CN116875014A - Lignin fiber/starch/polylactic acid master batch and preparation method thereof - Google Patents

Lignin fiber/starch/polylactic acid master batch and preparation method thereof Download PDF

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Publication number
CN116875014A
CN116875014A CN202311005811.6A CN202311005811A CN116875014A CN 116875014 A CN116875014 A CN 116875014A CN 202311005811 A CN202311005811 A CN 202311005811A CN 116875014 A CN116875014 A CN 116875014A
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CN
China
Prior art keywords
polylactic acid
starch
lignin
fiber
lignin fiber
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Pending
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CN202311005811.6A
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Chinese (zh)
Inventor
李禹函
赵忠超
冒显
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Henan Longdu Tianren Biology Material Co ltd
Zhengzhou University
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Henan Longdu Tianren Biology Material Co ltd
Zhengzhou University
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Priority to CN202311005811.6A priority Critical patent/CN116875014A/en
Publication of CN116875014A publication Critical patent/CN116875014A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2403/00Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/02Starch; Degradation products thereof, e.g. dextrin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2491/00Characterised by the use of oils, fats or waxes; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2497/00Characterised by the use of lignin-containing materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/13Phenols; Phenolates
    • C08K5/134Phenols containing ester groups
    • C08K5/1345Carboxylic esters of phenolcarboxylic acids

Abstract

The invention discloses a lignin fiber/starch/polylactic acid master batch, which is prepared by melt blending the following materials in percentage by weight: 5-10% of lignin fiber; 35-50% of starch; 35-55% of high-melting-point polylactic acid; 2-5% of epoxidized vegetable oil; 0.1-0.3% of antioxidant, wherein the sum of the materials is percentage. The compound powder of the fibrous lignin fiber and the amorphous starch can overcome the problem that the fiber is difficult to disperse in the polylactic acid matrix, and the high-melting-point polylactic acid matrix is favorable for filling high-content powder, and the epoxy vegetable oil promotes the disintegration and uniform dispersion of the powder agglomerate. The masterbatch disclosed by the invention has higher lignin fiber content, can reduce the dosage of the modified polylactic acid composite material, has better dispersion uniformity compared with a mode of directly adding lignin fibers for melt blending, and is beneficial to improving the tear resistance and toughness of a polylactic acid composite material product.

