CN114752198A - High-strength bio-based degradable PLA/PBS composite material for food packaging boxes and preparation method thereof - Google Patents
High-strength bio-based degradable PLA/PBS composite material for food packaging boxes and preparation method thereof Download PDFInfo
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- CN114752198A CN114752198A CN202210522852.1A CN202210522852A CN114752198A CN 114752198 A CN114752198 A CN 114752198A CN 202210522852 A CN202210522852 A CN 202210522852A CN 114752198 A CN114752198 A CN 114752198A
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004626 polylactic acid Substances 0.000 claims abstract description 43
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 40
- 229920002961 polybutylene succinate Polymers 0.000 claims abstract description 40
- 239000004631 polybutylene succinate Substances 0.000 claims abstract description 40
- 238000001125 extrusion Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- -1 polybutylene succinate Polymers 0.000 claims abstract description 7
- 238000005469 granulation Methods 0.000 claims abstract description 4
- 230000003179 granulation Effects 0.000 claims abstract description 4
- 230000000655 anti-hydrolysis Effects 0.000 claims abstract description 3
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 150000001718 carbodiimides Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 4
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 1
- 239000003112 inhibitor Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 6
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 5
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000020965 cold beverage Nutrition 0.000 description 1
- 235000012171 hot beverage Nutrition 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention discloses a high-strength bio-based degradable PLA/PBS composite material for a food packaging box and a preparation method thereof, wherein the composite material is prepared from the following materials in parts by weight: 70-90 parts of polylactic acid, 10-30 parts of polybutylene succinate, 1-3 parts of a chain extender, 1-4 parts of a compatilizer and 0.5-2 parts of an anti-hydrolysis agent. In the composite material prepared by the invention, in-situ fiber formation is carried out on PBS in a PLA matrix in the processing process by using micro-nano laminated co-extrusion equipment, so that the crystallinity and the melting temperature of the PBS are improved, and the mechanical strength of the PLA/PBS composite material is improved. In the extrusion granulation process, the two-phase interfacial tension of the composite material is greatly reduced through the effect of the compatilizer, and the PBS fiber of the composite material can better provide heterogeneous nucleation sites for PLA, so that the cold crystallization temperature of the PLA is reduced, the processing window of the composite material is widened, and the composite material is easy to form and process.
Description
Technical Field
The invention relates to the field of biodegradable polymer materials, in particular to a high-strength bio-based degradable PLA/PBS composite material for a food packaging box and a preparation method thereof.
Background
Polylactic acid (PLA) as a thermoplastic aliphatic polyester derived from renewable resources has good biodegradability and biocompatibility, and also has excellent mechanical strength and processability, so that the PLA has a wide application prospect in the fields of general plastics and biomedical materials. However, PLA has limited application due to its high cost, poor heat resistance, and low flexibility. PBS is poly butylene succinate, is a typical aliphatic polyester in nature, and has good heat resistance and mechanical properties compared with other biodegradable plastics. PBS has good heat resistance, heat distortion temperature close to 100 ℃, low tensile strength, and the like, and the PBS often has the problems of breakage, damage and the like when processing and preparing products such as packaging boxes for cold and hot drinks. By combining the two materials at a certain point, the toughness and the heat distortion temperature of the PLA material can be improved, and the tensile strength of the PBS material can be improved, so that the application fields of the PLA material and the PBS material are expanded. Therefore, the invention provides a high-strength bio-based degradable PLA/PBS composite material for a food packaging box 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 high-strength bio-based degradable PLA/PBS composite material for a food packaging box.
The technical problem to be solved by the invention is to provide a preparation method of the high-strength biodegradable PLA/PBS composite material for the food packaging box.
In order to solve the first technical problem, the invention discloses a high-strength bio-based degradable PLA/PBS composite material for a food packaging box, which is prepared from the following materials in parts by weight: 70-90 parts of polylactic acid (PLA), 10-30 parts of polybutylene succinate (PBS), 1-3 parts of a chain extender, 1-4 parts of a compatilizer and 0.5-2 parts of an anti-hydrolysis agent.
