CN117430835A - Polylactic acid color master batch and preparation method and application thereof - Google Patents

Polylactic acid color master batch and preparation method and application thereof Download PDF

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Publication number
CN117430835A
CN117430835A CN202311589332.3A CN202311589332A CN117430835A CN 117430835 A CN117430835 A CN 117430835A CN 202311589332 A CN202311589332 A CN 202311589332A CN 117430835 A CN117430835 A CN 117430835A
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polylactic acid
master batch
pigment
color master
intermediate product
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谢伟
王华平
徐毅明
吉鹏
王朝生
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Poly Plastic Masterbatch Suzhou Co ltd
Donghua University
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Poly Plastic Masterbatch Suzhou Co ltd
Donghua University
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/223—Packed additives
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/16—Nitrogen-containing compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
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    • C08K5/16—Nitrogen-containing compounds
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Abstract

The invention relates to a polylactic acid color master batch, a preparation method and application thereof, and a preparation method of the polylactic acid color master batch: uniformly mixing pigment, water and a coating agent to obtain an intermediate product I, sequentially carrying out coarse grinding, fine grinding and superfine grinding on the intermediate product I to obtain an intermediate product II, then dehydrating the intermediate product II to obtain color paste, finally blending the color paste with polylactic acid powder, removing a solvent in the blending process, uniformly mixing the obtained mixed powder with an anti-hydrolysis agent, and feeding the obtained mixed powder into a double-screw extruder for extrusion granulation to obtain polylactic acid color master batch, wherein the weight average relative molecular weight of the polylactic acid powder is 18-19 ten thousand (preferably 18 ten thousand). Application of polylactic acid color master batch: the polylactic acid color master batch prepared by the method is used for preparing the special-shaped fine denier polylactic acid fiber by adopting the master batch method. The master batch prepared by the invention solves the problems of easy agglomeration and difficult dispersion of pigment, and the fiber prepared by the master batch has good spinnability and physical properties.

Description

Polylactic acid color master batch and preparation method and application thereof
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a polylactic acid color master batch, a preparation method and application thereof.
Background
At present, the polylactic acid is dyed mainly in two ways, namely high-temperature dyeing and masterbatch melt spinning. The high-temperature dyeing has great influence on the physical properties of the polylactic acid fiber, serious strong damage and severe dyeing conditions, and can generate a large amount of wastewater and waste gas. The preparation method of the color master batch for chemical fiber is generally to uniformly stir carrier resin, toner and dispersing agent at high speed, then melt, disperse, extrude, cool and granulate the color master batch by a double screw extruder, for example, the color master batch is prepared by mixing polylactic acid powder, pigment and auxiliary materials, pressing the mixture into the screw extruder to melt, extrude and granulate the mixture to obtain the master batch, but the polylactic acid and pigment used by the method are added in powder, dust pollution is easy to be caused, the mixing method and the melt granulation by the screw extruder only can mix, but pigment cannot be refined, so the prepared color master batch has poor spinnability and the spun fiber has poor physical properties.
CN116023799a discloses a degradable superfine pigment preparation and a preparation method thereof, wherein the pigment is coated in the softened state of polylactic acid, water, polylactic acid and plasticizer are added into high shear equipment filled with grinding beads, the resin is softened by heating, pre-dispersion liquid of water, pigment and dispersing agent is added, pigment particles are coated by softened polylactic acid, and the prepared pigment preparation is free from dust pollution, is applied to coloring of polylactic acid fiber stock solution, and has strong mechanical property and high coloring strength.
However, CN116023799a requires the use of polylactic acid having a lower softening point or melting point, otherwise the pigment particles cannot be coated with softened polylactic acid, which means that the polylactic acid has a smaller molecular weight than conventional polylactic acid, and the spinning of the polylactic acid by adding the polylactic acid to normal polylactic acid in proportion causes the broadening of the molecular weight distribution of the whole polylactic acid system, which is disadvantageous for spinning, especially spinning fine denier textured yarns.
Therefore, there is a need to develop a method for preparing polylactic acid color master batch which can simultaneously have the advantages of reducing dust pollution, thinning pigment and avoiding the use of polylactic acid with small molecular weight.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a polylactic acid color master batch and a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the polylactic acid color master batch comprises the following steps:
(1) Uniformly mixing pigment, water and a coating agent by adopting a high-speed dispersing machine to obtain an intermediate product I, wherein the mixing temperature is 40-50 ℃;
(2) Sequentially carrying out coarse grinding, fine grinding and superfine grinding on the intermediate product I by adopting a sand mill to obtain an intermediate product II; the pre-mixed materials are ground by using a sand mill with three zirconium bead particle sizes, the pre-mixed materials are required to be firstly coarsely ground and then finely ground, and then superfine grinding is carried out, if the grinding sequence is lacking, the grinding sequence is reversed and spanned, the grinding efficiency is very easy to be low, and even the sand mill is blocked to cause production stop;
(3) The intermediate product II is dehydrated by adopting a decanter centrifuge to obtain color paste with the solid content of 70-80wt%, and the use of the decanter centrifuge for removing water has the advantages that the operation at normal temperature is not like the problems of unstable pigment dispersion, agglomeration and the like caused by overhigh temperature in the traditional drying process;
(4) Blending color paste and polylactic acid powder, removing solvent in the blending process, uniformly mixing the obtained mixed powder with an anti-hydrolysis agent, and feeding the mixture into a double-screw extruder for extrusion granulation to obtain the polylactic acid color master batch, wherein the weight average relative molecular weight of the polylactic acid powder is 18-19 ten thousand (preferably 18 ten thousand).
