CN115873385B - Preparation method and application of black master batch for polyester bottle material regenerated spinning - Google Patents
Preparation method and application of black master batch for polyester bottle material regenerated spinning Download PDFInfo
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- CN115873385B CN115873385B CN202310076179.8A CN202310076179A CN115873385B CN 115873385 B CN115873385 B CN 115873385B CN 202310076179 A CN202310076179 A CN 202310076179A CN 115873385 B CN115873385 B CN 115873385B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a preparation method and application of a black master batch for polyester bottle material regeneration spinning, which comprises the steps of blending and granulating carbon black and an ionic polymer according to a certain proportion to prepare a homogeneously dispersed black master batch; the mass fraction of the carbon black in the black master batch is 30-60%; the ionic polymer is prepared by esterifying dibasic acid containing sulfonate and dihydric alcohol containing sulfonate and then carrying out chain extension and viscosity increase; the application is as follows: and adding the black master batch for the polyester bottle material regeneration spinning into a polyester bottle material melt for spinning according to the mass fraction of 2-10% to obtain the black polyester fiber. The invention plays a role in plasticizing and promoting flow of the high-viscosity polyester bottle material in the blending process, reduces the viscosity drop of the high-viscosity polyester bottle material under the high-temperature processing condition, and is beneficial to improving the mechanical property of spun fibers; the strong binding force of ion pairs and ion clusters in the black master batch improves the adhesiveness of the melt in the fiber surface layer to the pigment, and the melt is not easy to fall off under the action forces of water washing, friction and the like.
Description
Technical Field
The invention belongs to the technical field of polyester fibers, and relates to a preparation method and application of black master batch for polyester bottle material regenerated spinning.
Background
The chemical fiber material is a basic raw material in the textile industry and has important functions. Technological innovation of fiber materials greatly promotes transformation upgrading and high-quality development of textile industry. Wherein the polyester fiber is the first large variety of fiber and has wide application. Polyester fiber materials are continuously developed towards differentiation and functionalization on one hand, and sustainable development on the other hand. Upstream raw materials for spinning polyester fiber materials are polymerized by petroleum-based chemical raw materials, and in recent years, biological fermentation technology continuously innovates on bio-based monomers to give new raw material sources. In addition, an important resource is waste polyester resources such as waste polyester fibers, polyester films, polyester bottles, etc. The waste polyester bottle materials have relatively higher quality compared with other resources, are favored by regeneration spinning enterprises, and are applied to a plurality of terminal brands. The regenerated polyester fiber prepared by melt spinning of waste polyester bottle materials is a high-value-added embodiment of recycling.
With the continuous development of downstream application of the regenerated polyester fiber, more requirements are put on the regeneration spinning of waste polyester bottle materials and the development of fiber products. Wherein the requirement on the color of the fiber regenerated and spun by the waste polyester bottle material becomes a basic requirement. The raw liquid coloring technology becomes the main technology in the field of regeneration spinning by virtue of the advantages of green, environment-friendly, low carbon and the like. The core in the development of the regenerated stock solution colored fiber of the waste polyester bottle material is color master batch for satisfying the spinning of the polyester bottle material.
Chinese patent No. 102964782A is a low-melting polyester masterbatch and a preparation method thereof, and relates to the preparation of a masterbatch suitable for low-melting polyester colored fibers. The incorporation of polyamide wax into the low melting polyester promotes dispersion of the pigment. Chinese patent No. 103556295A discloses a black polyester fiber and a preparation method thereof, wherein black polyester master batch is prepared by blending semi-dull polyester chips, black master batch and a brightening agent. CN103012902B is a carbon black master batch and a preparation method thereof, the carbon black master batch comprises: 100 parts by weight of a polyethylene resin; 50-150 parts by weight of carbon black; 0.1-14 parts by weight of amphiphilic comb type polymer compatibilizer; 0-10 parts by weight of a fluorocarbon polymer; the blue phase black master batch for the polyamide 6 fiber comprises 57.4-69.6wt% of polyamide 6 slices, 25-35 wt% of nanoscale carbon black powder, 5-7wt% of composite carbon black hyperdispersant powder and 0.4-0.6wt% of polyamide wax micropowder. The production period of the spinning component in the spinning process is 15-22 days. The particles with micro-nano size including carbon black are easy to generate secondary agglomeration and the like when being added into spinning melt due to the high specific surface area in the preparation of color master batches, so that the spinnability is reduced, the replacement period of a spinning component is shortened, and the processing continuity and stability are affected. Therefore, in addition to polymer carrier, certain dispersant must be introduced to coat carbon black in the preparation of master batch, so as to reduce agglomeration among particles and improve spinnability and fiber performance. However, the introduced dispersant is only a small amount, the dispersion regulation and control of particles such as carbon black is limited, the property difference between the dispersant and the polymer carrier of the master batch is large, and the dispersant is easy to be separated out from the master batch when the addition amount of the dispersant is higher, so that the processability is influenced.
