CN113736129B - Lignin-containing biodegradable polyester composite bead foaming material with high crystallization rate and preparation method thereof - Google Patents
Lignin-containing biodegradable polyester composite bead foaming material with high crystallization rate and preparation method thereof Download PDFInfo
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- C08J2203/06—CO2, N2 or noble gases
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
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- C08J2497/00—Characterised by the use of lignin-containing materials
Abstract
The invention discloses a lignin-containing biodegradable polyester compound bead foaming material with high crystallization rate and a preparation method thereof, wherein the preparation method comprises the following steps: (1) the preparation method comprises the following steps of (1) carrying out melt blending on polybutylene terephthalate adipate, an anhydride compound and a peroxide crosslinking agent to obtain MAH-g-PBAT particles; (2) blending and granulating the particles, the degradable resin, the lignin and the chain extender to obtain biodegradable polyester compound beads; (3) and (3) placing the biodegradable polyester compound beads in a high-pressure die, and performing die pressing foaming by using foaming gas as a foaming agent to obtain the biodegradable polyester compound bead. The MAH-g-PBAT and the chain extender can synergistically improve the compatibility of PBAT, PLA and lignin, promote the branching of chains and the mutual winding of the chains, successfully combine two melting points into one melting point, widen a foaming interval, improve the foaming performance and facilitate the steam forming of beads.
Description
Technical Field
The invention relates to the field of biodegradable polymer materials, in particular to a lignin-containing biodegradable polyester composite bead foaming material with high crystallization rate and a preparation method thereof.
Background
Biodegradable foaming materials such as polybutylene adipate terephthalate (PBAT), polylactic acid (PLA) and various composite materials thereof have better thermal stability and mechanical property, are important ways for solving the problem of white pollution of plastics, and particularly draw more and more attention in the fields of packaging, buffering, heat insulation, sound insulation and other foaming materials; however, at present, compared with traditional non-degradable plastics such as PS and PP, biodegradable plastics such as PBAT and PLA are expensive in market price and are prevented from being applied in large scale.
PBAT and PLA are both crystalline polymers, and have the defects of slow crystallization rate, low melt strength and the like, which may cause the undesirable results of cell collapse, large cell size, low foaming ratio and the like, and influence the application prospect of foaming. At present, a common method is to add a nucleating agent to solve the problem, and the nucleating agent can enable bubbles to form more nucleation sites, thereby being beneficial to improving the uniformity of the bubbles and preventing the bubbles from collapsing. In the steam bead forming process, if the crystallization rate is low, the diffusion and recrystallization of the chains in the bead interface region are not facilitated, and the formability of the product is impaired. The nucleating agents for biodegradation in the current market can be divided into inorganic material nucleating agents, organic compound nucleating agents, salts and polymer material nucleating agents, but the application range of the nucleating agents is limited by the defects that the nucleating agents are poor in compatibility, the performance of plastic products is easy to reduce or be unstable and the like, the nucleating agents can generate adverse effects on the environment, and some nanoscale nucleating agents are expensive; the high efficiency, greenness and harmlessness of the nucleating agent, and the development of the bio-based non-toxic nucleating agent is also one of the main directions of the future development.
The melting point difference of the PBAT composite material and the PLA composite material is large, so that a proper foaming temperature interval does not exist, foaming gas can escape in the foaming process due to the poor compatibility of the PBAT composite material and the PLA composite material, so that the foaming multiplying power is low, the sizes of foam pores are not uniform, the foam pores are merged and collapsed, the compatibility can be effectively improved through a chain extender at present, and the compatibility of the PBAT composite material and the PLA composite material still needs to be further improved. For example, patent CN111320845A provides a method for foaming a graphene reinforced and toughened PBAT/PLA composite material, using graphene as its nucleating agent, which increases the adverse effect of cost while improving the foaming performance of biodegradable polyester; and the kettle pressure foaming mode is adopted, so that the polyester biodegradable materials such as PLA, PBAT and the like are easy to be hydrolyzed and depolymerized under the condition of high-temperature hydrothermal, and the performance of the final product is adversely affected. Therefore, the invention provides a lignin-containing biodegradable polyester composite environment-friendly foaming material with high crystallization rate and a preparation method thereof.