The preparation method of the polylactic acid color master batch can simultaneously reduce dust pollution, refine pigment and avoid using polylactic acid with small molecular weight, because:
(1) according to the invention, the mixing temperature of the pigment, the water and the coating agent is controlled to be 40-50 ℃, if the mixing temperature of the pigment, the water and the coating agent is too low, the coating agent cannot be effectively emulsified and dispersed in the water, the coating agent is seriously and hardly and uniformly agglomerated pigment particles are opened and uniformly coated with the pigment after being agglomerated among the pigment particles, the pigment particles which are not completely coated are easy to raise dust in the mixing process, the mixing temperature is too high, the coating agent is completely emulsified in the water, but the agglomeration tendency of the coating agent and the pigment is also increased, the agglomerated pigment large particles are easily broken to form uncoated pigment in the process of drying the mixture of the follow-up color paste and the polylactic acid powder, the raised dust is difficult to be opened in the mixing process, and the pigment agglomerated large particles caused by the two conditions are difficult to be opened in the high-speed mixing and screw shearing processes, so that the pressure filtration difference of polylactic acid color master batch is large, the spinnability is poor, and the spun fiber breaking strength is also poor;
(2) according to the invention, the coating agent is added, and the color paste is ground for three times, the pigment is thoroughly ground and opened after the process of grinding the color paste for three times, and the surface of the pigment is coated in the process of grinding, so that the thinned pigment particles are not easy to agglomerate, and the pigment can be better thinned and dispersed in the polylactic acid;
(3) compared with the process that the superfine pigment preparation is not broken, the color paste and the polylactic acid powder are mixed, belong to the mixing from liquid state to dry state, have no dust emission in the liquid state mixing process, and are adhered together as a binding agent due to the fact that the coating agent is arranged on the surface of the pigment when the color paste is mixed to the dry state, so that the mixed material has high bulk density, is fine sand, is not easy to emit dust, and has less dust pollution; the liquid color paste and the solid polylactic acid powder are mixed, the pigment and the polylactic acid powder are gradually mixed in the process of gradually evaporating water, the mixing mode is slow but more uniform, if the color paste is directly dried to form the color powder and then is mixed with the polylactic acid powder, the mixing effect is poor, because the pigment forms agglomeration in the process of drying the color powder, the agglomeration is hard, and even if a coating auxiliary agent is added, the agglomeration is hard to open in the process of short-term double-screw extrusion;
(4) the solid content of the color paste is controlled to be 70-80wt%, if the solid content of the color paste is too high, the time from liquid state mixing to dry state mixing is too short, the pigment and the polylactic resin are not sufficiently bonded, the state of fine sand of the material is not easy to be achieved, and fine dust is easy to fly; if the solid content of the color paste is too low, the time from liquid state mixing to dry state mixing is too long, the pigment particles which are coated originally can be uncoated due to long-time high shearing, fine dust is caused, the uncoated pigment particles are agglomerated in the screw processing process, the pressure filtration difference of the polylactic acid color master batch is large, the spinnability is poor, and the breaking strength of the spun fibers is also poor;
(5) according to the invention, the hydrolysis inhibitor is added, so that the degradation of the polylactic acid carrier in the screw due to the existence of high temperature and trace moisture can be reduced, and the spinnability of the master batch is improved; the hydrolysis inhibitor needs to be added after the color paste and the polylactic acid are mixed to the dry powder state and the test moisture is below 0.5%, but cannot be added together when the color paste and the polylactic acid powder are mixed, because the color paste and the polylactic acid powder are mixed with water and the temperature of the water is high, if the hydrolysis inhibitor is added at the moment, the hydrolysis inhibitor is directly invalid;
(6) the invention does not need to coat pigment particles with polylactic acid, so that polylactic acid with lower softening point or melting point is not needed to be used, the weight average relative molecular weight of polylactic acid powder is 18-19 ten thousand (preferably 18 ten thousand), and the polylactic acid powder is consistent with polylactic acid used by downstream customers, so that the compatibility and spinnability are better.
As a preferential technical scheme:
in the preparation method of the polylactic acid color master batch, in the step (1), the pigment is more than one of pigment red 122, pigment violet 23, pigment green 7, pigment yellow 150, pigment black 7 and pigment blue 15:3; the coating agent consists of A and B in the mass ratio of 2-4:1, wherein A is polyethylene glycol with the relative molecular weight of more than or equal to 8000, and B is more than one of trimethylolethane, trimethylolpropane, neopentyl glycol, triethanolamine and trimethylamine; the mixing speed is 500-1000rpm, and the mixing time is 30-60min.
In the preparation method of the polylactic acid color master batch, in the step (1), when the polylactic acid color master batch is mixed, water is heated to 40-50 ℃, then the coating agent is added, the mixture is fully and uniformly stirred, and then the pigment is added, so that if the coating agent is not thoroughly dissolved, the particle size of the pigment in the subsequent grinding color paste is very easy to cause to be difficult to be reduced all the time, and even if the grinding rotating speed is adjusted in the later period or the grinding time is prolonged, the problem is difficult to be solved.
In the preparation method of the polylactic acid color master batch, in the step (2), zirconium beads with the diameter of 0.6-0.8mm are adopted for rough grinding for 30-60min; the fine grinding adopts zirconium beads with the diameter of 0.3-0.4mm for 30-60min; zirconium beads with the diameter of 0.08-0.12mm are adopted for superfine grinding, and the time is 60-120min.
According to the preparation method of the polylactic acid color master batch, in the step (2), the solid content of the intermediate product II is 20.0-30.4wt%, and the solid content of the intermediate product II is controlled to be 20.0-30.4wt%, so that the intermediate product II can have enough fluidity, the grinding efficiency is higher, and the particle size of the intermediate product II is smaller.
The preparation method of the polylactic acid color master batch comprises the following steps of (1), wherein the average particle size of the pigment is 0.5-6.5 mu m; in the step (3), the average particle size of the color paste is 0.1-0.3 mu m.
According to the preparation method of the polylactic acid color master batch, the color paste consists of 70-80wt% of pigment, 1.5-3.0wt% of coating agent and the balance of water according to weight percentage.
In the step (4), the color paste and the polylactic acid powder are blended, and the solvent is removed in the blending process, specifically, the color paste and the polylactic acid powder are mixed for 30-60min in a high-speed mixer with the temperature of 100-110 ℃ and the rotating speed of 500-1400 rpm.
In the preparation method of the polylactic acid color master batch, in the step (4), the addition amount of each component fed into the double-screw extruder is as follows in percentage by weight: 99.5 to 99.9 weight percent of mixed powder and 0.1 to 0.5 weight percent of hydrolysis inhibitor.
The invention also provides a polylactic acid color master batch, which is prepared by adopting the preparation method of the polylactic acid color master batch.
The invention also provides a preparation method of the special-shaped fine denier polylactic acid fiber, and the masterbatch is a polylactic acid color masterbatch as described above.
