CN115403904B - Biodegradable PBAT color master batch and fiber prepared from same - Google Patents

Biodegradable PBAT color master batch and fiber prepared from same Download PDF

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CN115403904B
CN115403904B CN202211246512.7A CN202211246512A CN115403904B CN 115403904 B CN115403904 B CN 115403904B CN 202211246512 A CN202211246512 A CN 202211246512A CN 115403904 B CN115403904 B CN 115403904B
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pbat
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CN115403904A (en
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倪钧
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Yancheng Ruize Color Masterbatch Co ltd
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    • 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
    • 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
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • D01F1/06—Dyes
    • 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
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2467/06—Unsaturated polyesters

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention relates to the technical field of degradable master batches, in particular to a biodegradable PBAT color master batch and fibers prepared by the same, which comprise the following processes: and (3) fully mixing PBAT powder, a biomass dye and a dispersing agent, blending and granulating, wherein the temperature of each region of the double-screw extruder is set to 140-150 ℃ and the temperature of a machine head is 145 ℃ to obtain color master batches, and the dispersing agent comprises KH550 and maleic acid lanthanum modified unsaturated polyester with a branched structure. According to the invention, the unsaturated polyester in the blend of the PBAT resin and the biomass dye can keep the degradability of the color master batch, reduce the viscosity, improve the processing performance, reduce the agglomeration of the biomass dye, ensure that the biomass dye is uniformly dispersed, improve the thermal stability, jointly induce crystallization, promote nucleation, improve the crystallization performance and strengthen and toughen the color master batch; and the modified polyurethane can be added with a silane coupling agent KH560, so that the initial decomposition temperature is increased, the degradation of the molecular chains of the masterbatch component is relieved, the melt strength is improved, and the application of the masterbatch in colored fibers is facilitated.

Description

Biodegradable PBAT color master batch and fiber prepared from same
Technical Field
The invention relates to the technical field of degradable master batches, in particular to a biodegradable PBAT color master batch and fibers prepared from the same.
Background
With the rapid development of the chemical fiber industry, the increasing environmental awareness and the promotion of sustainable development concept, biodegradable polymers are represented by poly (butylene adipate-terephthalate) (PBAT), poly (lactic acid) (PLA), poly (butylene succinate) (PBS), etc., and have been widely used because of their good thermal properties, mechanical properties and processability, and are gradually replacing traditional polymers. The application of the biodegradable polyester on the fiber material not only relieves the problem of environmental pollution, but also implements the ideas of green, environment protection and low carbon, and has wide development prospect and application advantage. The biomass dye is a pigment for dyeing processing, and can realize greenization of dye preparation, cleanliness of fiber coloring and ecologization of fiber products. People use the pigment as a component in the degradable colored fibers, prepare color master batches and apply the color master batches to the degradable colored fibers, and use the color master batches and the biodegradable polymers in a matching way, so that the green application of the colored fibers is realized. Before preparing the degradable colored fiber, the masterbatch is prepared, and then the masterbatch is mixed with polyester to realize fiber coloring. The dispersion degree of the biomass dye in the polyester resin influences the tinting strength and spinnability of the tinting masterbatch, the suitability of the biomass dye to the processing temperature in the melt spinning process, and the existing biomass dye also contains active amino groups which can react with polyester molecular chains, cut off macromolecules and accelerate polyester degradation, so that the performance of the finally prepared colored fiber can be significantly influenced. And, instead, the method comprises the steps of. Therefore, we propose a biodegradable PBAT masterbatch and fibers prepared therefrom.
Disclosure of Invention
The invention aims to provide biodegradable PBAT color master batch and fiber prepared by the same, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: a biodegradable PBAT masterbatch comprising the following process:
and (3) fully mixing PBAT powder, biomass dye and a dispersing agent, blending and granulating, wherein the temperature of each region of the double-screw extruder is set to 140-150 ℃, and the temperature of a machine head is 145 ℃ to obtain color master batches.
Further, the method comprises the following steps:
fully mixing the dried PBAT powder, the biomass dye and the dispersing agent, adding the mixture into a mixed solution of absolute ethyl alcohol and deionized water, carrying out constant-temperature water bath at 60-80 ℃, and carrying out ultrasonic dispersion for 10-16 h; vacuum drying in vacuum oven at 60-80 deg.c for 10-15 hr;
blending and granulating, wherein the temperature of each region of the twin-screw extruder is set to 140-150 ℃ and the temperature of the machine head is 145 ℃ to obtain the masterbatch.
Further, the drying process comprises the following steps: drying in a vacuum oven at 80 ℃ for 10 hours;
the temperatures of the zones of the twin-screw extruder were: one zone 140 ℃, two zones 145 ℃, three zones 150 ℃, four zones 150 ℃, five zones 150 ℃.
Further, the volume ratio of the absolute ethyl alcohol to the deionized water in the mixed solution is 9:1.