Disclosure of Invention
The invention aims to: the invention aims to solve the technical problem of the prior art and provides a preparation method of a biodegradable polyester composite bead foaming material.
In order to solve the technical problems, the invention discloses a preparation method of a biodegradable polyester composite bead foaming material, which comprises the following steps:
(1) preparing acid anhydride compound grafted polybutylene terephthalate particles: melting and blending polybutylene terephthalate adipate (PBAT), an anhydride compound and a peroxide crosslinking agent to obtain MAH-g-PBAT particles;
(2) preparation of lignin-containing biodegradable polyester composite: blending and granulating MAH-g-PBAT particles, degradable resin, lignin and a chain extender to obtain biodegradable polyester compound beads;
(3) supercritical die pressing foaming: and (3) placing the biodegradable polyester compound beads in a high-pressure die, and carrying out die pressing foaming by using foaming gas as a foaming agent to obtain the biodegradable polyester compound bead foaming material.
In the step (1), the PBAT includes but is not limited to a brand number produced by Jinhui million-Hippon technology Limited
The product of (1), a product with a mark number of 801T produced by Fuji corporation of Fuji province of blue mountain Tun river science and technology; preferably, the PBAT is
In step (1), the acid anhydride compound includes, but is not limited to, Maleic Anhydride (MAH).
In step (1), the peroxide crosslinking agent includes, but is not limited to, dicumyl peroxide (DCP).
In the step (1), the weight parts of the components are as follows:
100 portions of polybutylene terephthalate adipate
5-15 parts of acid anhydride compound
0.1-5 parts of peroxide crosslinking agent.
In the step (1), polybutylene terephthalate adipate, an anhydride compound and a peroxide crosslinking agent are melted and blended to obtain coarse MAH-g-PBAT particles; dissolving the obtained crude MAH-g-PBAT particles in an organic solvent, and then precipitating in water to obtain purified MAH-g-PBAT particles; preferably, the polybutylene terephthalate adipate, the anhydride compound and the peroxide crosslinking agent are melted and blended to obtain coarse MAH-g-PBAT particles; and dissolving the obtained crude MAH-g-PBAT particles in an organic solvent, pouring the solution into excessive water for precipitation after the solution is completely dissolved and clear, and removing unreacted anhydride compounds and peroxide crosslinking agents to obtain the precipitate which is the purified MAH-g-PBAT particles.
Wherein the organic solvent includes, but is not limited to, dichloromethane.
In the step (1), the melt blending is melt blending by a double-screw extruder; the double-screw extruder comprises 5 temperature zones, the extrusion temperature is 130-140 ℃, and the screw rotating speed is 30-100 r/min; repeating the processes for 3 times, and then cutting the particles by a granulator to obtain coarse MAH-g-PBAT particles.
In the step (1), the grafting ratio of the obtained MAH-g-PBAT particles is 0.8-2, and the grafting ratio refers to the mass of maleic anhydride groups contained in a certain mass of the graft polymer MAH-g-PBAT.
Wherein, the grafting rate is detected as follows:
dissolving 0.3g of dried MAH-g-PBAT particles in 30mL of dichloromethane, titrating with a sodium hydroxide/ethanol mixed solution (0.0125N) to the end point of the phenolphthalein/ethanol mixed solution, calculating by the following formula,
wherein M is the molecular weight of MAH (98g/mol), C is the concentration of the sodium hydroxide/ethanol mixed solution (mol/L), M is the mass of the sample (g), and V 0 Titrating the volume (mL) of the blank sample for the sodium hydroxide/ethanol mixed solution; v is the volume (mL) of the grafting sample titrated with the sodium hydroxide/ethanol mixed solution.