The beneficial effects are that:
(1) The invention firstly prepares color paste, then blends the color paste with polylactic acid powder, removes solvent in the blending process, finally mixes the obtained material with an anti-hydrolysis agent uniformly and feeds the mixture into a double screw extruder for extrusion to prepare polylactic acid color master batch, solves the problems that pigment in polylactic acid color master batch produced by the traditional method is easy to agglomerate and difficult to disperse, and can simultaneously reduce dust pollution, refine pigment and avoid using polylactic acid with small molecular weight. The prepared color master batch is more beneficial to spinning fine denier profiled polylactic acid fibers.
(2) The invention adopts a masterbatch method, takes polylactic acid color masterbatch as masterbatch to prepare the special-shaped fine denier polylactic acid fiber, has less waste liquid and dust in the production process, is simpler and more convenient for downstream spinning clients to apply, is clean and sanitary, and has good spinnability and physical properties of the finally prepared fiber.
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 of the correlation performance in the following embodiments:
solid content: placing the test sample in a constant temperature oven at 150 ℃ for 1h, recording the weights of color pastes before (W1) and after (W2) baking the test sample, and calculating the solid content according to the recorded data, wherein the calculation formula is as follows: solid content= (W1-W2)/w1×100%;
average particle diameter: diluting the color paste and deionized water according to the mass ratio of 1:100, and then testing the average particle diameter Dv50 of the color paste by using a laser particle sizer;
fineness: testing according to method A (beam fiber middle section weighing method) in GB/T14335-2008;
breaking strength: testing according to GB/T14337 standard method;
intrinsic viscosity: test according to method A (capillary viscosimetry) of method 5.1.1 of GB/T14190-2017;
filter pressing difference: tested according to the method of filter press difference (DF value) of 6.3 in FZ/T51019.
Example 1
A preparation method of polylactic acid color master batch comprises the following steps:
(1) Preparing raw materials;
and (3) pigment: pigment Red 122, manufactured by Clariant chemical (China) Co., ltd, with the brand PV Fast Pink E;
water;
coating agent: consists of A (polyethylene glycol with relative molecular weight of 8000) and B (trimethylolpropane) in a mass ratio of 4:1;
polylactic acid powder: manufacturer is Anhui Feng Yuanfu Talai lactic acid Co., ltd, trade mark is FY601, melt index is 9g/10min, weight-average relative molecular weight is 18 ten thousand;
hydrolysis inhibitor: monomeric carbodiimide;
(2) Mixing 20wt% of pigment, 1wt% of coating agent and the balance of water for 45min at 40 ℃ by adopting a high-speed dispersing machine at a rotating speed of 500rpm to obtain an intermediate product I;
(3) Firstly, carrying out rough grinding on the intermediate product I for 30min by using zirconium beads with the diameter of 0.6-0.8mm by adopting a sand mill, then, carrying out fine grinding on the intermediate product I after rough grinding for 60min by using zirconium beads with the diameter of 0.3-0.4mm, and finally, carrying out superfine grinding on the intermediate product I after fine grinding for 120min by using zirconium beads with the diameter of 0.08-0.12mm to obtain an intermediate product II with the solid content of 20.0 wt%;
(4) Dehydrating the intermediate product II by adopting a decanter centrifuge to obtain color paste with the solid content of 75.3 weight percent;
the average grain diameter of the prepared color paste is 0.29 mu m;
(5) Mixing color paste and polylactic acid powder in a high-speed mixer with the temperature of 100 ℃ and the rotating speed of 500rpm for 60min to remove the solvent, obtaining mixed powder with the trace moisture of 0.3 weight percent, uniformly mixing 99.7 weight percent of the mixed powder with the rest hydrolysis inhibitor according to the weight percent, and feeding the mixed powder and the rest hydrolysis inhibitor into a double-screw extruder for extrusion granulation, thus obtaining the polylactic acid color master batch.
The final pressure filtration difference of the prepared polylactic acid color master batch is 0.22MPa, and the intrinsic viscosity is 0.512dL/g.
The preparation method of the special-shaped fine denier polylactic acid fiber comprises the steps of adopting the prepared polylactic acid color master batch and polylactic acid chips (manufactured by Anhui Feng Yuanfu Talai lactic acid Co., ltd., brand FY601, melting point 175 ℃) to blend according to the mass ratio of 2:98, drying until the water content is below 0.004%, and carrying out melt spinning to obtain the special-shaped fine denier polylactic acid fiber;
the spinning process parameters are as follows: the shape of the spinneret orifice is cross-shaped, and the spinning temperature is as follows: screw one zone: 200 ℃, screw two zone: 210 ℃, screw three zone: 215 ℃, screw four zone: 220 ℃, 225 ℃ in a five-zone screw, 230 ℃ in a box body and 1200m/min spinning speed.
The special-shaped fine denier polylactic acid fiber finally prepared has the single filament number of 1.5D, the cross-section shape of the fiber, the pigment content of 0.6wt percent and the breaking strength of 3.22cN/dtex, and can be continuously spun without broken ends and floating filaments.
Comparative example 1
A method for preparing polylactic acid color master batch, which is basically the same as example 1, and only differs in that: the mixing temperature of the high-speed dispersing machine in the step (2) is 25 ℃.
The average particle size of the color paste prepared in the step (4) is 0.98 μm.
The final pressure filtration difference of the prepared polylactic acid color master batch is 2.4MPa, and the intrinsic viscosity is 0.516dL/g.
A method for preparing a special-shaped fine denier polylactic acid fiber, which is basically the same as that of example 1, and is different only in that: the polylactic acid color master batch is prepared by the method.
The filament number of the finally prepared special-shaped fine denier polylactic acid fiber is 1.5D, the pigment content is 0.6wt%, the breaking strength is 2.84cN/dtex, and the phenomena of 5 times of filament floating and 1 time of end breakage occur in the spinning process.
As can be seen from the comparison between the example 1 and the comparative example 1, the too low mixing temperature of the pigment, water and the coating agent in the comparative example 1 can cause more dust emission in the mixing and drying process of the color paste and the polylactic acid powder, and meanwhile, the prepared polylactic acid master batch has larger filter pressing difference and poor spinnability. This is because the low temperature during mixing in the high-speed disperser can not effectively emulsify and disperse the coating agent in water, if the coating agent is seriously agglomerated, the agglomerated pigment particles are difficult to uniformly permeate between the pigment particles to open and uniformly coat the pigment, the pigment particles which are not completely coated are easy to raise dust in the mixing process, and the agglomerated pigment particles are difficult to open in the high-speed mixing and screw shearing, so that the pressure filtration difference of the polylactic acid color master batch is larger, the spinnability of the polylactic acid color master batch is poor, and the fracture strength of the spun fiber is also poor.