Description

Lignin fiber/starch/polylactic acid master batch and preparation method thereof
Technical Field
The invention belongs to the technical field of modified plastics, and particularly relates to a lignin fiber/polylactic acid filling modified master batch and a preparation method thereof.
Background
Most of color master batches used in the modified plastic industry adopt polyolefin resin polyethylene as a carrier, but the color master batches have poor compatibility in the modified polylactic acid composite material, so that the reinforcing, toughening and coloring energy is low, and the mechanical property, appearance and usability are affected.
The patent application with publication number of CN113736232A discloses a modified biodegradable material and a preparation method thereof, wherein the modified biodegradable material is prepared from the following components in percentage by weight: biodegradable material, 50-90%, preferably 65-85%; starch, 5-40%, preferably 10-30%; 1-10%, preferably 2-7% of a high melting point solid dispersant; 0.1 to 1 percent of opening agent.
The patent application with publication number of CN101851429A discloses a preparation method of lignin composite material, which is formed by mixing lignin, accessory high molecular compound, fiber substance, chitin, plasticizer, compatibilizer, antioxidant and flame retardant, and drying lignin, accessory high molecular compound and flame retardant; then stirring the plasticizer, the compatibilizer, the antioxidant, the dried lignin, the accessory polymer compound and the flame retardant in a dried high-speed stirrer according to a certain weight ratio to uniformly mix the materials, then placing the materials into a double-screw extruder for reaction, cooling and granulating the extruded product, and drying the product to obtain a composite master batch; soaking the fiber material in silane coupling agent solution with concentration of 0.1-2% to obtain modified fiber; and adding the composite master batch, the chitin and the modified fiber into a double-screw extruder in sequence for composite processing to obtain the finished lignin composite material.
The lignin fiber is uniformly dispersed in the polylactic acid, so that the tear resistance can be effectively improved, and the method is particularly suitable for processing and preparing packaging materials and bags. The lignin fiber structure contains a large amount of functional groups such as phenolic hydroxyl groups, carbonyl groups, carboxyl groups and the like, has certain compatibility with polylactic acid, and is expected to realize high-value utilization in the industry of biodegradable polylactic acid materials. However, fibrous lignin fibers are difficult to uniformly disperse in low melt index blow molding grade polylactic acid. Therefore, from the viewpoints of melt processing and compounding, a new way and a new process are explored to realize uniform dispersion of lignin fibers in polylactic acid, and the aim is achieved, so that the method has challenging and industrial application value.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a lignin fiber/starch/polylactic acid master batch and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the lignin fiber/starch/polylactic acid master batch is prepared by melt blending the following materials in percentage by weight:
5-10% of lignin fiber;
35-50% of starch;
35-55% of high-melting-point polylactic acid;
2-5% of epoxidized vegetable oil;
0.1-0.3% of an antioxidant;
the sum of the materials is percentage.
The lignin fibers are staple fibers, and the fiber length is 0.2-1.0 mm.
The starch is one or more of corn starch, tapioca starch, sweet potato starch, potato starch and wheat starch, preferably corn starch.
The melt index of the high-melt-index polylactic acid is 50-500 g/10min under the conditions that the temperature is 210 ℃ and the load is 2.16kg, the polylactic acid is synthesized into low-molecular-weight polylactic acid by a one-step method or a two-step method, or the polylactic acid resin with the melt index less than 50 g/10min is prepared by a catalytic degradation method.
The epoxidized vegetable oil is one or a mixture of more of epoxidized soybean oil, epoxidized castor oil, epoxidized palm oil, epoxidized cotton seed oil and epoxidized tung oil.
The antioxidant is hindered phenol antioxidant.
The preparation method of the lignin fiber/polylactic acid master batch comprises the following steps:
(1) Putting lignin fibers and starch in a set proportion into a vertical drying tank, starting a spiral belt to stir and turn over materials, pumping hot air from the bottom, exhausting air from an air outlet at the top, controlling the temperature to be 80-110 ℃, baking dry powder for 4-8 hours, discharging, sealing and preserving for later use;
(2) Adding dry powder, polylactic acid, epoxidized vegetable oil and an antioxidant into an internal mixer according to a set proportion, controlling the temperature to be 160-220 ℃, controlling the rotating speed to be 10-60 revolutions per minute, carrying out melt blending for 15-30 minutes, pressing into a single screw extruder, bracing, air cooling and granulating to obtain lignin fiber/starch/polylactic acid master batch.
Has the positive beneficial effects that:
(1) The compound powder of the fibrous lignin fiber and the amorphous starch can overcome the problem of difficult dispersion of the fiber in the polylactic acid matrix, the high-melting-point polylactic acid matrix is favorable for filling high-content powder, and the epoxy vegetable oil promotes the disintegration and uniform dispersion of the powder agglomerate.
(2) The masterbatch has higher lignin fiber content, can reduce the dosage of the modified polylactic acid composite material, has better dispersion uniformity degree compared with a mode of directly adding lignin fibers for melt blending, and is beneficial to improving the tear resistance and toughness of a polylactic acid composite material product.
Detailed Description
The invention is further illustrated by the following examples:
the following raw materials are used for experiments in the examples and comparative examples of the present invention, but the present invention is not limited to the following raw materials, and the effects of the lignocellulosic starch polylactic acid master batch described in the present invention will be further specifically described by taking the following raw materials as specific examples.
Example 1
High melt index polylactic acid resin: melt fingers 50 g/10min (PLA 50), 200g/10min (PLA 200) and 500 g/10min (PLA 500) are self-made polylactic acid resin by a one-step method, and melt fingers 65 g/10min are Dandall Luminy PLA L105 polylactic acid resin.
Lignin fiber: lengths of 0.2 mm (0.2 lignin), 0.5 mm (0.5 lignin) and 1.0 mm (1.0 lignin).
Starch: corn starch.
Epoxidized vegetable oil: epoxidized Soybean Oil (ESO).
An antioxidant: and an antioxidant 1010.
Examples 1 to 11 are provided, and the formula is shown in Table 1:
example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11
0.2 lignin 2 1 2 2 2 2 2 2 2 2 2
0.5 lignin 2 2 4 2 4 2 4 2 4 2 4
1.0 lignin 1 4 4 1 4 1 4 1 4 1 4
Starch 37.8 40 50 37.8 50 37.8 50 37.8 50 37.8 50
PLA50 55 50.8 35 25 10
L105 55 35 10 10
PLA200 55 35 10 10
PLA500 55 35 10 5
ESO 2 2 4.8 2 4.8 2 4.8 2 4.8 2 4.8
1010 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Totalizing 100 100 100 100 100 100 100 100 100 100 100
TABLE 1
Comparative examples 1 to 4 were set up in the present invention, and the formulation thereof is shown in the following table 2:
comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
0.2 lignin 2 2 2 2
0.5 lignin 2 4 4 4
1.0 lignin 1 5 8 8
Starch 35.8 50.8 37.8 49
PLA50 57 33 16 7
L105 10 10
PLA200 10 10
PLA500 10 5
ESO 2 5 2 4.8
1010 0.2 0.2 0.2 0.2
Totalizing 100 100 100 100
Examples 1 to 11 and comparative examples 1 to 4 were prepared by the following processes:
(1) Adding lignin fiber and starch with a set proportion into a vertical drying tank, starting a spiral belt to stir and turn over materials, pumping hot air from the bottom, exhausting air from an air outlet at the top, controlling the temperature at 100 ℃, baking dry powder for 6 hours, discharging, sealing and preserving for later use;
(2) Adding dry powder, polylactic acid, epoxidized vegetable oil and an antioxidant into an internal mixer according to a set proportion, controlling the temperature at 180 ℃, controlling the rotating speed at 50 revolutions per minute, carrying out melt blending for 20 minutes, pressing into a single-screw extruder, bracing, air cooling and granulating to obtain lignin fiber/starch/polylactic acid master batch.
The master batches prepared in the examples and comparative examples were evaluated for uniformity by observing the appearance, cutting the particles into flakes with a blade, and observing whether there were significant agglomerates in a scanning electron microscope.
The master batches prepared in examples 1-11 were uniform in particle size, free of burrs when observed with naked eyes, and free of obvious lignin fiber agglomerates when observed under a scanning electron microscope. The comparative example showed burrs of different degrees, and lignin fiber agglomerates of different degrees were found under a scanning electron microscope. Thus, it was demonstrated that incorporation of too much length of lignin fibers resulted in agglomeration and that low melt index did not adequately disentangle the lignin fibers.
The compound powder of the fibrous lignin fiber and the amorphous starch can overcome the problem that the fiber is difficult to disperse in a polylactic acid matrix, and the high-melting-point polylactic acid matrix is favorable for filling high-content powder, and the epoxy vegetable oil promotes the disintegration and uniform dispersion of powder agglomerates; the masterbatch has higher lignin fiber content, can reduce the dosage of the modified polylactic acid composite material, has better dispersion uniformity degree compared with a mode of directly adding lignin fibers for melt blending, and is beneficial to improving the tear resistance and toughness of a polylactic acid composite material product.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims (6)