Further, the color master batch comprises the following components in parts by weight: 85-90 parts of PBAT powder, 10-15 parts of biomass dye and 5-15 parts of dispersing agent.
Further, the dispersing agent is one or two of silane coupling agent KH550 and unsaturated polyester.
PBAT (polybutylene adipate-terephthalate) powder: TH801T derived from the company of the mountain river, ltd, blue in Xinjiang;
biomass dye: indigo dye, life green dye, watermelon red dye, from Changzhou meisheng biological materials limited company;
silane coupling agent KH560: from Shanghai high-confidence glassware Co., ltd;
further, the unsaturated polyester is lanthanum ion modified branched polyester, and is prepared by the following process:
(1) Heating succinic acid and dimethylolpropionic acid to 175-180 ℃ for melting, cooling to 140-150 ℃, adding pentaerythritol, butanediol and catalyst p-toluenesulfonic acid, stirring in a nitrogen atmosphere, slowly adding unsaturated acid and caproic acid for esterification, carrying out heat preservation reaction for 50-75 min, decompressing and vacuumizing to 0.08-0.10 MPa, and reacting until the acid value is less than 10mgKOH/g to obtain branched polyester;
the molar ratio of succinic acid to dimethylolpropionic acid to pentaerythritol to butanediol to unsaturated acid to caproic acid is (1-2): 6-8): 1 (1.0-2.5): 1-2): 1.0-1.5;
the unsaturated acid is one or more of fumaric acid, maleic acid, linoleic acid and oleic acid;
in the technical scheme, succinic acid and dimethylolpropionic acid are taken as carboxyl sources, pentaerythritol, butanediol and dimethylolpropionic acid are taken as hydroxyl sources, esterification reaction is carried out under the action of catalyst p-toluenesulfonic acid to form an esterified polymer with a branched structure, the esterified polymer reacts with unsaturated acid, and unsaturated bonds are introduced at the end of the esterified polymer to obtain the polyester with unsaturated double bonds (namely branched polyester).
The branched polyester has a multi-branched structure, and can reduce the viscosity of the system, improve the processing performance of the system, avoid the generation of additional acting force due to melt flow in the melt blending process and relieve the degradation of the PBAT resin at high temperature when being co-extruded with materials; and the compatibility between the PBAT powder and the biomass dye can be improved, the uniform dispersion of the biomass dye in the PBAT resin is promoted, and the stability of the system is improved.
The branched polyester has biodegradability, and can maintain the biodegradation property of the color master batch after being blended with the PBAT resin; compared with PBAT resin, the branched polyester has more flexible molecular structure and lower modulus, can improve the toughness of the blend and toughen the color master batch.
In addition, oleic acid/linoleic acid with a long chain structure is preferable in unsaturated acid, the melt viscosity is reduced, the improvement of the melt strength is facilitated, the entanglement of long chains and the molecular chains of the PBAT resin is improved, the interfacial adhesion between the long chains and the PBAT resin is improved, and the heat resistance and the toughness of the prepared color master batch are improved.
(2) The branched polyester is placed in a blowing dryer at 60-80 ℃ for 10-15 hours, lanthanum maleate, glycollic acid and dicumyl peroxide are added, and banburying is carried out for 8-10 minutes under the conditions of the temperature of 165-170 ℃ and the rotating speed of 35-45 r/min, thus obtaining unsaturated polyester;
the mass ratio of the branched polyester to the maleic acid lanthanum to the glycollic acid to the dicumyl peroxide is 100 (3-10), 3-6 and 0.4-0.7.
In the technical scheme, under the action of dicumyl peroxide, the radical reaction between unsaturated double bonds in branched polyester and olefin bonds in lanthanum maleate is initiated, lanthanum maleate is grafted in the molecular chain of branched polyester, and the lanthanum ion modified branched polyester is obtained, and the addition of glycollic acid is beneficial to the improvement and improvement of the grafting rate, melt strength and crystallinity of the system, and the prepared modified product still has an unsaturated structure through the control of the dosage of lanthanum maleate.
The terminal group of branched polyester is alkyl by controlling the dosage of the components such as succinic acid, dimethylol propionic acid, pentaerythritol, butanediol, unsaturated acid, caproic acid and the like, and the introduction of lanthanum maleate preferentially generates ion-dipole action with polar groups such as amino, phenolic hydroxyl, carbonyl and the like in the biomass dye according to the difference of the polarities of the groups so as to carry out apparent crosslinking; the dye is coated, so that the chemical and physical actions among biomass dyes are reduced, agglomeration is reduced, metal lanthanum ions are cooperated, the stability of the masterbatch is improved, the dispersion uniformity of the biomass dyes in the PBAT resin is remarkably improved, the agglomeration and surface defects are reduced, the phenomenon of local thermal decomposition is avoided, and the stability of the mechanical property is maintained. The heterogeneous nucleation and the homogeneous nucleation can be performed, simultaneously, the biomass dye also plays a role of a nucleating agent, and the crystallization is synergistically induced, so that the crystallization capability of the blend is improved, the crystal nucleus is increased, the crystallization rate is accelerated, and the improvement of the mechanical property of the prepared color master batch is promoted.