Comparative example 2
A method for preparing polylactic acid color master batch, which is basically the same as example 1, and only differs in that: the mixing temperature of the high-speed dispersing machine in the step (2) is 70 ℃.
The average particle size of the color paste prepared in the step (4) is 0.78 μm.
The final pressure filtration difference of the prepared polylactic acid color master batch is 1.7MPa, and the intrinsic viscosity is 0.523dL/g.
A method for preparing a special-shaped fine denier polylactic acid fiber, which is basically the same as that of example 1, and is different only in that: the polylactic acid color master batch is prepared by the method.
The filament number of the finally prepared special-shaped fine denier polylactic acid fiber is 1.5D, the pigment content is 0.6wt%, the breaking strength is 2.95cN/dtex, and the phenomena of 4 times of floating yarn and 1 time of broken yarn occur in the spinning process.
As can be seen from comparing the example 1 with the comparative example 2, the too high mixing temperature of the pigment, water and the coating agent in the comparative example 2 can cause more dust emission in the mixing and drying process of the color paste and the polylactic acid powder, and meanwhile, the prepared polylactic acid master batch has larger pressure filtration difference and poor spinnability. This is because the temperature is high when the high-speed dispersion machine is mixed, although the coating agent can be thoroughly emulsified and dispersed in water, the aggregation tendency of the coating agent and the pigment respectively becomes large, the aggregated pigment large particles are easy to break up to form uncoated pigment in the process of drying the mixture of the back color paste and the polylactic acid powder although coated, dust is raised in the process of mixing, and the aggregated pigment particles are difficult to open in the process of high-speed mixing and screw shearing, so that the pressure filtration difference of the polylactic acid color master batch is large, the spinnability of the polylactic acid color master batch is poor, and the fracture strength of the spun fiber is also poor.
Comparative example 3
A method for preparing polylactic acid color master batch, which is basically the same as example 1, and only differs in that: no coating agent is prepared in step (1); the color paste was prepared without using steps (2) to (4), and the polylactic acid color master batch was prepared in step (5) by using pigment (the same mass as the pigment in step (2) of example 1) instead of the color paste.
The final pressure filtration difference of the prepared polylactic acid color master batch is 4.1MPa, and the intrinsic viscosity is 0.520dL/g.
A method for preparing a special-shaped fine denier polylactic acid fiber, which is basically the same as that of example 1, and is different only in that: the polylactic acid color master batch is prepared by the method.
The filament number of the finally prepared special-shaped fine denier polylactic acid fiber is 1.5D, the pigment content is 0.6wt%, the breaking strength is 2.53cN/dtex, and 8 filament waving and 2 filament breakage phenomena can occur in the spinning process.
Comparing example 1 with comparative example 3, it is known that the direct use of pigment to replace color paste in comparative example 3 to prepare polylactic acid color master batch results in larger pressure filtration difference of master batch and poor spinnability, because agglomerated pigment particles are difficult to open by a method of directly mixing pigment and polylactic acid powder at high speed and extruding and granulating by twin screws, the self-polymerization of pigment used in comparative example 3 is stronger, the pressure filtration difference of prepared polylactic acid color master batch is larger, the spinnability of polylactic acid color master batch is poor, and the fiber breaking strength is lower; in the embodiment 1, the pigment paste which is well ground and dispersed is blended with the polylactic acid powder, the pigment aggregate is opened in the process of grinding the pigment paste and is coated with a layer of coating agent on the surface, even if the pigment paste is dried, the pigment is easy to be cut and opened in a high-speed mixing and double screw, the filter pressing difference of the prepared polylactic acid color master batch is small, the spinnability is good, and the breaking strength of the fiber prepared by using the polylactic acid color master batch is high.
Comparative example 4
A method for preparing polylactic acid color master batch, which is basically the same as example 1, and only differs in that: in the step (5), the anti-hydrolysis agent is added when the color paste is mixed with the polylactic acid powder.
The final pressure filtration difference of the prepared polylactic acid color master batch is 0.75MPa, and the intrinsic viscosity is 0.39dL/g.
A method for preparing a special-shaped fine denier polylactic acid fiber, which is basically the same as that of example 1, and is different only in that: the polylactic acid color master batch is prepared by the method.
The special-shaped fine denier polylactic acid fiber finally prepared has the single filament number of 1.5D, the pigment content of 0.6wt percent, the breaking strength of 3.02cN/dtex and 3 times of filament floating phenomenon in the spinning process.
As can be seen from comparison between example 1 and comparative example 4, the comparative example 4 is that the simultaneous addition of the anti-hydrolysis agent during mixing of the color paste and the polylactic acid powder material results in a smaller intrinsic viscosity of the prepared master batch, because the anti-hydrolysis agent can be directly deactivated due to the presence of a large amount of water in the mixing process and cannot react with the carboxyl end groups of the polyester in the screw rod, the viscosity of the master batch is easily reduced after high-temperature extrusion, the molecular weight range is widened, and the addition of the master batch to the normal polylactic acid spinning melt directly affects the uniformity of the molecular weight of the whole system, thereby causing the breakage of the fiber at the weak section, causing the condition of multiple filament waving, and the breaking strength of the fiber is also lowered.
Example 2
A preparation method of polylactic acid color master batch comprises the following steps:
(1) Preparing raw materials;
and (3) pigment: pigment Yellow 150, manufacturer Lang Cheng Jituan, brand Bayplast Yellow 5GN;
water;
coating agent: consists of A (polyethylene glycol with relative molecular weight of 8000) and B (trimethylolethane) in a mass ratio of 4:1;
polylactic acid powder: manufacturer is Anhui Feng Yuanfu Talai lactic acid Co., ltd, trade mark is FY601, melt index is 9g/10min, weight-average relative molecular weight is 18 ten thousand;
hydrolysis inhibitor: monomeric carbodiimide;
(2) Mixing 25wt% of pigment, 1wt% of coating agent and the balance of water for 30min at 40 ℃ by adopting a high-speed dispersing machine at a rotating speed of 500rpm to obtain an intermediate product I;
(3) Firstly, carrying out rough grinding on the intermediate product I for 30min by using zirconium beads with the diameter of 0.6-0.8mm by adopting a sand mill, then, carrying out fine grinding on the intermediate product I after rough grinding for 45min by using zirconium beads with the diameter of 0.3-0.4mm, and finally, carrying out superfine grinding on the intermediate product I after fine grinding for 100min by using zirconium beads with the diameter of 0.08-0.12mm to obtain an intermediate product II with the solid content of 25.7wt%;
(4) Dehydrating the intermediate product II by adopting a decanter centrifuge to obtain color paste with the solid content of 80 wt%;
the average grain diameter of the prepared color paste is 0.25 mu m;
(5) Mixing color paste and polylactic acid powder in a high-speed mixer with the temperature of 105 ℃ and the rotating speed of 1000rpm for 40min to remove the solvent, obtaining mixed powder with the trace moisture of 0.2 weight percent, uniformly mixing 99.8 weight percent of the mixed powder and the balance of hydrolysis inhibitor according to the weight percent, and feeding the mixed powder and the balance of hydrolysis inhibitor into a double-screw extruder for extrusion granulation, thus obtaining the polylactic acid color master batch.
