated by means of electric thermal resistors or heat media (such as thermal oil) or steam.

[0124] It is understood that drying can remove residual moisture and polar organic solvents.

[0125] Specifically, the specific method of high-temperature heat treatment in post-processing includes: heating the dried fiber through a high-temperature hot chamber device and stretching it at the same time.

[0126] It can be understood that the effect of high temperature heat treatment is to further orient the polymer in the fiber along the fiber axis, further improve the physical and mechanical properties, and at the same time improve the heat resistance of the fiber after coloring.

[0127] A specific embodiment of the present invention discloses a spinning paste for colored fibers, comprising a colored polymer and a polar organic solvent, and is used for spinning to prepare the colored fibers;

[0128] The colored polymer comprises: The two structural units (Ⅰ) and (Ⅱ) are randomly distributed, and Aq contains an anthraquinone functional group or an aromatic azo group.

[0129] Specifically, the quantitative ratio of the two structural units (Ⅰ) and (Ⅱ) is 80-99.9:0.1-20.

[0130] Specifically, the polar organic solvent may be any one of N-dimethylacetamide, dimethylformamide (DMF), and N-methylpyrrolidone.

[0131] A specific embodiment of the present invention discloses a spinning paste for colored fibers, comprising a colored polymer and a polar organic solvent, and used for spinning to prepare a spinning solution;

[0132] The colored polymer comprises: The two structural units (Ⅰ) and (Ⅱ) are randomly distributed, and Aq contains an anthraquinone functional group or an aromatic azo group.

[0133] Specifically, the quantitative ratio of the two structural units (Ⅰ) and (Ⅱ) is: 0~99.9:0.1~100.

[0134] A specific embodiment of the present invention discloses a spinning solution for colored fibers, including a colored polymer and a polar organic solvent, for spinning to prepare the colored fibers;

[0135] The colored polymer comprises: The two structural units (Ⅰ) and (Ⅱ) are randomly distributed, and Aq contains an anthraquinone functional group or an aromatic azo group.

[0136] Preferably, the PMIA colored polymer mass concentration in the spinning solution is 16.1-23%.

[0137] Preferably, the viscosity [η] of the spinning solution is 2.10 to 2.43, preferably 1.8 to 2.50.

[0138] [η] represents the relative viscosity, which is the ratio of the dynamic viscosity of the spinning solution to the dynamic viscosity of the solvent in the spinning solution.

[0139] Specifically, the polar organic solvent may be any one of N-dimethylacetamide, dimethylformamide (DMF), and N-methylpyrrolidone.

[0140] A specific embodiment of the present invention discloses a colored fiber, wherein the colored fiber comprises randomly distributed two structural units (I) and (II):

[0141]

[0142] Among them, Aq contains an anthraquinone functional group.

[0143] Optionally, the colored fiber is prepared by the above-mentioned polymer coloring method.

[0144] Specifically, a PMIA colored spinning solution is prepared by reacting a chromogenic monomer, a first monomer and a second monomer, and the colored spinning solution is further spun to obtain colored fibers.

[0145] Specifically, the first monomer includes an amino group, and the second monomer includes a formyl group.

[0146] Preferably, the first monomer is m-phenylenediamine and the second monomer is isophthaloyl chloride.

[0147] Specifically, the chromophoric reaction monomer is a compound containing two primary amino groups.

[0148] Preferably, the chromophoric reactive monomer is an aromatic compound containing two primary amino groups.

[0149] Preferably, the chromogenic monomer is 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-diphenyloxyanthraquinone, 1,4-diamino-2,3-dichloroanthraquinone, 1,4-diamino-2-methoxy-9,10-anthraquinone, and 1,5-dihydroxy-4,8-diamino-2-chloroanthraquinone can be selected.

[0150] Preferably, the chromogenic monomer may be an azodiamine such as 4-[(4-nitrophenyl)azo]benzene-1,3-diamine.

[0151] Specifically, the dynamic viscosity of the spinning solution of the fiber is 26000-50000 / centipoise; the glass transition temperature of the colored fiber is 259-276°C; the relative strength of the fiber is 4.2-4.75 cN / dtex; the elongation at break of the fiber is 23%-33%; the color fastness to light is grade 3-5; and the color fastness to washing is grade 4-5.

[0152] In order to better illustrate the present invention, the following embodiments and comparative examples are further provided:

[0153] Example 1

[0154] (1) Preparation of colored paste: 1,5-diaminoanthraquinone and m-phenylenediamine were added to an appropriate amount of N-dimethylacetamide solvent in a molar ratio of 10:46, and isophthaloyl chloride was added twice within 2 hours in an amount equal to the total amount of diaminoanthraquinone and m-phenylenediamine, with the mass ratio of the first time to the second time being 19:1. In the prepolymerization stage, the polymerization reaction temperature and time were controlled at -5°C for 1 hour, and in the postpolymerization stage, the temperature was controlled at 20°C for 1 hour. The solute mass concentration in the paste was 16.1%.