In addition, the development of recycled polyester fibers has been in a trend, and recycling of waste polyester such as bottles is an important direction for recycling resources. Compared with common fiber-grade spinning polyester, the polyester bottle material has larger melt viscosity after melting and contains a certain amount of trisonomer (the intrinsic viscosity is 0.75-0.90 dl/g, and the mass fraction of isophthalic acid in the polyester bottle material is 0.2-2.5%). The existing fiber-grade polyester black master batch is difficult to realize a homogeneous mixing process in a high-viscosity polyester bottle material melt, and carbon black and the like are also extremely easy to agglomerate secondarily, so that spinnability and coloring effect are greatly influenced. The Chinese patent No. 106426618B discloses a preparation method of bottle flake color master batch, which is characterized in that nano-level toner and polyester bottle flakes are subjected to melt blending and multi-channel filtration, so that impurities are effectively removed, and the problem of color difference caused by the difference between the polyester bottle flakes and chemical fiber color master batch in the prior art is avoided. It can be seen that the prior art does not specifically combine the characteristics of the polyester bottle material, and specifically develops black master batch and the like special for the polyester bottle material.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method and application of black master batch for polyester bottle material regeneration spinning.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of black master batch for polyester bottle material regeneration spinning comprises the steps of blending and granulating carbon black and an ionic polymer according to a certain proportion to prepare a homogeneously dispersed black master batch;
the mass fraction of the carbon black in the black master batch is 30-60%;
the ionic polymer is prepared by esterifying dibasic acid containing sulfonate and dihydric alcohol containing sulfonate and then carrying out chain extension and viscosity increase, and the fluidity and the ionic bonding acting force are adjustable; the ionic polymer has self-dispersing and strong binding effects on the pigment by the ion pairs and the ion clusters.
The core of the invention is that the carbon black is added into a polymer carrier to be blended to prepare the high-dispersion black master batch, and the content of the carbon black is obviously higher than that in the prior art. The prior art for preparing the polyester black master batch takes polyester with certain fluidity as a carrier, and carbon black is blended with a dispersing agent with a special structure, and the dispersing agent is required to be introduced to regulate the dispersibility of the carbon black in the carrier. In addition, in the prior art, carbon black is regulated and controlled to be dispersed in master batches and fibers by a dispersing agent, but the regulating capability is limited, the shearing force applied to polyester is larger when fine denier fibers and superfine denier fibers are spun, the carbon black is difficult to uniformly disperse, and the fiber fastness, particularly the friction color fastness, is reduced.
The invention does not need to add dispersing agent, and the ionic polymer has the functions of both carrier and dispersing agent. The black master batch prepared by the method is introduced into the regenerated polyester for spinning, and has good compatibility with the regenerated polyester. Meanwhile, the rich ion clusters contained in the black master batch have good bonding force on the master batch, and carbon black in the fiber can be uniformly dispersed and is not easy to fall off when the spun fiber is used, especially when the fiber with fine denier and superfine denier specifications is spun.
As a preferable technical scheme:
the preparation method of the black master batch for the polyester bottle material regenerated spinning has the advantages that the particle size of the carbon black is less than or equal to 0.5 mu m.
The preparation method of the black master batch for polyester bottle material regenerated spinning comprises the step of preparing the ionic polymer with the intrinsic viscosity of 0.40-0.85 dl/g.
The preparation method of the black master batch for polyester bottle material regenerated spinning is characterized in that the esterification is segmented esterification;
the mole ratio of the carboxyl functional group number of the dibasic acid containing sulfonate to the hydroxyl functional group number of the dihydric alcohol containing sulfonate is 1.05-1.50; only adding dihydric alcohol containing sulfonate in the second stage of esterification reaction, wherein the addition amount is 0.1-0.6 of the molar amount of the dibasic acid containing sulfonate added in the first stage of esterification reaction;
the dibasic acid containing sulfonate is isophthalic acid-5-sodium sulfonate or terephthalic acid-2-sodium sulfonate;
the dihydric alcohol containing sulfonate is 2, 5-dihydroxybenzene sulfonate, N-di (2-hydroxyethyl) -2-sodium aminoethanesulfonate, 2- [ (tri (hydroxymethyl) methyl) amino ] -1-sodium ethanesulfonate or 3- [ N-tri (hydroxymethyl) methylamine ] -2-sodium hydroxypropanesulfonate;
the catalyst for the staged esterification reaction is benzenesulfonic acid, and is added in the first esterification reaction, wherein the dosage of the catalyst is 1000-5000 ppm of the mass of the dibasic acid containing sulfonate;
the temperature of the first stage esterification reaction is 220-250 ℃, the pressure is 0.05-0.5 MPa, and the time is 3.0-5.0 h;
the temperature of the second stage esterification reaction is 240-260 ℃, the pressure is 0.1-0.5 MPa, and the time is 0.5-1.0 h.