When PBAT powder, biomass dye (vital green dye) and dispersant unsaturated polyester are blended, michael addition is carried out on amino groups in the biomass dye and carbon-carbon double bonds in the unsaturated polyester to generate covalent bonds, so that the color fastness and initial decomposition temperature of the masterbatch are improved, and the thermal stability of the masterbatch is improved. When the silane coupling agent KH550 is added in the color master batch, the ion-dipole adsorption effect is adopted, and Michael addition is carried out on the unsaturated polyester, so that double bonds in the color master batch system are eliminated, and the thermal stability of the color master batch is improved; and the silicon hydroxyl in the silane coupling agent KH550 can react with water molecules in the system, so that the degradation of the molecular chain of the masterbatch component and the reduction of the melt strength are further relieved, and the application of the masterbatch in colored fibers is facilitated.
A fiber prepared from biodegradable PBAT color master batch, comprising the following processes:
and mixing the dried color master batch with PBAT slices, and carrying out melt spinning, wherein the temperature of each area of the screw is set to 247-271 ℃ to obtain the colored fiber.
Further, in the melt spinning process, the temperatures of each zone of the screw are as follows: one zone 247 ℃, two zones 271 ℃, three zones 271 ℃, four zones 270 ℃, the temperature of a metering pump is 270 ℃, the temperature of a bent pipe is 270 ℃, and the pump supply amount is 35g/min;
the number of the spinneret holes is 36, the diameter of the spinneret hole is 0.4mm, and the spinning speed is 500m/min.
Further, the drying process comprises the following steps: air drying at 80deg.C for 4 hr, and high vacuum drying at 80deg.C for 24 hr.
Further, the colored fiber comprises the following components in parts by weight: 90 parts of PBAT slice and 10 parts of color master batch.
Further, the colored fiber also comprises 0.3 to 1.0 part of silane coupling agent KH560.
In the technical scheme, the PBAT slice and the color master batch are blended, and the colored fiber is prepared by melt spinning, so that the mechanical property and the color effect of the prepared colored fiber are excellent and stable due to the excellent thermal stability and mechanical property of the color master batch. The addition of the dispersing agent unsaturated polyester in the color master batch improves the viscosity difference between the color master batch dyeing component and the PBAT resin in the colored fiber, reduces the fluidity difference during processing, has good stability in a processing temperature window, improves the ductility of an internal molecular chain, improves the spinnability of the fiber, and relieves the thermal degradation phenomenon in the spinning process.
The existence of maleic acid lanthanum (Lewis acid) in the color master batch can promote the ring opening of epoxy groups in the silane coupling agent KH560, react with carboxyl and hydroxyl generated by the thermal degradation of the PBAT resin to generate a cured product containing ester groups or hydroxyl, and perform transesterification reaction, so that the degradability of the colored fiber is maintained, and the prepared colored fiber can maintain excellent and stable mechanical properties and color effects.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the biodegradable PBAT color master batch, the unsaturated polyester with a branched structure and modified by lanthanum maleate is introduced into the PBAT resin and biomass dye blend, so that the degradability of the color master batch can be maintained, the viscosity is reduced, the processing performance is improved, meanwhile, the agglomeration of biomass dye is reduced, the biomass dye is uniformly dispersed, the thermal stability is improved, the crystallization is jointly induced, the nucleation is promoted, the crystallization performance is improved, and the color master batch is reinforced and toughened; and the modified polyurethane can be added with a silane coupling agent KH560, so that the initial decomposition temperature is increased, the degradation of the molecular chains of the masterbatch component is relieved, the melt strength is improved, and the application of the masterbatch in colored fibers is facilitated.