[0155] (2) mixing the obtained color paste with PMIA natural color paste of the same mass concentration at a mass ratio of 1:30 to obtain PMIA colored spinning solution;

[0156] (3) The PMIA colored spinning solution was filtered at a filtration pressure of 0.45 MPa, deaerated, and then wet-spun at a spinning pressure or a pressure in each spinning area of ​​0.55 MPa, a spinning temperature of 20°C, and a spinning feed rate of 6 m / min. The spinning process was smooth and there was basically no hair, and the nascent fiber was precipitated. The aperture of the spinning spinneret was 0.06 mm, and the precipitate was a mixture of N-dimethylacetamide, calcium chloride and water (mass ratio of 45:25:30).

[0157] (4) The spun fibers were subjected to 3-fold plasticization stretching, water washing, 120°C drying, and 370°C high-temperature heat treatment to directly obtain the corresponding PMIA colored fibers.

[0158] Example 2

[0159] (1) 1,4-diaminoanthraquinone and m-phenylenediamine are added to an appropriate amount of N-dimethylacetamide solvent in a molar ratio of 95:5, and isophthaloyl chloride is added in the same amount as the total amount of diaminoanthraquinone and m-phenylenediamine in four times within 2 hours, with the mass ratio of the first, second, third and fourth times being 60:30:8:2. After each reaction, sufficient ammonium carbonate is introduced to remove hydrogen chloride to obtain a color paste of supernormal concentration. In the prepolymerization stage, the polymerization reaction temperature and time are controlled at -5°C for 1 hour, and in the postpolymerization stage, the temperature is controlled at 20°C for 1 hour. The solute mass concentration in the color paste is 23%.

[0160] (2) mixing the obtained color paste with PMIA natural color paste of the same mass concentration in a mass ratio of 1:5 to obtain PMIA colored spinning solution;

[0161] (3) Filter the PMIA colored spinning solution at a filtration pressure of 0.37 MPa, degassing, and then wet spinning at a spinning pressure or a pressure in each spinning area of ​​0.67 MPa, a spinning temperature of 26°C, and a spinning feed rate of 6.5 m / min. After wet spinning, cool at 30°C for 2 minutes to coagulate into filaments. The spinning process is smooth and there is basically no hair, and the nascent fiber is obtained by precipitation. The aperture of the spinning spinneret is 0.04 mm; the coagulation bath is an N-dimethylacetamide solution with a mass percentage concentration of 40% and a temperature of 30°C.

[0162] (4) The spun fibers were plasticized and stretched 2.5 times, washed, dried at 125°C, and heat treated at 370°C to directly obtain the corresponding PMIA colored fibers.

[0163] Example 3

[0164] (1) 2,6-diaminoanthraquinone and m-phenylenediamine were added to an appropriate amount of N-dimethylacetamide solvent in a molar ratio of 0.5:99.5, and isophthaloyl chloride was added in an amount equal to the total amount of diaminoanthraquinone and m-phenylenediamine in six times within 2 hours. The mass ratio of the first, second, third, fourth, fifth and sixth times was 65:15:10:5:3:2. After each reaction, sufficient ammonia was introduced to remove hydrogen chloride to obtain a color paste of supernormal concentration. In the prepolymerization stage, the polymerization reaction temperature and time were controlled at 20°C for 1 hour, and in the postpolymerization stage, the temperature was controlled at 50°C for 1 hour. The solute mass concentration in the color paste was 16.1%.

[0165] (2) mixing the obtained color paste with PMIA natural color paste of the same mass concentration in a mass ratio of 1:1.5 to obtain PMIA colored spinning solution;

[0166] (3) The PMIA colored spinning solution was filtered at a filtration pressure of 0.50 MPa, deaerated, and then wet-spun at a spinning pressure or a spinning pressure of 0.50 MPa in each spinning area, a spinning temperature of 22°C, and a spinning feed rate of 5.6 / min. The spinning process was smooth and there was no hair, and the nascent fiber was obtained by precipitation. The aperture of the spinning spinneret was 0.10 mm, and the precipitate was a mixture of N-dimethylacetamide and water (45:25:30).

[0167] (4) The spun fibers were plasticized and stretched 2.5 times, washed, dried at 120°C, and heat treated at 370°C to directly obtain the corresponding PMIA colored fibers.