According to the preparation method of the black master batch for polyester bottle material regenerated spinning, chain extension and viscosity increase are carried out on the dibasic acid containing sulfonate and the dihydric alcohol esterification product containing sulfonate, diisocyanate is used as a chain extender, the chain extension reaction temperature is 150-250 ℃, and the reaction time is 30-60 min.
According to the preparation method of the black master batch for polyester bottle material regenerated spinning, the molar ratio of diisocyanate to the sulfonate-containing dibasic acid to the sulfonate-containing diol esterification product is 1.05-1.20:1.
The preparation method of the black master batch for polyester bottle material regeneration spinning comprises the step of preparing 1, 6-hexamethylene diisocyanate, toluene diisocyanate or dicyclohexyl methane diisocyanate serving as diisocyanate.
According to the preparation method of the black master batch for polyester bottle material regenerated spinning, the melt index of the black master batch is 10-30 g/10min, and the filter pressing value is less than or equal to 0.1MPa cm 2 ·g -1 。
The invention also provides application of the black master batch for polyester bottle material regeneration spinning, which is prepared by the method, wherein the black master batch for polyester bottle material regeneration spinning is added into a polyester bottle material melt for spinning according to the mass fraction of 2-10% to prepare the black polyester fiber.
As a preferable technical scheme:
in the application, the intrinsic viscosity of the polyester bottle material is 0.75-0.90 dl/g, and the mass fraction of isophthalic acid in the polyester bottle material is 0.2-2.5%.
According to the application, the monofilament diameter of the black polyester fiber is 0.5-2 mu m, the intrinsic viscosity of the oil-free silk is reduced to 0.02-0.10 dl/g, the breaking strength is more than or equal to 4.0cN/dtex, the color fastness is more than or equal to 4.0, and the service cycle of the fiber spinning component with the same specification is 1.2-2.0 times (compared with the service cycle of the fiber spinning component with the same specification, namely the fiber thickness is the same and the carbon black content is the same in the fiber, the component cycle needs to be replaced in a shorter time due to the dispersion problem of the carbon black in the masterbatch after the traditional black masterbatch is added, and the replacement cycle of the spinning component is prolonged due to the strong dispersion effect in the same specification of spinning, so that the black polyester fiber can be widely applied to the fields of home textiles, clothing, industrial textiles and the like.
The principle of the invention is as follows:
the carrier in the masterbatch for fibers is typically a thermoplastic polymer, and is generally compatible with the spinning melt. Pigments are generally inorganic or organic pigments having a micro-nano size scale, have a high specific surface area, act as a color developing function, but do not have fluidity, and thus need to be supported in a polymer carrier. The pigment has high specific surface area, so that secondary agglomeration and the like are easy to occur when the pigment is added into spinning melt, the spinnability is reduced, the replacement period of a spinning component is shortened, and the processing continuity and stability are affected. Therefore, a certain dispersing agent is usually introduced into the color master batch to perform a coating function on the pigment, so that agglomeration among the pigments is reduced, and the spinnability and the fiber performance are improved. Compared with common fiber-grade spinning polyester, the polyester bottle material has larger melt viscosity after melting and contains a certain amount of trisonomer (the intrinsic viscosity is 0.75-0.90 dl/g, and the mass fraction of isophthalic acid in the polyester bottle material is 0.2-2.5%). The existing fiber-grade polyester color master batch is difficult to realize a homogeneous mixing process in a high-viscosity polyester bottle material melt, and the pigment is easy to agglomerate for the second time, so that the spinnability and the coloring effect are greatly influenced. In order to ensure the dyeing performance of the fiber, the prior art disclosed is to remove agglomerated pigment through multistage filtration or reduce the high viscosity of spinning melt through color master batch so as to improve the mixing effect or to add the color master batch into the sheath conventional polyester by taking the polyester bottle material as the core layer of sheath-core composite spinning. It can be seen that the prior art does not specifically combine the characteristics of the polyester bottle material, and specifically develops the color master batch special for the polyester bottle material.