In the step (2), the degradable resin is polybutylene terephthalate and polylactic acid according to the mass ratio (100-60): (0-40), preferably (60-90): (40-10).
Preferably, the polylactic acid is low-crystalline polylactic acid; preferably, the low crystalline PLA includes, but is not limited to, LX175, a product of darco benne, thailand, and 2003D, a product of Natureworks, usa, and preferably, LX 175.
In the step (2), the chain extender is any one or combination of more of epoxy chain extenders, isocyanate chain extenders and oxazoline chain extenders, preferably epoxy chain extenders, and more preferably epoxy chain extenders
ADR-4468。
In the step (2), the lignin is one or more of kraft lignin, organic lignin, alkali lignin and enzymatic hydrolysis lignin.
In the step (2), the particle size of the lignin is 2-10 μm.
In the step (2), the weight parts of the components are as follows:
preferably, the weight parts of the degradable resin and the lignin are 100 parts: 10-20 parts.
Preferably, the weight parts of the degradable resin, the MAH-g-PBAT particles and the chain extender are 100 parts: 4-8 parts of: 1-3 parts, preferably 100 parts: 6 parts of: and 2 parts.
In the step (2), the blending granulation is carried out by a double-screw underwater granulator; the extrusion temperature of the double-screw underwater granulator is 100-190 ℃, and the screw rotating speed is 30-100 r/min; the rotating speed of the granulator is 1000-.
In step (3), the high-pressure die includes, but is not limited to, a supercritical die-pressing foaming machine.
In the step (3), the foaming gas is supercritical CO 2 And/or supercritical N 2 。
In the step (3), the biodegradable polyester compound beads are placed in a high-pressure die at the temperature of 80-160 ℃, the total volume of the biodegradable polyester compound beads is ensured to be less than 1/3 of the volume of the high-pressure die, 10-20MPa of foaming gas is injected into the high-pressure die, and the constant temperature and pressure are maintained for 10-30 min.
Wherein the constant temperature is 90-130 ℃.
In the step (3), the pressure relief rate of the high-pressure die is 10-20 MPa/s.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the lignin has wide sources and low price, is similar to and compatible with PBAT, and can effectively replace degradable polyester by applying the lignin to the degradable polyester foam material, thereby reducing the dosage of the degradable polyester and lowering the cost.
(2) The lignin can play the role of a bio-based nucleating agent, can improve the crystallization rate and the crystallinity of PBAT and PLA, and improve the foaming performance, so that the foam holes are more uniform, the foam holes are smaller, the foaming ratio is higher, and the nucleating effect is non-toxic and harmless.
(3) The MAH-g-PBAT and the chain extender can synergistically improve the compatibility of PBAT, PLA and lignin, promote the branching of chains and the mutual winding of the chains, successfully combine two melting points into one melting point, widen a foaming interval, improve the foaming performance and facilitate the steam forming of beads.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a comparison chart of the granules obtained in example 1 before and after foaming.