[0168] Example 4

[0169] (1) Preparation of colored spinning solution: 1,5-diamino-4,8-dihydroxyanthraquinone and m-phenylenediamine were added to an appropriate amount of N-dimethylacetamide solvent at a molar ratio of 0.5:99.5, and isophthaloyl chloride was added twice within 2 hours in an amount equal to the total amount of diaminoanthraquinone and m-phenylenediamine, with the mass ratio of the first time to the second time being 19:1. After each reaction, sufficient ammonia was introduced to remove hydrogen chloride to obtain a color paste of supernormal concentration. In the prepolymerization stage, the polymerization reaction temperature and time were controlled at -5°C for 1 hour, and in the postpolymerization stage, the temperature was controlled at 20°C for 1 hour. The solute mass concentration in the color paste was 16.1%.

[0170] (2) mixing the obtained color paste with PMIA natural color paste of the same mass concentration in a mass ratio of 1:1 to obtain PMIA colored spinning solution;

[0171] (3) The PMIA colored spinning solution was filtered at a filtration pressure of 0.40 MPa, deaerated, and then wet-spun at a spinning pressure or a pressure in each spinning area of ​​0.55 MPa, a spinning temperature of 20°C, and a spinning feed rate of 5.3 / min. The spinning process was smooth and there was basically no hair, and the nascent fiber was precipitated. The aperture of the spinning spinneret was 0.06 mm, and the precipitate was a mixture of N-dimethylacetamide, calcium chloride and water (mass ratio was 45:25:30).

[0172] (4) The spun fibers were plasticized and stretched 2.5 times, washed, dried at 120°C, and heat treated at 365°C to directly obtain the corresponding PMIA colored fibers.

[0173] Example 5

[0174] (1) Preparation of colored spinning solution: 1,5-diaminoanthraquinone and m-phenylenediamine were added to an appropriate amount of N-dimethylacetamide solvent in a molar ratio of 20:80, and isophthaloyl chloride was added twice within 2 hours in an amount equal to the total amount of diaminoanthraquinone and m-phenylenediamine, with the mass ratio of the first time to the second time being 19:1. After each reaction, sufficient ammonia was introduced to remove hydrogen chloride to obtain a color paste of supernormal concentration. In the prepolymerization stage, the polymerization reaction temperature and time were controlled at -5°C for 1 hour, and in the postpolymerization stage, the temperature was controlled at 20°C for 1 hour. The solute mass concentration in the color paste was 16.1%.

[0175] (2) mixing the obtained color paste with PMIA natural color paste of the same mass concentration at a mass ratio of 1:100 to obtain PMIA colored spinning solution;

[0176] (3) The PMIA colored spinning solution was filtered at a filtration pressure of 0.40 MPa, deaerated, and then wet-spun at a spinning pressure or a pressure in each spinning area of ​​0.55 MPa, a spinning temperature of 25°C, and a spinning feed rate of 5.5 / min. The spinning process was smooth and there was basically no hair, and the nascent fiber was precipitated. The aperture of the spinning spinneret was 0.06 mm, and the precipitate was a mixture of N-dimethylacetamide, calcium chloride and water (mass ratio was 45:25:30).

[0177] (4) The spun fibers were subjected to 3 plasticizing stretching, water washing, drying at 120°C, and high-temperature heat treatment at 370°C to directly obtain the corresponding PMIA colored fibers.

[0178] Example 6

[0179] (1) Preparation of colored spinning solution: 1,5-diaminoanthraquinone and m-phenylenediamine were added to an appropriate amount of N-dimethylacetamide solvent at a molar ratio of 0.1:99.9, and isophthaloyl chloride was added twice within 2 hours in an amount equal to the total amount of diaminoanthraquinone and m-phenylenediamine, with the mass ratio of the first time to the second time being 19:1. After each reaction, sufficient ammonia was introduced to remove hydrogen chloride to obtain a color paste of supernormal concentration. In the first stage, the polymerization reaction temperature and time were controlled at -20°C for 1 hour, and in the second stage, the temperature was controlled at 20°C for 1 hour. The solute mass concentration in the color paste was 16.1%.

[0180] (2) mixing the obtained color paste with PMIA natural color paste of the same mass concentration in a mass ratio of 1:1 to obtain PMIA colored spinning solution;

[0181] (3) The PMIA colored spinning solution was filtered at a filtration pressure of 0.39 MPa, deaerated, and then wet-spun at a spinning pressure or a pressure in each spinning area of ​​0.55 MPa, a spinning temperature of 25°C, and a spinning feed rate of 5.5 / min. The spinning process was smooth with basically no hair or precipitation, and the primary fiber was obtained. The aperture of the spinning spinneret was 0.06 mm, and the precipitate was a mixture of N-dimethylacetamide and water (mass ratio of 45:25:30).