The invention designs and develops a black master batch for regenerating and spinning polyester bottle materials. Mixing and blending carbon black and an ionic polymer according to a certain mass ratio, and granulating to prepare the homogeneously dispersed black master batch. Aiming at the problem that the added color master batch is difficult to mix homogeneously due to the high viscosity of the spinning melt of the polyester bottle material, compared with the polyester bottle material, the developed black master batch has low intrinsic viscosity, and the shearing and thinning behaviors of the black master batch are more obvious after the two are mixed under the same shearing acting force. The black master batch with more remarkable shear thinning behavior plays a role in plasticizing and promoting flow of the high-viscosity polyester bottle material in the blending process, reduces the viscosity drop of the high-viscosity polyester bottle material under the high-temperature processing condition, and is beneficial to improving the mechanical properties of spun fibers. The polyester bottle material contains 0.2-2.5wt% of trisonomeric sulfonate, and the black master batch also contains sulfonate with a certain mass fraction, so that sulfonate ionic bonds have strong bonding force, and obvious phase separation between the black master batch and the polyester bottle material is avoided, and the mechanical properties of fibers are not reduced. Compared with the prior color master batch for the fiber, the color master batch has the effect of being added into a spinning melt for uniform mixing, and has the effect of coloring under the condition of less addition amount. The carrier and the ionic polymer in the masterbatch are connected by ester bonds, contain a large number of ester bond functional groups, and ensure good compatibility with polyester bottle material melt. The alloy is blended in polyester bottle melt, has the structural characteristic of alloy, and ensures good mechanical property of the fiber.
In order to ensure that the fiber has higher color fastness, the black master batch carrier is an ionic polymer. The ionic polymer generally has better mechanical properties and thermal stability than the matrix polymer. Because of the existence of multiple ion pairs and ion clusters in the ionomer, the dispersion and strong combination effect on pigment particles are achieved, and agglomeration of pigments in the processing process and blending into spinning melt is avoided. The strong bonding force of the ion pairs and the ion clusters promotes the adhesiveness of the melt in the fiber surface layer to the carbon black, and the melt is not easy to fall off under the action forces of water washing, friction and the like. In addition, the ion cluster aggregates can perform crosslinking action to enhance molecular chain interaction, and the mechanical strength of the fiber can be obviously enhanced when the ion cluster aggregates are introduced into the fiber material. Meanwhile, the crosslinking is reversible crosslinking, and can be dissociated under a certain shearing acting force, so that the thermoplastic property of the master batch is ensured.
The synthesis of the ionic polymer in the invention aims at the reason that the steric hindrance of sulfonate is larger and ensures that the prepared oligomer has higher reactivity, and the invention is designed to be in segmented esterification. The first stage of esterification is to ensure that the alcohol monomer containing sulfonate ion groups fully reacts completely by excessively increasing the number of carboxyl functional groups of dibasic acid containing sulfonate ion groups. At the end of the first esterification reaction, the product is capped with a dibasic acid due to the excess carboxyl groups. And introducing excessive end capped dihydric alcohol to fully react with the first-stage esterification product during the second-stage esterification reaction. And then the final product is obtained through chain extension reaction.
Advantageous effects
(1) The black master batch plays a role in coloring under a small addition amount, reduces the use amount of the color master batch, and prolongs the replacement period of the spinning component;
(2) The black master batch and the polyester bottle melt both contain rich ester bond functional groups and sulfonate ionic bonds, the two are still in a combined property, only microphase separation occurs, and the obvious phase separation between the black master batch and the polyester bottle is prevented from being generated, so that the mechanical properties of the fibers are reduced;
(3) The black master batch developed by the invention has more remarkable shear thinning behavior, plays a role in plasticizing and promoting flow of the high-viscosity polyester bottle material in the blending process, reduces the viscosity drop of the high-viscosity polyester bottle material under the high-temperature processing condition, and is beneficial to improving the mechanical property of spun fibers;
(4) The strong binding force of the ion pairs and the ion clusters in the black master batch developed by the invention improves the adhesiveness of the melt in the fiber surface layer to the pigment, and is not easy to fall off under the forces of washing, friction and the like.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The test method adopted by the invention is as follows:
(1) Melt index: the melt index of the black master batch was determined according to the specification of GB/T3682.1-2018 at a temperature of 280℃and a load of 2.16 kg;
(2) Filter pressing value: reference BS EN13900-5:2005 part 5: measuring by a filter pressing value test;
(3) Oil-free intrinsic viscosity: testing the intrinsic viscosity of the black polyester fiber according to GB/T14190-2017; in the following examples of the invention, the mass ratio of phenol to 1, 2-tetrachloroethane was 50:50 for the test;
(4) Breaking strength: adopting a dry breaking strength test in GB/T14344-2008 chemical fiber filament tensile property test method;
(5) Color fastness: the spun fibers were woven into a base fabric and tested according to GB/T3920-2008 textile color fastness to abrasion resistance and color fastness.