2. According to the fiber prepared from the biodegradable PBAT color master batch, the viscosity difference between the biomass dye and the PBAT resin is reduced by adding the dispersing agent unsaturated polyester into the color master batch, the fluidity difference during processing is reduced, the fiber has good stability, the ductility of a molecular chain is improved, the spinnability of the fiber is improved, and the thermal degradation phenomenon in the spinning process is relieved; the existence of the maleic acid lanthanum structure can promote the ring opening of epoxy groups, so that the epoxy groups can react with carboxyl and hydroxyl generated by the thermal degradation of the PBAT resin, the curing is carried out, the transesterification is carried out, and the degradability, the mechanical property and the color effect of the colored fiber are kept excellent and stable.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
PBAT (polybutylene adipate-terephthalate) powder: TH801T derived from the company of the mountain river, ltd, blue in Xinjiang;
biomass dye: indigo dye, life green dye, watermelon red dye, from Changzhou meisheng biological materials limited company;
silane coupling agent KH560: from Shanghai high-confidence glassware Co., ltd;
example 1
(1) Preparation of unsaturated polyester:
1.1. heating 118g of succinic acid and 804g of dimethylolpropionic acid to 175 ℃ for melting, cooling to 140 ℃, adding 136g of pentaerythritol, 90g of butanediol and 6.4g of catalyst p-toluenesulfonic acid, stirring in a nitrogen atmosphere, slowly adding 116g of unsaturated acid fumaric acid and 116g of caproic acid for esterification, carrying out heat preservation reaction for 50min, decompressing and vacuumizing to 0.08MPa, and reacting until the acid value is less than 10mgKOH/g to obtain branched polyester;
1.2. drying 1000g of branched polyester in a blowing way at 60 ℃ for 10 hours, adding 30g of lanthanum maleate, 30g of glycolic acid and 4g of dicumyl peroxide, and banburying for 8 minutes at the temperature of 165 ℃ and the rotating speed of 45r/min to obtain unsaturated polyester;
(2) Preparation of color master batch:
taking 9.0kg of PBAT powder, 1.0kg of biomass dye indigo dye, 0.1kg of dispersing agent, namely silane coupling agent KH550 and 0.4kg of unsaturated polyester which are dried in a vacuum oven at 80 ℃ for 10 hours, fully mixing, adding the mixture of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 9:1), and carrying out ultrasonic dispersion for 10 hours in a constant-temperature water bath at 60 ℃; vacuum drying in a vacuum oven at 60 ℃ for 10 hours; blending and granulating, wherein the temperature of each region of the twin-screw extruder is set to 140-150 ℃ and the temperature of the machine head is 145 ℃ to obtain the masterbatch.
(3) Preparation of colored fibers:
taking 90kg of PBAT slices, 10kg of color master batch and 0.3kg of silane coupling agent KH560, mixing, carrying out melt spinning, wherein the temperature of each region of a screw in the melt spinning process is as follows: one zone 247 ℃, two zones 271 ℃, three zones 271 ℃, four zones 270 ℃, the temperature of a metering pump is 270 ℃, the temperature of a bent pipe is 270 ℃, and the pump supply amount is 35g/min; the number of spinneret holes is 36, the diameter of the spinneret hole is 0.4mm, and the spinning speed is 500m/min, so that the colored fiber is obtained.
Example 2
(1) Preparation of unsaturated polyester:
1.1. 177g of succinic acid and 938g of dimethylolpropionic acid are heated to 178 ℃ for melting, the temperature is reduced to 145 ℃, 136g of pentaerythritol, 158g of butanediol and 7.8g of catalyst p-toluenesulfonic acid are added, and in a nitrogen atmosphere, 560g of unsaturated acid linoleic acid and 145g of caproic acid are slowly added for esterification, the temperature is kept for 60min, vacuum pumping is carried out to 0.09MPa, and the reaction is carried out until the acid value is less than 10mgKOH/g, thus obtaining branched polyester;
1.2. drying 1000g of branched polyester in a blast at 70 ℃ for 12 hours, adding 65g of lanthanum maleate, 45g of glycolic acid and 5g of dicumyl peroxide, and banburying for 9 minutes at 168 ℃ and a rotating speed of 40r/min to obtain unsaturated polyester;
(2) Preparation of color master batch:
taking 8.8kg of PBAT powder, 1.2kg of biomass dye indigo dye, 0.2kg of dispersing agent silane coupling agent KH550 and 0.8kg of unsaturated polyester after drying in a vacuum oven at 80 ℃ for 10 hours, adding the mixture of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 9:1), carrying out ultrasonic dispersion for 15 hours in a constant-temperature water bath at 70 ℃; vacuum drying in a vacuum oven at 70deg.C for 12 hr; blending and granulating, wherein the temperature of each region of the twin-screw extruder is set to 140-150 ℃ and the temperature of the machine head is 145 ℃ to obtain the masterbatch.
(3) Preparation of colored fibers:
taking 90kg of PBAT slices, 10kg of color master batch and 0.6kg of silane coupling agent KH560, mixing, carrying out melt spinning, wherein the temperature of each region of a screw in the melt spinning process is as follows: one zone 247 ℃, two zones 271 ℃, three zones 271 ℃, four zones 270 ℃, the temperature of a metering pump is 270 ℃, the temperature of a bent pipe is 270 ℃, and the pump supply amount is 35g/min; the number of spinneret holes is 36, the diameter of the spinneret hole is 0.4mm, and the spinning speed is 500m/min, so that the colored fiber is obtained.