[0182] (4) The spun fibers are plasticized, stretched, washed, dried and subjected to high-temperature heat treatment to directly obtain the corresponding PMIA colored fibers; wherein the heat stretching temperature is 280° C. and the heat stretching multiple is 2.5 times.

[0183] Example 7

[0184] The preparation method of PMIA colored fiber is the same as that in Example 1, the only difference is that the 1,5-diaminoanthraquinone luminescent coloring monomer in Example 1 is replaced by 1,5-diaminoanthraquinone and 2,6-diaminoanthraquinone in a molar ratio of 1:1.

[0185] Example 8

[0186] The preparation method of PMIA colored fiber is the same as that of Example 1, except that the molar ratio of 1,5-diaminoanthraquinone to m-phenylenediamine is set to 50:50.

[0187] Example 9

[0188] (1) Preparation of colored paste: 1,4-diamino-2,3-diphenoxyanthraquinone and m-phenylenediamine in a molar ratio of 10:46, a total of 176.406 g, are added to an appropriate amount of N-dimethylacetamide solvent, and isophthaloyl chloride in an amount equal to the total amount of diaminoanthraquinone and m-phenylenediamine is added twice within 2 hours, with the mass ratio of the first to the second being 19:1. In the prepolymerization stage, the polymerization reaction temperature and time are controlled at -5°C for 1 hour, and in the post-polymerization stage, the temperature is controlled at 20°C for 1 hour. The solute mass concentration in the paste is 16.1%.

[0189] (2) mixing the obtained color paste with PMIA natural color paste of the same mass concentration at a mass ratio of 1:30 to obtain PMIA colored spinning solution;

[0190] (3) The PMIA colored spinning solution was filtered at a filtration pressure of 0.45 MPa, deaerated, and then wet-spun at a spinning pressure or a pressure in each spinning area of ​​0.55 MPa, a spinning temperature of 20°C, and a spinning feed rate of 6 m / min. The spinning process was smooth and there was basically no hair, and the nascent fiber was precipitated. The aperture of the spinning spinneret was 0.06 mm, and the precipitate was a mixture of N-dimethylacetamide, calcium chloride and water (mass ratio of 45:25:30).

[0191] (4) The spun fibers were subjected to 3-fold plasticization stretching, water washing, 120°C drying, and 370°C high-temperature heat treatment to directly obtain the corresponding PMIA colored fibers.

[0192] Example 10

[0193] (1) Preparation of colored paste: 1,4-diamino-2,3-dichloroanthraquinone and m-phenylenediamine in a molar ratio of 10:46, a total of 176.406 g, are added to an appropriate amount of N-dimethylacetamide solvent, and isophthaloyl chloride in an amount equal to the total amount of diaminoanthraquinone and m-phenylenediamine is added twice within 2 hours, with the mass ratio of the first to the second being 19:1. In the prepolymerization stage, the polymerization reaction temperature and time are controlled at -5°C for 1 hour, and in the post-polymerization stage, the temperature is controlled at 20°C for 1 hour. The solute mass concentration in the paste is 16.1%.

[0194] (2) mixing the obtained color paste with PMIA natural color paste of the same mass concentration at a mass ratio of 1:30 to obtain PMIA colored spinning solution;

[0195] (3) The PMIA colored spinning solution was filtered at a filtration pressure of 0.45 MPa, deaerated, and then wet-spun at a spinning pressure or a pressure in each spinning area of ​​0.55 MPa, a spinning temperature of 20°C, and a spinning feed rate of 6 m / min. The spinning process was smooth and there was basically no hair, and the nascent fiber was precipitated. The aperture of the spinning spinneret was 0.06 mm, and the precipitate was a mixture of N-dimethylacetamide, calcium chloride and water (mass ratio of 45:25:30).

[0196] (4) The spun fibers were subjected to 3-fold plasticization stretching, water washing, 120°C drying, and 370°C high-temperature heat treatment to directly obtain the corresponding PMIA colored fibers.

[0197] Embodiment 11

[0198] (1) Preparation of colored paste: 1,4-diamino-2-methoxy-9,10-anthraquinone and m-phenylenediamine in a molar ratio of 10:46, a total of 176.406 g, are added to an appropriate amount of N-dimethylacetamide solvent, and isophthaloyl chloride in an amount equal to the total amount of diaminoanthraquinone and m-phenylenediamine is added twice within 2 hours, with the mass ratio of the first to the second being 19:1. In the prepolymerization stage, the polymerization reaction temperature and time are controlled at -5°C for 1 hour, and in the post-polymerization stage, the temperature is controlled at 20°C for 1 hour. The solute mass concentration in the paste is 16.1%.