The technological parameters for preparing the black polyester fiber by spinning in each embodiment of the invention are as follows:
melt spinning temperature 270 ℃, cooling blowing temperature 22 ℃, relative humidity 85%, wind pressure 60kPa, fiber oil content 1.2%, speed 1600m/min of hot roller GR1, temperature 80 ℃ of hot roller GR1, speed 4500m/min of hot roller GR2, temperature 120 ℃ of hot roller GR2, winding speed 4500m/min.
In the embodiment of the invention, the fiber with the same specification refers to a black polyester fiber prepared by adopting a method in the prior art as a comparison sample, wherein the comparison sample has the same fiber thickness as the embodiment, and the carbon black content in the fiber is the same.
Example 1
The preparation method of the black master batch for the polyester bottle material regenerated spinning comprises the following specific steps:
(1) Carrying out sectional esterification reaction on isophthalic acid-5-sodium sulfonate and 2, 5-dihydroxybenzene potassium sulfonate under the condition that benzenesulfonic acid is used as a catalyst to obtain an esterification product;
the mole ratio of the carboxyl functional group number of the sodium isophthalic acid-5-sulfonate and the hydroxyl functional group number of the potassium 2, 5-dihydroxybenzene sulfonate added in the first stage esterification reaction is 1.05; the temperature of the first stage esterification reaction is 250 ℃, the pressure is 0.05MPa, and the time is 5.0h;
the second stage esterification reaction only adds 2, 5-dihydroxybenzene sulfonic acid potassium, the addition amount is 0.1 of the mole amount of isophthalic acid-5-sodium sulfonate added in the first stage esterification reaction; the temperature of the second stage esterification reaction is 260 ℃, the pressure is 0.1MPa, and the time is 1.0h;
benzene sulfonic acid is added in the first esterification reaction, and the dosage of the benzene sulfonic acid is 1000ppm of the mass of the isophthalic acid-5-sodium sulfonate;
(2) The 1, 6-hexamethylene diisocyanate is used as a chain extender, and the esterification product obtained in the step (1) is subjected to chain extension reaction to obtain an ionic polymer with the intrinsic viscosity of 0.40 dl/g; wherein, the molar ratio of the 1, 6-hexamethylene diisocyanate to the esterification product is 1.05:1; the chain extension reaction temperature is 250 ℃, and the reaction time is 30min;
(3) Blending and granulating carbon black with the average particle diameter of 0.3 mu m and the ionic polymer prepared in the step (2) according to a certain proportion to prepare a homogeneously dispersed black master batch; wherein the mass fraction of the carbon black in the black master batch is 30%; the melt index of the black master batch is 30g/10min, and the filter pressing value is 0.05MPa cm 2 ·g -1 。
Adding the black master batch prepared in the above into a polyester bottle melt with the intrinsic viscosity of 0.75dl/g according to the mass fraction of 2%, and spinning to obtain black polyester fibers; wherein, in the polyester bottle material, the mass fraction of isophthalic acid is 0.2%;
the monofilament diameter of the prepared black polyester fiber is 0.5 mu m, the intrinsic viscosity of the oil-free fiber is reduced to 0.02dl/g, the breaking strength is 4.9cN/dtex, the color fastness is 4.5, and the service cycle of the black polyester fiber is 2.0 times compared with that of a fiber spinning component with the same specification.