The final pressure filtration difference of the prepared polylactic acid color master batch is 0.11MPa, and the intrinsic viscosity is 0.521dL/g.
The preparation method of the special-shaped fine denier polylactic acid fiber comprises the steps of adopting the prepared polylactic acid color master batch and polylactic acid chips (manufactured by Anhui Feng Yuanfu Talai lactic acid Co., ltd., brand FY601, melting point 175 ℃) to blend according to the mass ratio of 2.5:97.5, drying until the water content is below 0.004%, and then carrying out melt spinning to obtain the special-shaped fine denier polylactic acid fiber;
the spinning process parameters are as follows: the spinneret holes are cross-shaped, the temperature of the first area of the screw is 200 ℃, the temperature of the second area of the screw is 210 ℃, the temperature of the third area of the screw is 215 ℃, the temperature of the fourth area of the screw is 220 ℃, the temperature of the fifth area of the screw is 225 ℃, the temperature of the box body is 230 ℃, and the spinning speed is 600m/min.
The special-shaped fine denier polylactic acid fiber finally prepared has the single filament number of 1.5D, the cross-section shape of the fiber, the pigment content of 0.8wt percent and the breaking strength of 3.20cN/dtex, and can be continuously spun without broken ends and floating filaments.
Comparative example 5
A method for preparing polylactic acid color master batch, which is basically the same as example 2, and only differs in that: and (3) dehydrating the intermediate product II by adopting a decanter centrifuge in the step (4), and reducing the time for centrifuging the intermediate product II by adopting the decanter centrifuge to obtain the color paste with the solid content of 52.3 weight percent.
The final pressure filtration difference of the prepared polylactic acid color master batch is 0.78MPa, and the intrinsic viscosity is 0.515dL/g.
A method for preparing a special-shaped fine denier polylactic acid fiber, which is basically the same as that of example 2, and is different only in that: the polylactic acid color master batch is prepared by the method.
The special-shaped fine denier polylactic acid fiber finally prepared has the single filament number of 1.5D, the pigment content of 0.8wt percent, the breaking strength of 2.99cN/dtex and the phenomenon of yarn floating for 2 times in the spinning process.
As can be seen from comparison between example 2 and comparative example 5, the solid content of the color paste obtained in comparative example 5 is too low, which results in more dust emission in the mixing and drying process of the color paste and the polylactic acid powder, and the pressure filtration difference of the prepared polylactic acid master batch is larger, and the spinnability is poor, because the solid content of the color paste is too low, the time from liquid mixing to dry mixing is too long, the coated pigment particles can be uncoated due to long-time high shearing, so that fine dust emission is caused, and the uncoated complete pigment particles are agglomerated in the screw processing process, so that the pressure filtration difference of the polylactic acid master batch is larger, the spinnability is poor, and the fracture strength of the spun fibers is also poor.
Comparative example 6
A method for preparing polylactic acid color master batch, which is basically the same as example 2, and only differs in that: and (3) dehydrating the intermediate product II by adopting a decanter centrifuge in the step (4), and increasing the time for centrifuging the intermediate product II by adopting the decanter centrifuge to obtain the color paste with the solid content of 95.5 weight percent.
The final pressure filtration difference of the prepared polylactic acid color master batch is 0.17MPa, and the intrinsic viscosity is 0.525dL/g.
A method for preparing a special-shaped fine denier polylactic acid fiber, which is basically the same as that of example 2, and is different only in that: the polylactic acid color master batch is prepared by the method.
The special-shaped fine denier polylactic acid fiber finally prepared has the single filament number of 1.5D, the pigment content of 0.8wt percent, the breaking strength of 3.15cN/dtex and 1 yarn floating phenomenon in the spinning process.
As can be seen from comparing example 2 with comparative example 6, the intermediate product II obtained in comparative example 6 has too high solid content, which results in more dust emission during the mixing and drying process of the color paste and the polylactic acid powder, because the mixing time from the liquid state to the dry state is too short, the pigment and the polylactic acid resin are not sufficiently bonded, and the state of fine sand of the material is not easily reached, so that the fine dust is easy to fly.
Example 3
A preparation method of polylactic acid color master batch comprises the following steps:
(1) Preparing raw materials;
and (3) pigment: pigment Black 7, manufactured by European Union engineering charcoal (Qingdao Co., ltd., trade name Aro)sperse TM F138A；
Water;
coating agent: consists of A (polyethylene glycol with relative molecular weight of 8000) and B (triethanolamine) in a mass ratio of 4:1;
polylactic acid powder: manufacturer is Anhui Feng Yuanfu Talai lactic acid Co., ltd, trade mark is FY601, melt index is 9g/10min, weight-average relative molecular weight is 18 ten thousand;
hydrolysis inhibitor: monomeric carbodiimide;
(2) Mixing 30wt% of pigment, 1wt% of coating agent and the balance of water for 30min at 45 ℃ and a rotating speed of 800rpm by adopting a high-speed dispersing machine to obtain an intermediate product I;
(3) Firstly, carrying out rough grinding on the intermediate product I for 30min by using zirconium beads with the diameter of 0.6-0.8mm by adopting a sand mill, then, carrying out fine grinding on the intermediate product I after rough grinding for 45min by using zirconium beads with the diameter of 0.3-0.4mm, and finally, carrying out superfine grinding on the intermediate product I after fine grinding for 60min by using zirconium beads with the diameter of 0.08-0.12mm to obtain an intermediate product II with the solid content of 30.4 wt%;
(4) Dehydrating the intermediate product II by adopting a decanter centrifuge to obtain color paste with the solid content of 78.1 weight percent;
the average grain diameter of the prepared color paste is 0.15 mu m;
(5) Mixing color paste and polylactic acid powder in a high-speed mixer with the temperature of 105 ℃ and the rotating speed of 1000rpm for 40min to remove the solvent, obtaining mixed powder with the trace moisture of 0.5 weight percent, uniformly mixing 99.5 weight percent of the mixed powder with the rest hydrolysis inhibitor according to the weight percent, and feeding the mixed powder and the rest hydrolysis inhibitor into a double-screw extruder for extrusion granulation, thus obtaining the polylactic acid color master batch.