[0199] (2) mixing the obtained color paste with PMIA natural color paste of the same mass concentration at a mass ratio of 1:30 to obtain PMIA colored spinning solution;

[0200] (3) The PMIA colored spinning solution was filtered at a filtration pressure of 0.45 MPa, deaerated, and then wet-spun at a spinning pressure or a pressure in each spinning area of ​​0.55 MPa, a spinning temperature of 20°C, and a spinning feed rate of 6 m / min. The spinning process was smooth and there was basically no hair, and the nascent fiber was precipitated. The aperture of the spinning spinneret was 0.06 mm, and the precipitate was a mixture of N-dimethylacetamide, calcium chloride and water (mass ratio of 45:25:30).

[0201] (4) The spun fibers were subjected to 3-fold plasticization stretching, water washing, 120°C drying, and 370°C high-temperature heat treatment to directly obtain the corresponding PMIA colored fibers.

[0202] Example 12

[0203] (1) Preparation of colored paste: 1,5-dihydroxy-4,8-diamino-2-chloroanthraquinone and m-phenylenediamine in a molar ratio of 10:46, a total of 176.406 g, are added to an appropriate amount of N-dimethylacetamide solvent, and isophthaloyl chloride in an amount equal to the total amount of diaminoanthraquinone and m-phenylenediamine is added twice within 2 hours, with the mass ratio of the first to the second being 19:1. In the prepolymerization stage, the polymerization reaction temperature and time are controlled at -5°C for 1 hour, and in the post-polymerization stage, the temperature is controlled at 20°C for 1 hour. The solute mass concentration in the paste is 16.1%.

[0204] (2) mixing the obtained color paste with PMIA natural color paste of the same mass concentration at a mass ratio of 1:30 to obtain PMIA colored spinning solution;

[0205] (3) The PMIA colored spinning solution was filtered at a filtration pressure of 0.45 MPa, deaerated, and then wet-spun at a spinning pressure or a pressure in each spinning area of ​​0.55 MPa, a spinning temperature of 20°C, and a spinning feed rate of 6 m / min. The spinning process was smooth and there was basically no hair, and the nascent fiber was precipitated. The aperture of the spinning spinneret was 0.06 mm, and the precipitate was a mixture of N-dimethylacetamide, calcium chloride and water (mass ratio of 45:25:30).

[0206] (4) The spun fibers were subjected to 3-fold plasticization stretching, water washing, 120°C drying, and 370°C high-temperature heat treatment to directly obtain the corresponding PMIA colored fibers.

[0207] Embodiment 13

[0208] (1) Preparation of colored paste: 4-[(4-nitrophenyl)azo]benzene-1,3-diamine and m-phenylenediamine in a molar ratio of 10:46, a total of 176.406 g, are added to an appropriate amount of N-dimethylacetamide solvent, and isophthaloyl chloride in an amount equal to the total amount of diaminoanthraquinone and m-phenylenediamine is added twice within 2 hours, with the mass ratio of the first to the second being 19:1. In the prepolymerization stage, the polymerization reaction temperature and time are controlled at -5°C for 1 hour, and in the post-polymerization stage, the temperature is controlled at 20°C for 1 hour. The solute mass concentration in the paste is 16.1%.

[0209] (2) mixing the obtained color paste with PMIA natural color paste of the same mass concentration at a mass ratio of 1:30 to obtain PMIA colored spinning solution;

[0210] (3) The PMIA colored spinning solution was filtered at a filtration pressure of 0.45 MPa, deaerated, and then wet-spun at a spinning pressure or a pressure in each spinning area of ​​0.55 MPa, a spinning temperature of 20°C, and a spinning feed rate of 6 m / min. The spinning process was smooth and there was basically no hair, and the nascent fiber was precipitated. The aperture of the spinning spinneret was 0.06 mm, and the precipitate was a mixture of N-dimethylacetamide, calcium chloride and water (mass ratio of 45:25:30).

[0211] (4) The spun fibers were subjected to 3-fold plasticization stretching, water washing, 120°C drying, and 370°C high-temperature heat treatment to directly obtain the corresponding PMIA colored fibers.

[0212] Embodiment 14

[0213] The difference from the embodiment is that isophthaloyl chloride having the same amount as the total amount of diaminoanthraquinone and meta-phenylenediamine is added twice within 2 hours, and the mass ratio of the first time to the second time is 50:50.