FIG. 2 is a cell morphology diagram of the PBAT/PLA/lignin composite foamed material prepared in example 1, wherein a is 200 μm and b is 100 μm.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
(1) Drying at 70 deg.C for 10h
Melting and blending MAH (10 parts) and DCP (3 parts) in a double-screw extruder, wherein the melt blending comprises five temperature zones, the temperature from one zone to five zones is 130 ℃, 135 ℃, 140 ℃, 135 ℃ and 130 ℃, and the rotating speed of the extruding double screws is 80 rpm; repeating the process for three times, and granulating by a granulator to obtain coarse MAH-g-PBAT particles; the crude MAH-g-PBAT particles were dissolved in dichloromethane,after the solution is completely dissolved and clear, pouring the solution into excessive ultrapure water for precipitation, and removing unreacted Maleic Anhydride (MAH) and dicumyl peroxide (DCP), wherein the obtained precipitate is a purified MAH-g-PBAT master batch with the grafting rate of 1.24;
(2) drying at 70 ℃ for 10h to obtain PLA-LX175(30 parts),
MAH-g-PBAT master batch (6 parts), kraft lignin with particle size of 2 mu m (20 parts), chain extender
ADR-4468(2 parts) was extruded in a twin-screw underwater pelletizing extruder, which contained nine temperature zones, the temperatures of zone one to nine being 155 ℃, 180 ℃, 180 ℃, 185 ℃, 185 ℃, 190 ℃, 190 ℃, 185 ℃, 190 ℃, 230 ℃, the die head temperature being 230 ℃, the screw speed being 80 revolutions per minute; the granulator rotates at 1500 rpm and cuts the mixture into 5mg granules (fig. 1, left);
(3) placing the obtained granules in a supercritical molding foaming machine to ensure that the total volume of the granules does not exceed 1/3(3000 cm) of the container volume 3 ) Supercritical CO at 20MPa 2 Is used as a foaming agent, is saturated for 10min at the temperature of 112 ℃, is decompressed at the speed of 20MPa/s to obtain the biodegradable composite foaming material (figure 1, right), and the cell morphology is shown in figure 2.
Comparative example 1
The preparation method of the MAH-g-PBAT master batch was the same as in example 1. Drying at 70 deg.C for 10h
PLA-LX175(30 parts), MAH-g-PBAT master batch (6 parts), chain extender
ADR-4468(2 parts) was extruded in a twin screw underwater pelletizing extruder containing nine temperature zones, 155 ℃ C, 180 ℃ C from zone one to nine,185 ℃, 185 ℃, 190 ℃, 190 ℃, 185 ℃, 190 ℃, 230 ℃ of a die head and 80 revolutions per minute of a screw; the granulator was rotated at 1500 rpm and cut into 5mg pellets.
Placing the obtained granules in a supercritical molding foaming machine to ensure that the total volume of the granules does not exceed 1/3(3000 cm) of the container volume 3 ) Supercritical CO at 20MPa 2 Is used as a foaming agent, is saturated for 10min at the temperature of 112 ℃, and is decompressed at the speed of 20MPa/s to obtain the biodegradable composite foaming material.
Comparative example 2
Drying at 70 deg.C for 10h
(70 parts), PLA-LX175(30 parts) and kraft lignin with the particle size of 2 mu m (20 parts) are extruded in a twin-screw underwater pelletizing extruder, and the twin-screw underwater pelletizing extruder comprises nine temperature zones, wherein the temperature from one zone to nine zones is 155 ℃, 180 ℃, 180 ℃, 185 ℃, 185 ℃, 190 ℃, 190 ℃, 230 ℃ of a die head, and the rotation speed of a screw is 80 revolutions per minute; the granulator was rotated at 1500 rpm and cut into 5mg pellets.
Placing the obtained granules in a supercritical molding foaming machine to ensure that the total volume of the granules does not exceed 1/3(3000 cm) of the container volume 3 ) Supercritical CO at 20MPa 2 Is used as a foaming agent, is saturated for 10min at the temperature of 112 ℃, and is decompressed at the speed of 20MPa/s to obtain the biodegradable composite foaming material.
Comparative example 3
Drying at 70 deg.C for 10h
PLA-LX175(30 parts), kraft lignin with particle size of 2 mu m (20 parts), and chain extender
ADR-4468(2 parts) was extruded in a twin-screw underwater pelletizing extruder, which contained nine temperature zones, the temperatures of zone one to nine being 155 ℃, 180 ℃, 180 ℃, 185 ℃, 185 ℃, 190 ℃, 190 ℃, 185 ℃, 190 ℃, 230 ℃, the die head temperature being 230 ℃, the screw speed being 80 revolutions per minute; rotational speed of granulatorCut into 5mg granules at 1500 rpm.
Placing the obtained granules in a supercritical molding foaming machine to ensure that the total volume of the granules does not exceed 1/3(3000 cm) of the container volume 3 ) Supercritical CO at 20MPa 2 Is used as a foaming agent, is saturated for 10min at the temperature of 112 ℃, and is decompressed at the speed of 20MPa/s to obtain the biodegradable composite foaming material.