Example 2
The preparation method of the black master batch for the polyester bottle material regenerated spinning comprises the following specific steps:
(1) Carrying out sectional esterification reaction on isophthalic acid-5-sodium sulfonate and 2, 5-dihydroxybenzene potassium sulfonate under the condition that benzenesulfonic acid is used as a catalyst to obtain an esterification product;
the molar ratio of the carboxyl functional group number of the sodium isophthalic acid-5-sulfonate added in the first stage esterification reaction to the hydroxyl functional group number of the potassium 2, 5-dihydroxybenzenesulfonate is 1.15; the temperature of the first stage esterification reaction is 245 ℃, the pressure is 0.10MPa, and the time is 4.5h;
the second stage esterification reaction only adds 2, 5-dihydroxybenzene sulfonic acid potassium, the addition amount is 0.2 of the mole amount of isophthalic acid-5-sodium sulfonate added in the first stage esterification reaction; the temperature of the second stage esterification reaction is 255 ℃, the pressure is 0.2MPa, and the time is 0.9h;
benzene sulfonic acid is added in the first esterification reaction, and the dosage of the benzene sulfonic acid is 1000ppm of the mass of the isophthalic acid-5-sodium sulfonate;
(2) The 1, 6-hexamethylene diisocyanate is used as a chain extender, and the esterification product obtained in the step (1) is subjected to chain extension reaction to obtain an ionic polymer with the intrinsic viscosity of 0.55 dl/g; wherein, the molar ratio of the 1, 6-hexamethylene diisocyanate to the esterification product is 1.10:1; the chain extension reaction temperature is 220 ℃, and the reaction time is 35min;
(3) Blending and granulating carbon black with the average particle diameter of 0.35 mu m and the ionic polymer prepared in the step (2) according to a certain proportion to prepare a homogeneously dispersed black master batch; wherein the mass fraction of the carbon black in the black master batch is 40%; the melt index of the black master batch is 25g/10min, and the filter pressing value is 0.06MPa cm 2 ·g -1 。
Adding the black master batch prepared in the above into a polyester bottle melt with an intrinsic viscosity of 0.78dl/g according to the mass fraction of 5%, and spinning to obtain black polyester fibers; wherein, in the polyester bottle material, the mass fraction of isophthalic acid is 0.5%;
the monofilament diameter of the prepared black polyester fiber is 1.0 mu m, the intrinsic viscosity of the oil-free fiber is reduced to 0.03dl/g, the breaking strength is 4.7cN/dtex, the color fastness is 4.5, and the service cycle of the black polyester fiber is 1.8 times compared with that of a fiber spinning component with the same specification.
Example 3
The preparation method of the black master batch for the polyester bottle material regenerated spinning comprises the following specific steps:
(1) Carrying out sectional esterification reaction on isophthalic acid-5-sodium sulfonate and 2, 5-dihydroxybenzene potassium sulfonate under the condition that benzenesulfonic acid is used as a catalyst to obtain an esterification product;
the molar ratio of the carboxyl functional group number of the sodium isophthalic acid-5-sulfonate added in the first stage esterification reaction to the hydroxyl functional group number of the potassium 2, 5-dihydroxybenzenesulfonate is 1.20; the temperature of the first stage esterification reaction is 240 ℃, the pressure is 0.20MPa, and the time is 4.0h;
the second stage esterification reaction only adds 2, 5-dihydroxybenzene sulfonic acid potassium, the addition amount is 0.4 of the mole amount of isophthalic acid-5-sodium sulfonate added in the first stage esterification reaction; the temperature of the second stage esterification reaction is 250 ℃, the pressure is 0.3MPa, and the time is 0.8h;
benzene sulfonic acid is added in the first esterification reaction, and the dosage of the benzene sulfonic acid is 2000ppm of the mass of isophthalic acid-5-sodium sulfonate;
(2) Using toluene diisocyanate as a chain extender, and carrying out chain extension reaction on the esterified product obtained in the step (1) to obtain an ionic polymer with the intrinsic viscosity of 0.58 dl/g; wherein, the molar ratio of toluene diisocyanate to esterification product is 1.12:1; the chain extension reaction temperature is 200 ℃ and the reaction time is 40min;
(3) Blending and granulating carbon black with the average particle diameter of 0.40 mu m and the ionic polymer prepared in the step (2) according to a certain proportion to prepare a homogeneously dispersed black master batch; wherein the mass fraction of the carbon black in the black master batch is 50%; the melt index of the black master batch is 20g/10min, and the filter pressing value is 0.07MPa cm 2 ·g -1 。
Adding the black master batch prepared above into a polyester bottle melt with an intrinsic viscosity of 0.85dl/g according to the mass fraction of 6%, and spinning to obtain black polyester fibers; wherein, in the polyester bottle material, the mass fraction of isophthalic acid is 1.5%;
the monofilament diameter of the prepared black polyester fiber is 1.2 mu m, the intrinsic viscosity of the oil-free fiber is reduced to 0.05dl/g, the breaking strength is 4.6cN/dtex, the color fastness is 4.0, and the service cycle of the black polyester fiber is 1.6 times compared with that of a fiber spinning component with the same specification.