[0214] Comparative Example 1

[0215] Comparative Example 1 discloses a method for preparing PMIA colored fibers, which differs from Example 1 in that when preparing the colored color paste, no color-forming reaction monomer is added (i.e., the color-forming reaction monomer and meta-phenylenediamine are in a molar ratio of 0:100), and undyed PMIA fibers are further prepared.

[0216] Comparative Example 2 (Inorganic Dye Dyeing Method)

[0217] A method for preparing PMIA colored fiber, comprising the following steps:

[0218] (1) Grinding: Add the nano-scale inorganic pigment lead yellow into a ball mill for dispersion, and the maximum particle diameter after ball milling is less than 180 nm;

[0219] (2) preparing a dyeing solution: placing 4800 ml of dimethylacetamide in a ball mill circulation system, starting the circulation, adding 6 g of inorganic pigment into the circulation grinding three times, mixing the inorganic pigment and N-dimethylacetamide solvent at a mass ratio of 1:800, adding a dispersant, and placing the mixed solution on an ultrasonic oscillator to oscillate to obtain a uniform dyeing solution;

[0220] (3) preparing a spinning solution: dissolving 113.50 g of m-phenylenediamine in 10670 ml of N-dimethylacetamide solvent, cooling, adding 213.10 g of isophthaloyl chloride to carry out low-temperature solution polymerization, neutralizing with calcium hydroxide to obtain a poly(m-phenylene isophthalamide) spinning solution, and degassing, wherein the mass percentage concentration of salt is 8% and the mass percentage concentration of poly(m-phenylene isophthalamide) is 20%;

[0221] (4) Mixed solution: The dyeing solution and the spinning solution are added to the extruder head and mixed, and the mass ratio of the dyeing solution to the spinning solution is 1:650;

[0222] (5) The pre-spinning filtration pressure is 0.80 MPa, and the wet spinning process finds hairy fibers and broken finger lines, and then stretches, washes, dries, curls, cuts and packages to obtain PMIA colored fibers. The wet spinning process uses a coagulation bath to process the fibers, and the coagulation bath is an N-dimethylacetamide solution with a mass percentage concentration of 40% and a temperature of 30°C; the stretching temperature is 280°C, and the stretching multiple is 2.5 times.

[0223] Comparative Example 3 (Organic Dyeing Method)

[0224] PMIA was colored by referring to the method of Example 1 of CN202011083100.7. Compared with the scheme of CN202011083100.7, the dye of Comparative Example 2 was replaced with an equal amount of 1,5-diaminoanthraquinone, and the dyed fiber was the colorless PMIA fiber prepared in Comparative Example 1, which was composed of the following steps:

[0225] A. Degreasing: Add 8.5 g / L of sodium hydroxide to PMIA fiber, degrease for 20 min at 95°C, then wash and dry;

[0226] B. Pretreatment: The PMIA fiber treated in step A is placed in N-methylpyrrolidone solvent with a bath ratio of 1:15 and soaked at 60°C for 60 minutes; then, washed with water at 80°C for 30 minutes, dried in an oven at 80°C for standby use;

[0227] C. Dyeing: The PMIA fiber treated in step B is placed in a high-temperature dye solution for dyeing; the dye solution formula: 3% by mass of 1,5-diaminoanthraquinone, 30 g / L of N,N-diethyl-3-methylbenzamide, and 30 g / L of sodium chloride; dyeing conditions: pH value = 3 (adjusted by acetic acid), temperature 140°C, time 60 min, bath ratio 1:15;

[0228] D. Post-treatment: The PMIA fiber treated in step C is placed in a 2 g / L soap solution, cleaned for 30 min, washed with water for 30 min, dehydrated, and dried to obtain the dyed PMIA fiber.

[0229] Comparative Example 4

[0230] The PMIA colored fiber was prepared by the method disclosed in Example 1, wherein the difference from Example 1 is that the PMIA colored paste is generated and the polymerization temperature is controlled at 60°C.

[0231] Comparative Example 5

[0232] PMIA colored fiber was prepared by the method disclosed in Example 1, wherein the difference from Example 1 is that PMIA colored color paste was generated and the polymerization temperature was controlled at -30°C.

[0233] Comparative Example 6

[0234] PMIA colored fibers were prepared by the method disclosed in Example 1, wherein the difference from Example 1 is that PMIA colored spinning solution was generated and the temperature of the entire polymerization reaction was controlled at 30°C.

[0235] Comparative Example 7

[0236] PMIA colored fibers were prepared by the method disclosed in Example 1, wherein the difference from Example 1 was that no acid-binding agent was used to treat the by-products after prepolymerization when preparing the spinning slurry.