Example 3
(1) Preparation of unsaturated polyester:
1.1. taking 236g of succinic acid and 1072g of dimethylolpropionic acid, heating to 180 ℃ for melting, cooling to 150 ℃, adding 136g of pentaerythritol, 225g of butanediol and 9.2g of catalyst p-toluenesulfonic acid, stirring in a nitrogen atmosphere, slowly adding 116g of unsaturated acid maleic acid and 174g of caproic acid for esterification, carrying out heat preservation reaction for 75min, decompressing and vacuumizing to 0.10MPa, and reacting until the acid value is less than 10mgKOH/g to obtain branched polyester;
1.2. drying 1000g of branched polyester in 80 ℃ for 15h by blowing, adding 100g of lanthanum maleate, 60g of glycolic acid and 7g of dicumyl peroxide, and banburying for 10min at 170 ℃ and a rotating speed of 45r/min to obtain unsaturated polyester;
(2) Preparation of color master batch:
taking 8.5kg of PBAT powder, 1.5kg of biomass dye indigo dye, 0.3kg of dispersing agent silane coupling agent KH550 and 1.2kg of unsaturated polyester after drying in a vacuum oven at 80 ℃ for 10 hours, adding the mixture of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 9:1), carrying out ultrasonic dispersion for 16 hours in a constant-temperature water bath at 80 ℃; vacuum drying in a vacuum oven at 80 ℃ for 15h; blending and granulating, wherein the temperature of each region of the twin-screw extruder is set to 140-150 ℃ and the temperature of the machine head is 145 ℃ to obtain the masterbatch.
(3) Preparation of colored fibers:
taking 90kg of PBAT slices, 10kg of color master batch and 1.0kg of silane coupling agent KH560, which are subjected to forced air drying at 80 ℃ for 4 hours and high vacuum drying at 80 ℃ for 24 hours, mixing, and carrying out melt spinning, wherein in the melt spinning process, the temperatures of all regions of a screw are as follows: one zone 247 ℃, two zones 271 ℃, three zones 271 ℃, four zones 270 ℃, the temperature of a metering pump is 270 ℃, the temperature of a bent pipe is 270 ℃, and the pump supply amount is 35g/min; the number of spinneret holes is 36, the diameter of the spinneret hole is 0.4mm, and the spinning speed is 500m/min, so that the colored fiber is obtained.
Example 4
(1) Preparation of unsaturated polyester:
1.1. 177g of succinic acid and 938g of dimethylolpropionic acid are heated to 178 ℃ for melting, the temperature is reduced to 145 ℃, 136g of pentaerythritol, 158g of butanediol and 7.8g of catalyst p-toluenesulfonic acid are added, and in a nitrogen atmosphere, 560g of unsaturated acid linoleic acid and 145g of caproic acid are slowly added for esterification, the temperature is kept for 60min, vacuum pumping is carried out to 0.09MPa, and the reaction is carried out until the acid value is less than 10mgKOH/g, thus obtaining branched polyester;
1.2. drying 1000g of branched polyester in a blast at 70 ℃ for 12 hours, adding 65g of lanthanum maleate, 45g of glycolic acid and 5g of dicumyl peroxide, and banburying for 9 minutes at 168 ℃ and a rotating speed of 40r/min to obtain unsaturated polyester;
(2) Preparation of color master batch:
taking 8.8kg of PBAT powder, 1.2kg of biomass dye vital green dye and 1.0kg of dispersing agent unsaturated polyester after drying for 10 hours in a vacuum oven at 80 ℃, fully mixing, adding the mixture of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 9:1), and carrying out ultrasonic dispersion for 15 hours in a constant-temperature water bath at 70 ℃; vacuum drying in a vacuum oven at 70deg.C for 12 hr; blending and granulating, wherein the temperature of each region of the twin-screw extruder is set to 140-150 ℃ and the temperature of the machine head is 145 ℃ to obtain the masterbatch.
(3) Preparation of colored fibers:
taking 90kg of PBAT slices, 10kg of color master batch and 0.6kg of silane coupling agent KH560, mixing, carrying out melt spinning, wherein the temperature of each region of a screw in the melt spinning process is as follows: one zone 247 ℃, two zones 271 ℃, three zones 271 ℃, four zones 270 ℃, the temperature of a metering pump is 270 ℃, the temperature of a bent pipe is 270 ℃, and the pump supply amount is 35g/min; the number of spinneret holes is 36, the diameter of the spinneret hole is 0.4mm, and the spinning speed is 500m/min, so that the colored fiber is obtained.