Example 4
The preparation method of the black master batch for the polyester bottle material regenerated spinning comprises the following specific steps:
(1) Carrying out sectional esterification reaction on terephthalic acid-2-sodium sulfonate, N-di (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt and 2- [ (tri (hydroxymethyl) methyl) amino ] -1-ethanesulfonic acid sodium salt under the condition that benzenesulfonic acid is used as a catalyst to obtain an esterification product;
the mole ratio of the carboxyl functional group number of the terephthalic acid-2-sodium sulfonate added in the first stage esterification reaction to the hydroxyl functional group number of the N, N-di (2-hydroxyethyl) -2-sodium aminoethanesulfonate and 2- [ (tri (hydroxymethyl) methyl) amino ] -1-sodium ethanesulfonate is 1.48; the temperature of the first stage esterification reaction is 230 ℃, the pressure is 0.40MPa, and the time is 4.5h;
the second stage of esterification is carried out by adding N, N-bis (2-hydroxyethyl) -2-sodium aminoethanesulfonate and 2- [ (tri (hydroxymethyl) methyl) amino ] -1-sodium ethanesulfonate with the addition amount being 0.5 of the mole amount of terephthalic acid-2-sodium sulfonate added in the first stage of esterification; the temperature of the second stage esterification reaction is 245 ℃, the pressure is 0.4MPa, and the time is 0.6h;
benzene sulfonic acid is added in the first esterification reaction, and the dosage of benzene sulfonic acid is 3200ppm of the mass of terephthalic acid-2-sodium sulfonate;
(2) Using toluene diisocyanate as a chain extender, and carrying out chain extension reaction on the esterified product obtained in the step (1) to obtain an ionic polymer with the intrinsic viscosity of 0.80 dl/g; wherein, the molar ratio of toluene diisocyanate to esterification product is 1.15:1; the chain extension reaction temperature is 180 ℃ and the reaction time is 50min;
(3) Blending and granulating carbon black with the average particle diameter of 0.45 mu m and the ionic polymer prepared in the step (2) according to a certain proportion to prepare a homogeneously dispersed black master batch; wherein the mass fraction of the carbon black in the black master batch is 55%; the melt index of the black master batch is 15g/10min, and the filter pressing value is 0.08MPa cm 2 ·g -1 。
Adding 8% of the black master batch into a polyester bottle melt with the intrinsic viscosity of 0.88dl/g according to the mass fraction to spin to obtain black polyester fibers; wherein, in the polyester bottle material, the mass fraction of isophthalic acid is 2%;
the monofilament diameter of the prepared black polyester fiber is 1.5 mu m, the intrinsic viscosity of the oil-free fiber is reduced to 0.08dl/g, the breaking strength is 4.4cN/dtex, the color fastness is 4.0, and the service cycle of the black polyester fiber is 1.5 times compared with that of a fiber spinning component with the same specification.
Example 5
The preparation method of the black master batch for the polyester bottle material regenerated spinning comprises the following specific steps:
(1) Carrying out sectional esterification reaction on terephthalic acid-2-sodium sulfonate and 3- [ N-tris (hydroxymethyl) methylamine ] -2-hydroxy propane sodium sulfonate under the condition that benzenesulfonic acid is used as a catalyst to obtain an esterification product;
the molar ratio of the carboxyl functional group number of the terephthalic acid-2-sodium sulfonate added in the first stage esterification reaction to the hydroxyl functional group number of the 3- [ N-tris (hydroxymethyl) methylamine ] -2-hydroxy propane sodium sulfonate is 1.50; the temperature of the first stage esterification reaction is 220 ℃, the pressure is 0.50MPa, and the time is 3.0h;
the second stage of esterification is only added with 3- [ N-tris (hydroxymethyl) methylamine ] -2-hydroxy propane sodium sulfonate, and the addition amount is 0.6 of the mole amount of terephthalic acid-2-sodium sulfonate added in the first stage of esterification; the temperature of the second stage esterification reaction is 240 ℃, the pressure is 0.5MPa, and the time is 0.5h;
benzenesulfonic acid was added at the first esterification reaction in an amount of 5000ppm by mass of sodium terephthalate-2-sulfonate;
(2) Performing chain extension reaction on the esterified product obtained in the step (1) by taking dicyclohexyl methane diisocyanate as a chain extender to obtain an ionic polymer with the intrinsic viscosity of 0.85 dl/g; wherein, the molar ratio of dicyclohexyl methane diisocyanate to the esterification product is 1.20:1; the chain extension reaction temperature is 150 ℃ and the reaction time is 60min;
(3) Blending and granulating carbon black with the average particle diameter of 0.50 mu m and the ionic polymer prepared in the step (2) according to a certain proportion to prepare a homogeneously dispersed black master batch; wherein the mass fraction of the carbon black in the black master batch is 60%; the melt index of the black master batch is 10g/10min, and the filter pressing value is 0.10MPa cm 2 ·g -1 。
Adding 10% of the black master batch into a polyester bottle melt with the intrinsic viscosity of 0.9dl/g according to the mass fraction to spin to obtain black polyester fibers; wherein, in the polyester bottle material, the mass fraction of isophthalic acid is 2.5%;
the monofilament diameter of the prepared black polyester fiber is 2.0 mu m, the intrinsic viscosity of the oil-free silk is reduced to 0.10dl/g, the breaking strength is 4.0cN/dtex, the color fastness is 4.0, and the service cycle of the black polyester fiber is 1.2 times compared with that of a fiber spinning component with the same specification.