The final pressure filtration difference of the prepared polylactic acid color master batch is 0.07MPa, and the intrinsic viscosity is 0.540dL/g.
The preparation method of the special-shaped fine denier polylactic acid fiber comprises the steps of blending the prepared polylactic acid color master batch and polylactic acid slices (manufactured by Anhui Feng Yuanfu Talai lactic acid Co., ltd., brand FY601, melting point 175 ℃) according to the mass ratio of 6:94, drying until the water content is below 0.004%, and carrying out melt spinning to obtain the special-shaped fine denier polylactic acid fiber;
the spinning process parameters are as follows: the spinneret holes are cross-shaped, the temperature of the first area of the screw is 200 ℃, the temperature of the second area of the screw is 210 ℃, the temperature of the third area of the screw is 215 ℃, the temperature of the fourth area of the screw is 220 ℃, the temperature of the fifth area of the screw is 225 ℃, the temperature of the box body is 230 ℃, and the spinning speed is 1300m/min.
The special-shaped fine denier polylactic acid fiber finally prepared has the single filament number of 1.5D, the cross-section shape of the fiber, the pigment content of 2.0wt percent and the breaking strength of 3.40cN/dtex, and can be continuously spun without broken ends and floating filaments.
Example 4
A preparation method of polylactic acid color master batch comprises the following steps:
(1) Preparing raw materials;
and (3) pigment: pigment violet 23, manufacturer titanium cation chemical pigment (Shanghai) limited, brand D5800;
water;
coating agent: consists of A (polyethylene glycol with relative molecular weight of 12000) and B (neopentyl glycol) in a mass ratio of 3:1;
polylactic acid powder: manufacturer is Anhui Feng Yuanfu Talai lactic acid Co., ltd, trade mark is FY601, melt index is 9g/10min, weight-average relative molecular weight is 18 ten thousand;
hydrolysis inhibitor: monomeric carbodiimide;
(2) Mixing 25wt% of pigment, 0.8wt% of coating agent and the balance of water for 35min at 45 ℃ with a high-speed dispersing machine at a rotating speed of 800rpm to obtain an intermediate product I;
(3) Firstly, carrying out rough grinding on the intermediate product I for 45min by using zirconium beads with the diameter of 0.6-0.8mm by adopting a sand mill, then, carrying out fine grinding on the intermediate product I after rough grinding for 50min by using zirconium beads with the diameter of 0.3-0.4mm, and finally, carrying out superfine grinding on the intermediate product I after fine grinding for 90min by using zirconium beads with the diameter of 0.08-0.12mm to obtain an intermediate product II with the solid content of 25.3 wt%;
(4) Dehydrating the intermediate product II by adopting a decanter centrifuge to obtain color paste with the solid content of 70.0 wt%;
the average grain diameter of the prepared color paste is 0.22 mu m;
(5) Mixing color paste and polylactic acid powder in a high-speed mixer with the temperature of 110 ℃ and the rotating speed of 1200rpm for 30min to remove the solvent, obtaining mixed powder with the trace moisture of 0.4 weight percent, uniformly mixing 99.6 weight percent of the mixed powder and the balance of hydrolysis inhibitor according to the weight percent, and feeding the mixed powder and the balance of hydrolysis inhibitor into a double-screw extruder for extrusion granulation, thus obtaining the polylactic acid color master batch.
The final pressure filtration difference of the prepared polylactic acid color master batch is 0.18MPa, and the intrinsic viscosity is 0.528dL/g.
The preparation method of the special-shaped fine denier polylactic acid fiber comprises the steps of blending the prepared polylactic acid color master batch and polylactic acid slices (manufactured by Anhui Feng Yuanfu Talai lactic acid Co., ltd., brand FY601, melting point 175 ℃) according to the mass ratio of 1:99, drying until the water content is below 0.004%, and carrying out melt spinning to obtain the special-shaped fine denier polylactic acid fiber;
the spinning process parameters are as follows: the spinneret holes are in a trilobal shape, the temperature of a first area of a screw is 200 ℃, the temperature of a second area of the screw is 210 ℃, the temperature of a third area of the screw is 215 ℃, the temperature of a fourth area of the screw is 220 ℃, the temperature of a fifth area of the screw is 225 ℃, the temperature of a box body is 230 ℃, and the spinning speed is 1000m/min.
The special-shaped fine denier polylactic acid fiber finally prepared has the single filament number of 1.2D, the cross section of the fiber is trilobal, the pigment content is 0.1wt%, the breaking strength is 3.26cN/dtex, and the special-shaped fine denier polylactic acid fiber can be continuously spun without broken ends and floating filaments.
Example 5
A preparation method of polylactic acid color master batch comprises the following steps:
(1) Preparing raw materials;
and (3) pigment: pigment green 7, manufacturer is Clariant chemical (China) Co., ltd, brand PV Fast Green GNX;
water;
coating agent: consists of A (polyethylene glycol with relative molecular weight of 12000) and B (trimethylamine) in a mass ratio of 3:1;
polylactic acid powder: manufacturer is Anhui Feng Yuanfu Talai lactic acid Co., ltd, trade mark is FY601, melt index is 9g/10min, weight-average relative molecular weight is 18 ten thousand;
hydrolysis inhibitor: polymeric carbodiimides;
(2) Mixing 30wt% of pigment, 0.8wt% of coating agent and the balance of water for 35min at the temperature of 50 ℃ and the rotating speed of 1000rpm by adopting a high-speed dispersing machine to obtain an intermediate product I;
(3) Firstly, carrying out rough grinding on the intermediate product I for 45min by using zirconium beads with the diameter of 0.6-0.8mm by adopting a sand mill, then, carrying out fine grinding on the intermediate product I after rough grinding for 50min by using zirconium beads with the diameter of 0.3-0.4mm, and finally, carrying out superfine grinding on the intermediate product I after fine grinding for 80min by using zirconium beads with the diameter of 0.08-0.12mm to obtain an intermediate product II with the solid content of 30 wt%;
(4) Dehydrating the intermediate product II by adopting a decanter centrifuge to obtain color paste with the solid content of 74.6 wt%;
the average grain diameter of the prepared color paste is 0.30 mu m;
(5) Mixing color paste and polylactic acid powder in a high-speed mixer with the temperature of 100 ℃ and the rotating speed of 1200rpm for 30min to remove the solvent, obtaining mixed powder with the trace moisture of 0.3 weight percent, uniformly mixing 99.7 weight percent of the mixed powder with the rest hydrolysis inhibitor according to the weight percent, and feeding the mixed powder into a double-screw extruder for extrusion granulation, thus obtaining the polylactic acid color master batch.