[0237] Comparative Example 8

[0238] PMIA colored fibers were prepared by the method disclosed in Example 1, wherein the difference from Example 1 was that when generating PMIA colored spinning slurry, the acid binding agent was replaced by an equal amount of diethylamine.

[0239] The PMIA spinning solutions and PMIA fibers prepared in Examples 1-13 and Comparative Examples 1-8 were tested, wherein the color fastness to light grade was determined using the standard of GB / T 8426-1998 Textiles - Tests for color fastness to light - Daylight; the viscosity of the spinning solution was determined using the relative viscosity [η]: the ratio of the dynamic viscosity of the spinning solution to the dynamic viscosity of the pure solvent at the same temperature. The results are shown in Table 1:

[0240] Table 1 Data related to spinning solution and fiber properties

[0241]

[0242]

[0243]

[0244] Test conclusion:

[0245] As can be seen from Table 1, in Examples 1 to 14, when the molar ratio of the chromogenic reaction monomer to the first monomer is in the range of 0.1 to 100:0 to 99.9 and the mass ratio of PMIA color paste to PMIA natural color paste is in the range of 1:1 to 30, the viscosity [η] of the prepared spinning solution is 2.1 to 2.43, the spinning solution has good spinnability, and the fiber color can be adjusted based on the different chromogenic reaction monomers, and there is no fuzzy fibers or broken lines in the spinning process. The present invention significantly improves the fuzzy fibers and broken lines phenomenon compared with the existing inorganic dye dyeing method. The relative strength and elongation at break performance indicators of the colored fiber prepared by the method of the present invention in Example 1 are significantly improved over the conventional pigment coloring in Comparative Examples 2 and 3.

[0246] As can be seen from Table 1, in Examples 1 to 14, when the mass ratio of the chromogenic reaction monomer to the first monomer is in the range of 0.1 to 100: 0 to 99.9 and the mass ratio of the PMIA color paste to the PMIA natural color paste is in the range of 1:1 to 30, the glass transition temperature of the prepared colored fiber is in the range of 259°C-276°C; the dynamic viscosity of the fiber is 26,000 centipoise to 50,000 centipoise; the relative strength of the fiber is in the range of 4.2 cN / dtex to 4.75 cN / dtex; the elongation at break of the fiber is in the range of 23% to 33%; the color fastness to light is 3 to 5 levels; the color fastness to washing is 4 to 5 levels. Among them, different chromogenic reaction monomers have different coloring effects, and different combinations of chromogenic reaction monomers can prepare new coloring effects different from any chromogenic reaction monomers.

[0247] The structures of 1,2-diaminoanthraquinone and 1,8-diaminoanthraquinone are similar to those of 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone and 2,6-diaminoanthraquinone. The experimental data of their use as chromogenic reaction monomers are similar to those of the latter three. Due to space limitations, they are not described one by one.

[0248] By comparing Example 1 and Comparative Example 2, it can be seen that the coloring scheme of the present invention has significantly improved the relative strength and light fastness grade of the fiber compared with ordinary inorganic dye dyeing, wherein the relative strength of the fiber is increased from 3.3 cN / dtex to 4.35 cN / dtex, the elongation at break of the fiber is increased from 15% to 24%, and the pre-spinning filtration pressure is reduced from 0.80 MPa to 0.55 MPa, which greatly reduces the filtration energy consumption.

[0249] By comparing Example 1 and Comparative Example 3, it can be seen that the coloring scheme of the present invention has significantly improved the relative strength and light fastness grade of the fiber compared with ordinary organic dye dyeing, wherein the relative strength of the fiber is increased from 3.5 cN / dtex to 4.35 cN / dtex, the light fastness grade is increased from level 2-3 to level 4, and the water washing color fastness grade is increased from level 3 to level 4.

[0250] Comparing Example 1 and Comparative Example 4, it can be seen that the polymerization temperature in the second stage is higher than 50°C. Due to the increase of side reactions and the decrease of polymerization degree, the molecular weight of the colored fiber decreases, resulting in a decrease in spinnability, the phenomenon of broken finger lines, and the relative strength of the fiber and the elongation at break of the fiber are significantly reduced; at the same time, comparing Example 1 and Comparative Example 5, it can be seen that if the polymerization temperature is too low, it will also affect the final polymerization degree, and the relative strength of the fiber will decrease. When the polymerization temperature is in the range of -20°C to 50°C, the relative strength of the prepared colored fiber and the elongation at break of the fiber are in a good range. Comparing Example 1 and Comparative Example 6, it can be seen that the relative strength and elongation at break of the colored fiber prepared in Comparative Example 6, which did not undergo a low-temperature polymerization stage at a temperature less than or equal to 20°C, are significantly deteriorated.