Claims (10)
1. A preparation method of black master batch for polyester bottle material regeneration spinning is characterized by comprising the following steps: blending and granulating carbon black and an ionic polymer according to a certain proportion to prepare a homogeneously dispersed black master batch;
the mass fraction of the carbon black in the black master batch is 30-60%;
the ionic polymer is prepared by esterifying dibasic acid containing sulfonate and dihydric alcohol containing sulfonate and then carrying out chain extension and viscosity increase;
esterification to staged esterification;
the mole ratio of the carboxyl functional group number of the dibasic acid containing sulfonate to the hydroxyl functional group number of the dihydric alcohol containing sulfonate is 1.05-1.50; only adding dihydric alcohol containing sulfonate in the second stage of esterification reaction, wherein the addition amount is 0.1-0.6 of the molar amount of the dibasic acid containing sulfonate added in the first stage of esterification reaction;
the dibasic acid containing sulfonate is isophthalic acid-5-sodium sulfonate or terephthalic acid-2-sodium sulfonate;
the dihydric alcohol containing sulfonate is 2, 5-dihydroxybenzene sulfonate, N-di (2-hydroxyethyl) -2-sodium aminoethanesulfonate, 2- [ (tri (hydroxymethyl) methyl) amino ] -1-sodium ethanesulfonate or 3- [ N-tri (hydroxymethyl) methylamine ] -2-sodium hydroxypropanesulfonate;
the catalyst for the staged esterification reaction is benzenesulfonic acid, and is added in the first esterification reaction, wherein the dosage of the catalyst is 1000-5000 ppm of the mass of the dibasic acid containing sulfonate;
the temperature of the first stage esterification reaction is 220-250 ℃, the pressure is 0.05-0.5 MPa, and the time is 3.0-5.0 h;
the temperature of the second stage esterification reaction is 240-260 ℃, the pressure is 0.1-0.5 MPa, and the time is 0.5-1.0 h.
2. The method for preparing the black master batch for polyester bottle material regenerated spinning according to claim 1, wherein the carbon black has a particle size of less than or equal to 0.5 μm.
3. The method for preparing the black master batch for polyester bottle material regenerated spinning according to claim 1, wherein the intrinsic viscosity of the ionic polymer is 0.40-0.85 dl/g.
4. The preparation method of the black master batch for polyester bottle material regenerated spinning according to claim 1, wherein the chain extension and viscosity increase are carried out on a sulfonate-containing dibasic acid and sulfonate-containing dihydric alcohol esterification product, diisocyanate is used as a chain extender, the chain extension reaction temperature is 150-250 ℃, and the reaction time is 30-60 min.
5. The method for preparing the black master batch for polyester bottle material regenerated spinning according to claim 4, wherein the molar ratio of diisocyanate to sulfonate-containing diacid to sulfonate-containing diol esterification product is 1.05-1.20:1.
6. The method for preparing black master batch for polyester bottle material regeneration spinning according to claim 5, wherein the diisocyanate is 1, 6-hexamethylene diisocyanate, toluene diisocyanate or dicyclohexylmethane diisocyanate.
7. The preparation method of the black master batch for polyester bottle material regenerated spinning according to claim 1, wherein the melt index of the black master batch is 10-30 g/10min, and the filter pressing value is less than or equal to 0.1MPa cm 2 ·g -1 。
8. The use of the black master batch for polyester bottle material regenerated spinning, which is prepared by the method according to any one of claims 1 to 7, is characterized in that: and adding the black master batch for the polyester bottle material regeneration spinning into a polyester bottle material melt for spinning according to the mass fraction of 2-10% to obtain the black polyester fiber.
9. The use according to claim 8, wherein the intrinsic viscosity of the polyester bottle is 0.75 to 0.90dl/g, and the mass fraction of isophthalic acid in the polyester bottle is 0.2 to 2.5%.
10. The use according to claim 9, characterized in that the monofilament diameter of the black polyester fiber is 0.5-2 μm, the intrinsic viscosity of the oil-free filaments is reduced to 0.02-0.10 dl/g, the breaking strength is not less than 4.0cN/dtex, the color fastness is not less than 4.0, and the service period of the fiber spinning component with the same specification is 1.2-2.0 times.
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