Example 5
(1) Preparation of unsaturated polyester:
1.1. 177g of succinic acid and 938g of dimethylolpropionic acid are heated to 178 ℃ for melting, the temperature is reduced to 145 ℃, 136g of pentaerythritol, 158g of butanediol and 7.8g of catalyst p-toluenesulfonic acid are added, and in a nitrogen atmosphere, 560g of unsaturated acid linoleic acid and 145g of caproic acid are slowly added for esterification, the temperature is kept for 60min, vacuum pumping is carried out to 0.09MPa, and the reaction is carried out until the acid value is less than 10mgKOH/g, thus obtaining branched polyester;
1.2. drying 1000g of branched polyester in a blast at 70 ℃ for 12 hours, adding 65g of lanthanum maleate, 45g of glycolic acid and 5g of dicumyl peroxide, and banburying for 9 minutes at 168 ℃ and a rotating speed of 40r/min to obtain unsaturated polyester;
(2) Preparation of color master batch:
taking 8.8kg of PBAT powder, 1.2kg of biomass dye watermelon red dye, 0.2kg of dispersing agent silane coupling agent KH550 and 0.8kg of unsaturated polyester after drying in a vacuum oven at 80 ℃ for 10 hours, adding the mixture of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 9:1), carrying out ultrasonic dispersion for 15 hours in a constant-temperature water bath at 70 ℃; vacuum drying in a vacuum oven at 70deg.C for 12 hr; blending and granulating, wherein the temperature of each region of the twin-screw extruder is set to 140-150 ℃ and the temperature of the machine head is 145 ℃ to obtain the masterbatch.
(3) Preparation of colored fibers:
taking 90kg of PBAT slices, 10kg of color master batch and 0.6kg of silane coupling agent KH560, mixing, carrying out melt spinning, wherein the temperature of each region of a screw in the melt spinning process is as follows: one zone 247 ℃, two zones 271 ℃, three zones 271 ℃, four zones 270 ℃, the temperature of a metering pump is 270 ℃, the temperature of a bent pipe is 270 ℃, and the pump supply amount is 35g/min; the number of spinneret holes is 36, the diameter of the spinneret hole is 0.4mm, and the spinning speed is 500m/min, so that the colored fiber is obtained.
Comparative example 1
(1) Preparation of unsaturated polyester:
1.1. taking 590g of succinic acid, heating to 178 ℃ to melt, cooling to 145 ℃, adding 972g of butanediol and 5.9g of catalyst p-toluenesulfonic acid, stirring in a nitrogen atmosphere, slowly adding 560g of unsaturated acid linoleic acid and 116g of caproic acid, esterifying, carrying out heat preservation reaction for 60min, decompressing and vacuumizing to 0.09MPa, and reacting until the acid value is less than 10mgKOH/g to obtain polyester;
1.2. drying 1000g of polyester in a blast at 70 ℃ for 12 hours, adding 65g of lanthanum maleate, 45g of glycolic acid and 5g of dicumyl peroxide, and banburying for 9 minutes at 168 ℃ and a rotating speed of 40r/min to obtain unsaturated polyester;
steps (2) and (3) were the same as in example 2 to obtain a masterbatch and a colored fiber.
Comparative example 2
(1) Preparation of unsaturated polyester:
177g of succinic acid and 938g of dimethylolpropionic acid are heated to 178 ℃ for melting, the temperature is reduced to 145 ℃, 136g of pentaerythritol, 158g of butanediol and 7.8g of catalyst p-toluenesulfonic acid are added, and in a nitrogen atmosphere, 560g of unsaturated acid linoleic acid and 145g of caproic acid are slowly added for esterification, the temperature is kept for 60min, vacuum pumping is carried out to 0.09MPa, and the reaction is carried out until the acid value is less than 10mgKOH/g, thus obtaining unsaturated polyester;
steps (2) and (3) were the same as in example 2 to obtain a masterbatch and a colored fiber.
Comparative example 3
(1) Preparation of color master batch:
taking 8.8kg of PBAT powder, 1.2kg of biomass dye indigo dye and 0.2kg of dispersing agent silane coupling agent KH550 after drying for 10 hours in a vacuum oven at 80 ℃, adding the mixture into a mixed solution of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 9:1), and performing ultrasonic dispersion for 15 hours in a constant-temperature water bath at 70 ℃; vacuum drying in a vacuum oven at 70deg.C for 12 hr; blending and granulating, wherein the temperature of each region of the twin-screw extruder is set to 140-150 ℃ and the temperature of the machine head is 145 ℃ to obtain the masterbatch.
(3) Preparation of colored fibers:
taking 90kg of PBAT slices, 10kg of color master batch and 0.6kg of silane coupling agent KH560, mixing, carrying out melt spinning, wherein the temperature of each region of a screw in the melt spinning process is as follows: one zone 247 ℃, two zones 271 ℃, three zones 271 ℃, four zones 270 ℃, the temperature of a metering pump is 270 ℃, the temperature of a bent pipe is 270 ℃, and the pump supply amount is 35g/min; the number of spinneret holes is 36, the diameter of the spinneret hole is 0.4mm, and the spinning speed is 500m/min, so that the colored fiber is obtained.
Comparative example 4
(1) Preparation of color master batch:
mixing 8.8kg of PBAT powder and 1.2kg of biomass dye indigo dye after drying for 10 hours in a vacuum oven at 80 ℃, adding the mixture of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 9:1), and performing ultrasonic dispersion for 15 hours in a constant-temperature water bath at 70 ℃; vacuum drying in a vacuum oven at 70deg.C for 12 hr; blending and granulating, wherein the temperature of each region of the twin-screw extruder is set to 140-150 ℃ and the temperature of the machine head is 145 ℃ to obtain the masterbatch.