Comparative example 4
The preparation method of the MAH-g-PBAT master batch was the same as in example 1. Drying at 70 deg.C for 10h
Extruding PLA-LX175(30 parts) and MAH-g-PBAT master batches (6 parts) in a double-screw underwater pelletizing extruder, wherein the temperature of the first zone to the ninth zone is 155 ℃, 180 ℃, 180 ℃, 185 ℃, 185 ℃, 190 ℃, 190 ℃, 190 ℃, 230 ℃ of a die head, and the rotation speed of a screw is 80 revolutions per minute; the granulator was rotated at 1500 rpm and cut into 5mg pellets.
Placing the obtained granules in a supercritical molding foaming machine to ensure that the total volume of the granules does not exceed 1/3(3000 cm) of the container volume 3 ) Supercritical CO at 20MPa 2 Is used as a foaming agent, is saturated for 10min at the temperature of 112 ℃, and is decompressed at the speed of 20MPa/s to obtain the biodegradable composite foaming material.
Comparative example 5
The same dosage ratio as that of the example 1 is adopted, but the MAH-g-PBAT master batch is not prepared, and the PLA-LX175(30 portions) is dried for 10 hours at 70℃,
MAH (0.6 part), DCP (0.18 part), kraft lignin with particle size of 2 μm (20 parts), chain extender
ADR-4468(2 parts) was extruded in a twin-screw underwater pelletizing extruder, which contained nine temperature zones, the temperatures of zone one to nine being 155 ℃, 180 ℃, 180 ℃, 185 ℃, 185 ℃, 190 ℃, 190 ℃, 185 ℃, 190 ℃, 230 ℃, the die head temperature being 230 ℃, the screw speed being 80 revolutions per minute; granulatingCutting into 5mg granules at a rotation speed of 1500 rpm;
placing the obtained granules in a supercritical molding foaming machine to ensure that the total volume of the granules does not exceed 1/3(3000 cm) of the container volume 3 ) Supercritical CO at 20MPa 2 Is used as a foaming agent, is saturated for 10min at the temperature of 112 ℃, and is decompressed at the speed of 20MPa/s to obtain the biodegradable composite foaming material.
Comparative example 6
Same as example 1, but in step (1)
Replaced by PLA-LX175, namely MAH-g-PLA granules are prepared firstly.
Comparative example 7
Like example 1, only PLA-LX175 in step (2) was replaced with semi-crystalline PLA-LX 575.
Comparative example 8
As in example 1, only the PLA-LX175 in step (2) was replaced with crystalline PLA-L175.
Example 2
The preparation method of the MAH-g-PBAT master batch is the same as that of example 1. Drying at 70 deg.C for 10h
PLA-LX175(30 parts), MAH-g-PBAT master batch (6 parts), kraft lignin with the particle size of 2 mu m (10 parts), and chain extender
ADR-4468(2 parts) was extruded in a twin-screw underwater pelletizing extruder, which contained nine temperature zones, the temperatures of zone one to nine being 155 ℃, 180 ℃, 180 ℃, 185 ℃, 185 ℃, 190 ℃, 190 ℃, 185 ℃, 190 ℃, 230 ℃, the die head temperature being 230 ℃, the screw speed being 80 revolutions per minute; the granulator was rotated at 1500 rpm and cut into 5mg pellets.
Placing the obtained granules in a supercritical molding foaming machine to ensure that the total volume of the granules does not exceed 1/3(3000 cm) of the container volume 3 ) Supercritical CO at 20MPa 2 As foaming agent, the mixture is saturated at 112 deg.C for 10min at a rate of 20MPa/sAnd (4) decompressing to obtain the biodegradable composite foaming material.