1. The lignin fiber/starch/polylactic acid master batch is prepared by melt blending the following materials in percentage by weight:
5-10% of lignin fiber;
35-50% of starch;
35-55% of high-melting-point polylactic acid;
2-5% of epoxidized vegetable oil;
0.1 to 0.3 percent of antioxidant,
the sum of the materials is percentage.
2. The lignin fiber/starch/polylactic acid master batch according to claim 1, wherein the lignin fiber is a staple fiber with a fiber length of 0.2-1.0 mm.
3. The lignin fiber/starch/polylactic acid masterbatch according to claim 1 wherein the starch is one or more of corn starch, tapioca starch, sweet potato starch, wheat starch, preferably corn starch.
4. The lignin fiber/starch/polylactic acid master batch according to claim 1, wherein the high melt index polylactic acid has a melt index of 50-500 g/10min under the conditions of 210 ℃ and 2.16kg load, and the polylactic acid is synthesized into low molecular weight polylactic acid by a one-step method or a two-step method, or is prepared from polylactic acid resin with a melt index of less than 50 g/10min by catalytic degradation.
5. The lignocellulosic/starch/polylactic acid masterbatch of claim 1 wherein the epoxidized vegetable oil is one or more of epoxidized soybean oil, epoxidized castor oil, epoxidized palm oil, epoxidized cottonseed oil, epoxidized tung oil.
6. The lignin fiber/starch/polylactic acid master batch according to claim 1, wherein the preparation method of the lignin fiber/polylactic acid master batch comprises the following steps:
(1) Putting lignin fibers and starch in a set proportion into a vertical drying tank, starting a spiral belt to stir and turn over materials, pumping hot air from the bottom, exhausting air from an air outlet at the top, controlling the temperature to be 80-110 ℃, baking dry powder for 4-8 hours, discharging, sealing and preserving for later use;
(2) Adding dry powder, polylactic acid, epoxidized vegetable oil and an antioxidant into an internal mixer according to a set proportion, controlling the temperature to be 160-220 ℃, controlling the rotating speed to be 10-60 revolutions per minute, carrying out melt blending for 15-30 minutes, pressing into a single screw extruder, bracing, air cooling and granulating to obtain lignin fiber/starch/polylactic acid master batch.
CN202311005811.6A 2023-08-10 2023-08-10 Lignin fiber/starch/polylactic acid master batch and preparation method thereof Pending CN116875014A (en)

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CN202311005811.6A CN116875014A (en) 2023-08-10 2023-08-10 Lignin fiber/starch/polylactic acid master batch and preparation method thereof

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Publication Number Publication Date
CN116875014A true CN116875014A (en) 2023-10-13

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