(3) Preparation of colored fibers:
taking 90kg of PBAT slices, 10kg of color master batch and 0.6kg of silane coupling agent KH560, mixing, carrying out melt spinning, wherein the temperature of each region of a screw in the melt spinning process is as follows: one zone 247 ℃, two zones 271 ℃, three zones 271 ℃, four zones 270 ℃, the temperature of a metering pump is 270 ℃, the temperature of a bent pipe is 270 ℃, and the pump supply amount is 35g/min; the number of spinneret holes is 36, the diameter of the spinneret hole is 0.4mm, and the spinning speed is 500m/min, so that the colored fiber is obtained.
Comparative example 5
(1) Preparation of color master batch:
mixing 8.8kg of PBAT powder and 1.2kg of biomass dye indigo dye after drying for 10 hours in a vacuum oven at 80 ℃, adding the mixture of absolute ethyl alcohol and deionized water (the volume ratio of the absolute ethyl alcohol to the deionized water is 9:1), and performing ultrasonic dispersion for 15 hours in a constant-temperature water bath at 70 ℃; vacuum drying in a vacuum oven at 70deg.C for 12 hr; blending and granulating, wherein the temperature of each region of the twin-screw extruder is set to 140-150 ℃ and the temperature of the machine head is 145 ℃ to obtain the masterbatch.
(3) Preparation of colored fibers:
taking 90kg PBAT slices after drying for 4 hours at 80 ℃ in a blowing way and drying for 24 hours at 80 ℃ in a high vacuum way, mixing 10kg color master batches, and carrying out melt spinning, wherein in the melt spinning process, the temperature of each area of a screw rod is as follows: one zone 247 ℃, two zones 271 ℃, three zones 271 ℃, four zones 270 ℃, the temperature of a metering pump is 270 ℃, the temperature of a bent pipe is 270 ℃, and the pump supply amount is 35g/min; the number of spinneret holes is 36, the diameter of the spinneret hole is 0.4mm, and the spinning speed is 500m/min, so that the colored fiber is obtained.
Experiment
The color master batches and colored fibers obtained in examples 1 to 5 and comparative examples 1 to 5 were taken to prepare test pieces, and the properties thereof were measured and the measurement results were recorded, respectively:
(1) Brightness: detecting the brightness of the sample by adopting a color measuring instrument to judge the coloring effect of the color master batch and the colored fiber;
(2) Depth: reflectance of the test sample was measured, and the color depth of the color master batch and the colored fiber was evaluated by using the K/S value of the maximum absorption peak, and the absorption coefficient K/S= (1-0.01R) 2 /(2×0.01R), R is the reflectance of the sample;
(3) Intrinsic viscosity: the FZ/T51004-2011 is used as a reference standard for testing, and the Ubbelohde viscometer is used for testing the intrinsic viscosity of the color master batch and the colored fibers. The sample was dried in a vacuum oven at 80℃for 5 hours, 0.1g of the sample was taken in chloroform solution, the temperature of the thermostatic waterbath was kept at 25℃and the time of the sample's solution flow through was recorded, calculated using the following formula: relative viscosity eta r ＝t/t 0 The method comprises the steps of carrying out a first treatment on the surface of the Increase specific viscosity eta sp ＝η r -1; intrinsic viscosity iv= v2 (η) sp -lnη r ) C; t is the outflow time; t is t 0 Is the flow-through time of the solvent (96% chloroform); c is the concentration of the sample solution.
(4) Mechanical properties: testing the mechanical properties of the colored fibers by adopting a multifilament strength tester, wherein the clamping distance is 200mm, the stretching speed is 250mm/min, and the pre-tension is 5cN;
(5) Color fastness experiments:
the method is characterized in that GB/T3920-2008 is used as a reference standard, the color fastness to rubbing of the colored fibers is tested, the test temperature is 30 ℃, the relative humidity is 22%, the colored fibers and the dry friction cloth are rubbed, the test mode is reciprocating friction circulation, and the test speed is 1 s/circulation.
Table 1:
table 2:
from the data in the above table, the following conclusions can be clearly drawn:
the color concentrates and colored fibers obtained in examples 1 to 5 were compared with the color concentrates and colored fibers obtained in comparative examples 1 to 5, and the results of the detection revealed,
the biomass dye in examples 1-3 is an indigo dye; compared with example 2, the biomass dye in example 4 is a life green dye and is not provided with a component silane coupling agent KH550, and the biomass dye in example 5 is a watermelon red dye; compared with comparative examples 1-5, the intrinsic viscosity of the color master batch and the colored fiber obtained in examples 1-5 is closer to that of the PBAT resin, the brightness and depth data are relatively higher, and the mechanical property data of the colored fiber are better; the invention fully demonstrates that the stability and improvement of the dyeing and processing properties of the prepared color master batch are realized, and the color master batch has better spinnability, mechanical properties and dyeing properties when being applied to colored fibers.