Example 3
The preparation method of the MAH-g-PBAT master batch is the same as that of example 1. Drying at 70 deg.C for 10h
PLA-LX175(30 parts), MAH-g-PBAT master batch (6 parts), kraft lignin with the particle size of 2 mu m (40 parts), and chain extender
ADR-4468(2 parts) was extruded in a twin-screw underwater pelletizing extruder, which contained nine temperature zones, the temperatures of zone one to nine being 155 ℃, 180 ℃, 180 ℃, 185 ℃, 185 ℃, 190 ℃, 190 ℃, 185 ℃, 190 ℃, 230 ℃, the die head temperature being 230 ℃, the screw speed being 80 revolutions per minute; the granulator was rotated at 1500 rpm and cut into 5mg pellets.
Placing the obtained granules in a supercritical molding foaming machine to ensure that the total volume of the granules does not exceed 1/3(3000 cm) of the container volume 3 ) Supercritical CO at 20MPa 2 Is used as a foaming agent, is saturated for 10min at the temperature of 112 ℃, and is decompressed at the speed of 20MPa/s to obtain the biodegradable composite foaming material.
Example 4
And (3) changing the foaming saturation time to be 30min and keeping the foaming saturation time consistent with the rest of the foaming saturation time to obtain the biodegradable composite foaming material in the same way as in the example 1.
Example 5
The preparation method of the MAH-g-PBAT master batch was the same as in example 1. Drying at 70 deg.C for 10h
PLA-LX175(10 parts), MAH-g-PBAT master batch (6 parts), kraft lignin with the particle size of 2 mu m (20 parts), and chain extender
ADR-4468(2 parts) was extruded in a twin screw underwater pelletizing extruder having nine temperature zones, 155 deg.C, 180 deg.C, 185 deg.C, 190 deg.C190 ℃, 185 ℃, 190 ℃, 230 ℃ of die head and 80 r/min of screw rotating speed; the granulator was rotated at 1500 rpm and cut into 5mg pellets.
Placing the obtained granules in a supercritical molding foaming machine to ensure that the total volume of the granules does not exceed 1/3(3000 cm) of the container volume 3 ) Supercritical CO at 20MPa 2 Is used as a foaming agent, is saturated for 10min at the temperature of 112 ℃, and is decompressed at the speed of 20MPa/s to obtain the biodegradable composite foaming material.
Example 6
The preparation method of the MAH-g-PBAT master batch was the same as in example 1. Drying at 70 deg.C for 10h
PLA-LX175(20 parts), MAH-g-PBAT master batch (6 parts), kraft lignin with the particle size of 2 mu m (20 parts), and chain extender
ADR-4468(2 parts) was extruded in a twin-screw underwater pelletizing extruder, which contained nine temperature zones, the temperatures of zone one to nine being 155 ℃, 180 ℃, 180 ℃, 185 ℃, 185 ℃, 190 ℃, 190 ℃, 185 ℃, 190 ℃, 230 ℃, the die head temperature being 230 ℃, the screw speed being 80 revolutions per minute; the granulator was rotated at 1500 rpm and cut into 5mg pellets.
Placing the obtained granules in a supercritical molding foaming machine to ensure that the total volume of the granules does not exceed 1/3(3000 cm) of the container volume 3 ) Supercritical CO at 20MPa 2 Is used as a foaming agent, is saturated for 10min at the temperature of 112 ℃, and is decompressed at the speed of 20MPa/s to obtain the biodegradable composite foaming material.
Example 7
The preparation method of the MAH-g-PBAT master batch is the same as that of example 1. Drying at 70 deg.C for 10h
PLA-LX175(40 parts), MAH-g-PBAT master batch (6 parts), kraft lignin with the particle size of 2 mu m (20 parts), and chain extender
ADR-4468(2 parts) was extruded in a twin screw underwater pelletizing extruder containing nine temperature zones at 155 deg.C, 180 deg.C, 185 deg.C, 190 deg.C, 230 deg.C at die head temperature and 80rpm of the screws; the granulator was rotated at 1500 rpm and cut into 5mg pellets.