[0251] By comparing Example 1 with Comparative Example 7, it can be seen that the coloring scheme of the present invention without using an acid-binding agent significantly improves the relative strength and elongation at break of the fiber.

[0252] By comparing Example 1 with Comparative Example 8, it can be seen that the fiber prepared using the inorganic acid binding agent has better relative strength and elongation at break.

[0253] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by any technician familiar with the technical field within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention.

Claims

1. A method for preparing polymer colored silk, characterized in that: The following steps are involved: Step 1: Mixing a chromogenic monomer, a first monomer and a polar solvent, adding a second monomer twice or more to react to obtain a poly(m-phenylene isophthalamide) color paste, wherein the by-products generated by the reaction are removed before the second and subsequent additions of the second monomer; the molar ratio of the chromogenic monomer to the first monomer in step 1 is in the range of 10:46 to 100:0; the first monomer is m-phenylene diamine, and the second monomer is isophthaloyl chloride; the preparation of the poly(m-phenylene isophthalamide) color paste in step 1 includes: S101: dissolving the chromogenic reaction monomer and the first monomer in a polar organic solvent to obtain a mixed system; S102: adding the second monomer to the mixed system obtained in S101 for multiple times, performing multiple prepolymerizations, adding an acid binding agent to remove byproducts in the product when the amount of the second monomer added reaches 50% to 95%, and then adding the second monomer to continue the reaction, and when the system completes the reaction, an acid binding agent is also needed to remove the reaction byproducts that have not been removed in the system, to obtain poly(m-phenylene isophthalamide) color paste; The acid binding agent is one or more of ammonia, calcium hydroxide, calcium oxide, ammonium carbonate and ammonium bicarbonate; In step 1, the second monomer is added twice or more times, and the amount of the second monomer added each time satisfies: M1%: M2%: M3%: ...: M n %, among which M n The ratio of the second monomer actually added for the nth time to the total amount of the second monomer satisfies: M n-1 >M n ; The poly(m-phenylene isophthalamide) color paste prepared in step 1 includes a coloring polymer; The colored polymer comprises: and The two structural units (Ⅰ) and (Ⅱ) are randomly distributed, and Aq contains anthraquinone functional groups or aromatic azo groups; the quantitative ratio of the two structural units (Ⅰ) and (Ⅱ) is 10:46 to 100:0; Step 2: Mixing the poly(metaphenylene isophthalamide) color paste prepared in step 1 with the poly(metaphenylene isophthalamide) natural color paste to prepare a colored spinning solution, and performing pre-spinning solution pretreatment; the mass ratio of the poly(metaphenylene isophthalamide) color paste to the poly(metaphenylene isophthalamide) natural color paste is 1:1 to 30; Step 3: wet spinning and precipitation of the pretreated poly(m-phenylene isophthalamide) colored spinning solution to obtain primary fibers; Step 4: post-treating the raw fiber to obtain poly(m-phenylene isophthalamide) colored yarn; The relative strength of the fiber is in the range of 4.2cN / dtex to 4.75cN / dtex; the elongation at break of the fiber is 23% to 33%; the color fastness to light is 4 to 5; the color fastness to washing is 4 to 5; The chromogenic reaction monomer is diaminoanthraquinone or an azo aromatic diamine; 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-diphenyloxyanthraquinone, 1,4-diamino-2,3-dichloroanthraquinone, 1,4-diamino-2-methoxy-9,10-anthraquinone, and / or the azo aromatic diamine is 4-[(4-nitrophenyl)azo]benzene-1,3-diamine.

2. A spinning paste for colored silk, characterized in that: Prepared by step 1 in the method of claim 1, the spinning paste comprises a colored polymer and a polar organic solvent, and is used to prepare a spinning solution; The colored polymer comprises: and The two structural units (Ⅰ) and (Ⅱ) are randomly distributed, and Aq contains an anthraquinone functional group or an aromatic azo group.

3. The spinning paste according to claim 2, characterized in that: The quantitative ratio of the two structural units (Ⅰ) and (Ⅱ) is 10:46 to 100:

0.

4. A colored spinning solution for colored silk, characterized in that: Prepared by the steps 1 and 2 in the method of claim 1, the colored spinning solution comprises a colored polymer and a polar organic solvent; The colored polymer comprises: and The two structural units (Ⅰ) and (Ⅱ) are randomly distributed, and Aq contains an anthraquinone functional group or an aromatic azo group.

5. The spinning solution according to claim 4, characterized in that The viscosity [η] of the colored spinning solution is 1.8 to 2.

50.

6. The spinning solution according to claim 5, characterized in that The viscosity [η] of the colored spinning solution is 2.10 to 2.43.

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