The pressure filtration difference of the finally prepared polylactic acid color master batch is 0.24MPa, and the intrinsic viscosity is 0.526dL/g.
The preparation method of the special-shaped fine denier polylactic acid fiber comprises the steps of blending the prepared polylactic acid color master batch and polylactic acid slices (manufactured by Anhui Feng Yuanfu Talai lactic acid Co., ltd., brand FY601, melting point 175 ℃) according to the mass ratio of 3:97, drying until the water content is below 0.004%, and carrying out melt spinning to obtain the special-shaped fine denier polylactic acid fiber;
the spinning process parameters are as follows: the spinneret holes are in a trilobal shape, the temperature of a first area of a screw is 200 ℃, the temperature of a second area of the screw is 210 ℃, the temperature of a third area of the screw is 215 ℃, the temperature of a fourth area of the screw is 220 ℃, the temperature of a fifth area of the screw is 225 ℃, the temperature of a box body is 230 ℃, and the spinning speed is 1200m/min.
The special-shaped fine denier polylactic acid fiber finally prepared has the single filament number of 1.2D, the cross section of the fiber is trilobal, the pigment content is 1wt%, the breaking strength is 3.3cN/dtex, and the special-shaped fine denier polylactic acid fiber can be continuously spun without broken ends and floating filaments.
Example 6
A preparation method of polylactic acid color master batch comprises the following steps:
(1) Preparing raw materials;
and (3) pigment: pigment Blue 15:3, manufacturer is Clariant chemical (China) Co., ltd, and the brand is PV Fast Blue BG;
water;
coating agent: consists of A (polyethylene glycol with relative molecular weight of 12000) and B (neopentyl glycol) in a mass ratio of 2:1;
polylactic acid powder: manufacturer is Anhui Feng Yuanfu Talai lactic acid Co., ltd, trade mark is FY601, melt index is 9g/10min, weight-average relative molecular weight is 18 ten thousand;
hydrolysis inhibitor: a mixture of polymeric carbodiimide and monomeric carbodiimide in a mass ratio of 1:1;
(2) Mixing 25wt% of pigment, 0.5wt% of coating agent and the balance of water for 60min at the temperature of 50 ℃ and the rotating speed of 1000rpm by adopting a high-speed dispersing machine to obtain an intermediate product I;
(3) Firstly, carrying out rough grinding on the intermediate product I for 60min by using zirconium beads with the diameter of 0.6-0.8mm by adopting a sand mill, then, carrying out fine grinding on the intermediate product I after rough grinding for 30min by using zirconium beads with the diameter of 0.3-0.4mm, and finally, carrying out superfine grinding on the intermediate product I after fine grinding for 90min by using zirconium beads with the diameter of 0.08-0.12mm to obtain an intermediate product II with the solid content of 25.1 wt%;
(4) Dehydrating the intermediate product II by adopting a decanter centrifuge to obtain color paste with the solid content of 74.8 wt%;
the average grain diameter of the prepared color paste is 0.24 mu m;
(5) Mixing color paste and polylactic acid powder in a high-speed mixer with the temperature of 110 ℃ and the rotating speed of 1400rpm for 30min to remove the solvent, obtaining mixed powder with the trace moisture of 0.3 weight percent, uniformly mixing 99.7 weight percent of the mixed powder with the rest hydrolysis inhibitor according to the weight percent, and feeding the mixed powder into a double-screw extruder for extrusion granulation, thus obtaining the polylactic acid color master batch.
The pressure filtration difference of the finally prepared polylactic acid color master batch is 0.15MPa, and the intrinsic viscosity is 0.500dL/g.
The preparation method of the special-shaped fine denier polylactic acid fiber comprises the steps of blending the prepared polylactic acid color master batch and polylactic acid slices (manufactured by Anhui Feng Yuanfu Talai lactic acid Co., ltd., brand FY601, melting point 175 ℃) according to the mass ratio of 4:96, drying until the water content is below 0.004%, and carrying out melt spinning to obtain the special-shaped fine denier polylactic acid fiber;
the spinning process parameters are as follows: the spinneret holes are hollow, the temperature of the first area of the screw is 200 ℃, the temperature of the second area of the screw is 210 ℃, the temperature of the third area of the screw is 215 ℃, the temperature of the fourth area of the screw is 220 ℃, the temperature of the fifth area of the screw is 225 ℃, the temperature of the box body is 230 ℃, and the spinning speed is 1000m/min.
The special-shaped fine denier polylactic acid fiber finally prepared has the single filament number of 1D, the cross section of the fiber is hollow, the pigment content is 1.2wt%, the breaking strength is 3.2cN/dtex, and the special-shaped fine denier polylactic acid fiber can be continuously spun without broken ends and floating filaments.