In comparison with example 2, the masterbatch obtained in comparative example 1, the polyester structure of which is made of succinic acid, butanediol, linoleic acid and caproic acid; the masterbatch obtained in comparative example 2, in which the unsaturated polyester was not provided with the grafting component lanthanum maleate; the masterbatch obtained in comparative example 3, the dispersant selected the silane coupling agent KH550; the intrinsic viscosity, brightness and depth data of the obtained color master batch are reduced, the relative viscosity data of the intrinsic viscosity and the PBAT resin are enlarged, the melt with low viscosity is easier to be placed on the outer layer along with the extrusion swelling effect, the crystallinity of the colored fiber is reduced, and the mechanical property and color fastness data of the prepared colored fiber are deteriorated; the brightness and depth decrease obviously, and the thermal stability of the color master batch is deteriorated;
the masterbatch obtained in comparative example 4 was not provided with a component dispersant; on the basis of comparative example 4, the colored fiber obtained in comparative example 5 was not provided with the component silane coupling agent KH560; the obtained masterbatch and colored fiber further deteriorate the performance data. Therefore, the color master batch, the color fiber component and the process thereof can promote the improvement of the processing performance of the color master batch, are beneficial to the application of the color master batch in the color fiber, and can improve the dyeing performance and the mechanical property of the color fiber.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (4)

1. A biodegradable PBAT masterbatch, characterized by: the method comprises the following steps:
fully mixing PBAT powder, biomass dye and a dispersing agent, blending and granulating, wherein the temperature of each region of a double-screw extruder is set to 140-150 ℃, and the temperature of a machine head is 145 ℃ to obtain color master batches;
the color master batch comprises the following components in parts by weight: 85-90 parts of PBAT powder, 10-15 parts of biomass dye and 5-15 parts of dispersing agent;
the dispersing agent is unsaturated polyester; the unsaturated polyester is lanthanum ion modified branched polyester, and is prepared by the following process:
(1) Heating succinic acid and dimethylolpropionic acid to 175-180 ℃ for melting, cooling to 140-150 ℃, adding pentaerythritol, butanediol and catalyst p-toluenesulfonic acid, stirring in a nitrogen atmosphere, slowly adding unsaturated acid and caproic acid for esterification, and carrying out heat preservation reaction for 50-75 min to obtain branched polyester;
(2) The branched polyester is placed in a blowing dryer at 60-80 ℃ for 10-15 hours, lanthanum maleate, glycollic acid and dicumyl peroxide are added, and banburying is carried out for 8-10 minutes under the conditions of the temperature of 165-170 ℃ and the rotating speed of 35-45 r/min, thus obtaining unsaturated polyester;
the molar ratio of the succinic acid to the dimethylolpropionic acid to the pentaerythritol to the butanediol to the unsaturated acid to the caproic acid is (1-2), the molar ratio of the succinic acid to the dimethylolpropionic acid to the pentaerythritol to the butanediol to the unsaturated acid to the caproic acid is (6-8), the molar ratio of the succinic acid to the dimethylolpropionic acid to the caproic acid is (1.0-2.5), the molar ratio of the succinic acid to the dimethylolpropionic acid to the pentaerythritol to the butanediol to the unsaturated acid to the caproic acid is (1.0-1.5);
the unsaturated acid is one or more of fumaric acid, maleic acid, linoleic acid and oleic acid;
the mass ratio of the branched polyester to the maleic acid lanthanum to the glycollic acid to the dicumyl peroxide is 100 (3-10): 3-6): 0.4-0.7.
2. The biodegradable PBAT masterbatch of claim 1, wherein: the method comprises the following steps:
fully mixing the dried PBAT powder, the biomass dye and the dispersing agent, adding the mixture into a mixed solution of absolute ethyl alcohol and deionized water, carrying out constant-temperature water bath at 60-80 ℃, and carrying out ultrasonic dispersion for 10-16 h; vacuum drying in vacuum oven at 60-80 deg.c for 10-15 hr;
blending and granulating, wherein the temperature of each region of the twin-screw extruder is set to 140-150 ℃ and the temperature of the machine head is 145 ℃ to obtain the masterbatch.
3. A fiber made from biodegradable PBAT masterbatch according to any one of claims 1-2, characterized in that: the method comprises the following steps:
mixing the dried color master batch, PBAT slices and a silane coupling agent KH560, and carrying out melt spinning, wherein the temperature of each area of a screw is set at 247-271 ℃ to obtain the fiber.
4. A fiber made from biodegradable PBAT masterbatch according to claim 3, characterized in that: the fiber comprises the following components in parts by weight: 90 parts of PBAT slice, 10 parts of color master batch and 0.3 to 1.0 part of silane coupling agent KH560.
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