Placing the obtained granules in a supercritical molding foaming machine to ensure that the total volume of the granules does not exceed 1/3(3000 cm) of the container volume 3 ) Supercritical CO at 20MPa 2 Is used as a foaming agent, is saturated for 10min at the temperature of 112 ℃, and is decompressed at the speed of 20MPa/s to obtain the biodegradable composite foaming material.
Example 8
The preparation method of the MAH-g-PBAT master batch was the same as in example 1. Drying at 70 deg.C for 10h
PLA-LX175(30 parts), MAH-g-PBAT master batch (3 parts), kraft lignin with the particle size of 2 mu m (20 parts), and chain extender
ADR-4468(1 part) is extruded in a twin-screw underwater pelletizing extruder, which comprises nine temperature zones, wherein the temperature from zone one to zone nine is 155 ℃, 180 ℃, 180 ℃, 185 ℃, 185 ℃, 190 ℃, 190 ℃, 185 ℃, 190 ℃, 230 ℃ of a die head, and the screw rotation speed is 80 revolutions per minute; the granulator was rotated at 1500 rpm and cut into 5mg pellets.
Placing the obtained granules in a supercritical molding foaming machine to ensure that the total volume of the granules does not exceed 1/3(3000 cm) of the container volume 3 ) Supercritical CO at 20MPa 2 Is used as a foaming agent, is saturated for 10min at the temperature of 112 ℃, and is decompressed at the speed of 20MPa/s to obtain the biodegradable composite foaming material.
Example 9
The preparation method of the MAH-g-PBAT master batch was the same as in example 1. Drying at 70 deg.C for 10h
PLA-LX175(30 parts), MAH-g-PBAT master batch (1 part), kraft lignin with the particle size of 2 mu m (20 parts), and chain extender
ADR-4468(1 part) was extruded in a twin-screw underwater pelletizing extruder containing nine temperature zones at 155 deg.C, 180 deg.C, 185 deg.C, 190 deg.C, 230 deg.C at die head temperature and 80rpm of the screws; the granulator was rotated at 1500 rpm and cut into 5mg pellets.
Placing the obtained granules in a supercritical molding foaming machine to ensure that the total volume of the granules does not exceed 1/3(3000 cm) of the container volume 3 ) Supercritical CO at 20MPa 2 Is used as a foaming agent, is saturated for 10min at the temperature of 112 ℃, and is decompressed at the speed of 20MPa/s to obtain the biodegradable composite foaming material.
Example 10
Like example 1, only
And changing the mixture into a PBAT-801T product to obtain the biodegradable composite foaming material.
Example 11
Just changing PLA-LX175 into a product of PLA-2003D as in example 1, a biodegradable composite foamed material was obtained.
TABLE 1
From the experimental data and the phenomena during the experiment, the following conclusions can be drawn:
(1) compared with the comparative example 1, the foaming ratio of the biodegradable polyester composite bead foaming material containing lignin with high crystallization rate obtained after adding the lignin is slightly improved, but the addition of the lignin enables the cost of the raw material of the biodegradable polyester composite to be obviously reduced, the average pore diameter of the foam to be obviously improved, the cell density to be obviously reduced, the foaming performance of the biodegradable material to be improved, and good biodegradation performance to be still achieved.
(2) Compared with the comparative example 2, the comparative example 3 and the comparative example 4, the MAH-g-PBAT master batch and the chain extender have the effect of synergistically increasing the chain extension compatibility of the PBAT/PLA/lignin composite system, and the foaming ratio is improved.
(3) Example 1 is compared with example 2 and example 3, and the lignin is used as a bio-based nucleating agent with a proper filling amount, and the foaming performance of the biodegradable material is affected by the high filling amount.