Example 7
A preparation method of polylactic acid color master batch comprises the following steps:
(1) Preparing raw materials;
and (3) pigment: pigment green 7 and pigment violet 23 in a mass ratio of 1:1; pigment green 7 is manufactured by Clariant chemical (China) Co., ltd, with the brand name of PV Fast Green GNX; pigment violet 23 is available from titanium cation chemical pigment (Shanghai) Co., ltd, under the designation D5800;
water;
coating agent: consists of A (polyethylene glycol with relative molecular weight of 12000) and B (mixture of neopentyl glycol and trimethylamine with mass ratio of 1:1) in mass ratio of 3:1;
polylactic acid powder: manufacturer is Anhui Feng Yuanfu Talai lactic acid Co., ltd, trade mark is FY601, melt index is 9g/10min, weight-average relative molecular weight is 18 ten thousand;
hydrolysis inhibitor: polymeric carbodiimides;
(2) Mixing 25wt% of pigment, 0.8wt% of coating agent and the balance of water for 40min at 45 ℃ by adopting a high-speed dispersing machine at a rotating speed of 1000rpm to obtain an intermediate product I;
(3) Firstly, carrying out rough grinding on the intermediate product I for 60min by using zirconium beads with the diameter of 0.6-0.8mm by adopting a sand mill, then, carrying out fine grinding on the intermediate product I after rough grinding for 50min by using zirconium beads with the diameter of 0.3-0.4mm, and finally, carrying out superfine grinding on the intermediate product I after fine grinding for 100min by using zirconium beads with the diameter of 0.08-0.12mm to obtain an intermediate product II with the solid content of 25.3 wt%;
(4) Dehydrating the intermediate product II by adopting a decanter centrifuge to obtain color paste with 77.2 weight percent of solid content;
the average grain diameter of the prepared color paste is 0.26 mu m;
(5) Mixing color paste and polylactic acid powder in a high-speed mixer with the temperature of 110 ℃ and the rotating speed of 1200rpm for 30min to remove the solvent, obtaining mixed powder with the trace moisture of 0.1 weight percent, uniformly mixing 99.9 weight percent of the mixed powder and the balance of hydrolysis inhibitor according to the weight percent, and feeding the mixed powder and the balance of hydrolysis inhibitor into a double-screw extruder for extrusion granulation, thus obtaining the polylactic acid color master batch.
The final pressure filtration difference of the prepared polylactic acid color master batch is 0.21MPa, and the intrinsic viscosity is 0.522dL/g.
The preparation method of the special-shaped fine denier polylactic acid fiber comprises the steps of blending the prepared polylactic acid color master batch and polylactic acid slices (manufactured by Anhui Feng Yuanfu Talai lactic acid Co., ltd., brand FY601, melting point 175 ℃) according to the mass ratio of 4:96, drying until the water content is below 0.004%, and carrying out melt spinning to obtain the special-shaped fine denier polylactic acid fiber;
the spinning process parameters are as follows: the spinneret holes are hollow, the temperature of the first area of the screw is 200 ℃, the temperature of the second area of the screw is 210 ℃, the temperature of the third area of the screw is 215 ℃, the temperature of the fourth area of the screw is 220 ℃, the temperature of the fifth area of the screw is 225 ℃, the temperature of the box body is 230 ℃, and the spinning speed is 1000m/min.
The special-shaped fine denier polylactic acid fiber finally prepared has the single filament number of 1D, the cross section of the fiber is hollow, the pigment content is 1.2 weight percent, the breaking strength is 3.29cN/dtex, and the special-shaped fine denier polylactic acid fiber can be continuously spun without broken ends and floating filaments.

Claims (10)

1. The preparation method of the polylactic acid color master batch is characterized by comprising the following steps:
(1) Uniformly mixing pigment, water and a coating agent to obtain an intermediate product I, wherein the mixing temperature is 40-50 ℃;
(2) Sequentially carrying out coarse grinding, fine grinding and superfine grinding on the intermediate product I to obtain an intermediate product II;
(3) Dehydrating the intermediate product II to obtain color paste with the solid content of 70-80 wt%;
(4) Blending color paste and polylactic acid powder, removing solvent in the blending process, uniformly mixing the obtained mixed powder with an anti-hydrolysis agent, and feeding the mixture into a double-screw extruder for extrusion granulation to obtain the polylactic acid color master batch, wherein the weight average relative molecular weight of the polylactic acid powder is 18-19 ten thousand.
2. The method for preparing polylactic acid color master batch according to claim 1, wherein in the step (1), the pigment is more than one of pigment red 122, pigment violet 23, pigment green 7, pigment yellow 150, pigment black 7 and pigment blue 15:3; the coating agent consists of A and B in the mass ratio of 2-4:1, wherein A is polyethylene glycol with the relative molecular weight of more than or equal to 8000, and B is more than one of trimethylolethane, trimethylolpropane, neopentyl glycol, triethanolamine and trimethylamine; the mixing speed is 500-1000rpm, and the mixing time is 30-60min.
3. The method for preparing polylactic acid color master batch according to claim 1, wherein in the step (2), zirconium beads with the diameter of 0.6-0.8mm are adopted for rough grinding for 30-60min; the fine grinding adopts zirconium beads with the diameter of 0.3-0.4mm for 30-60min; zirconium beads with the diameter of 0.08-0.12mm are adopted for superfine grinding, and the time is 60-120min.
4. The method for preparing polylactic acid color master batch according to claim 1, wherein in the step (2), the solid content of the intermediate product II is 20.0-30.4wt%.
5. The method for producing polylactic acid color master batch according to claim 1, wherein in the step (1), the average particle diameter of the pigment is 0.5 to 6.5 μm; in the step (3), the average particle size of the color paste is 0.1-0.3 mu m.
6. The method for preparing polylactic acid color master batch according to claim 1, wherein in the step (3), the color paste consists of 70-80wt% of pigment, 1.5-3.0wt% of coating agent and the balance of water according to weight percentage.
7. The method for preparing the polylactic acid color master batch according to claim 1, wherein in the step (4), the color paste and the polylactic acid powder are blended, and the solvent is removed in the blending process, specifically, the color paste and the polylactic acid powder are mixed for 30-60min in a high-speed mixer with the temperature of 100-110 ℃ and the rotating speed of 500-1400 rpm.
8. The method for preparing polylactic acid color master batch according to claim 1, wherein in the step (4), the addition amount of each component fed into the twin-screw extruder is as follows in percentage by weight: 99.5 to 99.9 weight percent of mixed powder and 0.1 to 0.5 weight percent of hydrolysis inhibitor.
9. A polylactic acid color master batch, characterized by being prepared by the method for preparing a polylactic acid color master batch according to any one of claims 1 to 8.
10. A method for preparing special-shaped fine denier polylactic acid fibers by adopting a masterbatch method, which is characterized in that the masterbatch is a polylactic acid color masterbatch as defined in claim 9.
CN202311589332.3A 2023-11-27 2023-11-27 Polylactic acid color master batch and preparation method and application thereof Pending CN117430835A (en)

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