(4) Compared with the embodiment 1 and the embodiment 4, the saturation time of the die pressing foaming is very short, the die pressing foaming can be basically and completely saturated within 10min, the saturation time is subsequently prolonged, the influence on the foaming is not great, the hydrolysis influence of the conventional bead foaming on the biodegradable material can be prevented, the biodegradable material still has good biodegradation performance, the production efficiency and the quality of the bead foam are improved, and the large-scale market application is facilitated.
(5) Example 1 was compared with examples 10 and 11, and it was found that the foaming properties were better when different grades of PBAT and PLA were used instead.
(6) Compared with the comparative example 6, the embodiment 1 finds that the system for preparing MAH-g-PBAT by reacting MAH, DCP and PBAT has better foaming effect than the system for preparing MAH-g-PLA by reacting with PLA, and the system for preparing MAH-g-PLA firstly has little improvement on foaming performance.
(7) Compared with the comparative examples 7 and 8, the PBAT/PLA composite system in example 1 has the advantages that the low-crystallinity PLA is more favorable for foaming, the foaming ratio is higher, the semi-crystallinity PLA and the crystallinity PLA are partially crystallized, the lignin also plays the role of a bio-based nucleating agent, the crystallization can be further promoted, the too high crystallization is caused, the cell growth is inhibited, and the foaming ratio is low.
The invention provides a biodegradable polyester composite bead foaming material containing lignin with high crystallization rate and a method for preparing the same, and a method and a way for realizing the technical scheme are many. All the components not specified in the present embodiment can be realized by the prior art.
Claims (8)
1. A preparation method of a biodegradable polyester composite bead foaming material is characterized by comprising the following steps:
(1) the preparation method comprises the following steps of (1) carrying out melt blending on polybutylene terephthalate adipate, an anhydride compound and a peroxide crosslinking agent to obtain MAH-g-PBAT particles;
(2) blending and granulating MAH-g-PBAT particles, degradable resin, lignin and a chain extender to obtain biodegradable polyester compound beads;
(3) placing the biodegradable polyester composite beads in a high-pressure die, and carrying out die pressing foaming by using foaming gas as a foaming agent to obtain a biodegradable polyester composite bead foaming material;
in the step (2), the degradable resin is polybutylene terephthalate adipate and polylactic acid according to the mass ratio (100-60): (0-40); the polylactic acid is low-crystallinity polylactic acid;
in the step (2), the weight parts of the components are as follows:
2. the preparation method according to claim 1, wherein in the step (1), the weight parts of the components are as follows:
100 portions of polybutylene terephthalate adipate
5-15 parts of anhydride compound
0.1-5 parts of peroxide crosslinking agent.
3. The method according to claim 1, wherein in the step (1), polybutylene terephthalate adipate is melt-blended with an acid anhydride compound and a peroxide crosslinking agent to obtain crude MAH-g-PBAT particles; and dissolving the obtained crude MAH-g-PBAT particles in an organic solvent, and precipitating in water to obtain purified MAH-g-PBAT particles.
4. The preparation method according to claim 1, wherein in the step (2), the chain extender is any one or more of epoxy chain extenders, isocyanate chain extenders and oxazoline chain extenders.
5. The preparation method according to claim 1, wherein in the step (2), the blending granulation is blending granulation by a twin-screw underwater granulator; the extrusion temperature of the double-screw underwater granulator is 190 ℃, and the rotation speed of the screws is 30-100 r/min; the rotating speed of the granulator is 1000-2000 rpm.
6. The method according to claim 1, wherein in the step (3), the foaming gas is supercritical CO 2 And/or supercritical N 2 。
7. The preparation method according to claim 1, wherein in the step (3), the biodegradable polyester composite beads are placed in a high pressure mold at a temperature of 80 to 160 ℃ and the total volume of the biodegradable polyester composite beads is ensured to be 1/3 or less of the volume of the high pressure mold, and 10 to 20MPa of foaming gas is injected into the high pressure mold and the pressure is maintained at a constant temperature for 10 to 30 min.
8. The production method according to claim 1, wherein in the step (3), the high-pressure mold is depressurized at a rate of 10 to 20 MPa/s.
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