Wherein, the PLA includes but is not limited to Dadalco Bienyi brand PLA-LX175, PLA-LX 575; the American NatureWorks corporation brand is PLA-4032D; the Guangzhou Bijia Material Co.Ltd is PLA-301P; preferably, the PLA is American NatureWorks corporation under the trademark PLA-4032D.
Wherein the polybutylene succinate comprises but is not limited to Xinjiang blue mountain Tungheu brand PBS-TH801 or PBS-TH 803S; the company KMI USA is PBS-KM 804; thai PTT chemical company under the trademark FZ71 PB; preferably, the polybutylene succinate is Sinkiang blue Shantun river brand PBS-TH 801.
Wherein the chain extender is an epoxy chain extender; the epoxy chain extender is ADR-4368 and/or ADR-4370S.
The compatilizer is EsunBio5004K, and is a low-carbon environment-friendly compatilizer which can reduce the shrinkage rate of a product, has good dimensional stability and strong anti-warping capability.
Wherein the hydrolysis resistant agent is a carbodiimide hydrolysis resistant agent; the carbodiimide hydrolysis-resistant agent is
1010 and/or UN-150.
In order to solve the second technical problem, the invention discloses a preparation method of the composite material, which comprises the steps of placing polylactic acid (PLA) and polybutylene succinate (PBS) in a drying oven at 65 ℃ for drying for 6 hours for later use; weighing the materials according to the formula ratio, dispersing and stirring in a high-speed mixer, melting, mixing, extruding and granulating through a double-screw extruder, and extruding through micro-nano laminated co-extrusion equipment to obtain the nano-composite material.
Wherein the rotating speed of the high-speed mixer is 500-2000 r/min; preferably, the high speed mixer speed is 1500 r/min.
Wherein the time of dispersing and stirring is 5-6 min.
Wherein the temperature of the double-screw extruder is 150-190 ℃.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) according to the high-strength bio-based degradable PLA/PBS composite material for the food packaging box, in-situ fiber formation is carried out on PBS in a PLA matrix in the processing process by using micro-nano laminated co-extrusion equipment, so that the crystallinity and the melting temperature of the PBS are improved, and the mechanical strength of the PLA/PBS composite material is improved.
(2) In the extrusion granulation process of PLA/PBS, the two-phase interfacial tension is greatly reduced through the action of the compatilizer, and the fibers of the PBS better provide heterogeneous nucleation sites for the PLA, so that the cold crystallization temperature of the PLA is reduced to a certain extent, the processing window of the PLA/PBS composite material is widened, and the forming processing is easy.
Description of the drawings:
FIG. 1 shows the tensile strength of the PLA/PBS composite modified material.
Detailed Description
The following further describes the embodiments of the present invention. The technical features mentioned in the embodiments of the present invention described below are all in accordance with the requirements as long as they do not conflict with each other. The starting materials and reagents are commercially available.
The temperatures in the first to ninth zones of the twin-screw extruder described in the examples below were 150 ℃, 180 ℃, 180 ℃, 185 ℃, 185 ℃, 190 ℃, 190 ℃, 185 ℃, 190 ℃ and 230 ℃ for the die temperature.
The micro-nano laminated coextrusion equipment manufacturers described in the following examples: suzhou jin latitude machinery manufacturing, Inc.; the lamination die temperature was 220 ℃.
Example 1
(1) Drying PLA-4032D and PBS-TH801 at 65 ℃ for 6 hours for later use;
(2) after drying, taking 70 parts of PLA-4032D and 30 parts of PBS-TH801 (by weight), and then weighing a chain extender: ADR-4368 (1.5 parts by weight), a compatilizer: EsunBio5004K (4 parts by weight), hydrolysis resistant agent: sequentially adding carbodiimide with the brand number of UN-150 (1 part by weight) into a high-speed mixer, stirring for 5-8 minutes, and discharging for later use;
(3) adding the mixture obtained in the step (2) into a double-screw extruder for melt blending extrusion, and extruding the mixture through micro-nano laminated co-extrusion equipment to obtain the product;
wherein the rotating speed of the high-speed mixer is 1500 revolutions per minute; the temperature range of the double-screw extruder is 150-190 ℃.
The tensile strength of the obtained PLA/PBS composite material is 8MPa, and the impact strength is 20.8 MPa.
Example 2
(1) Drying PLA-4032D and PBS-TH801 at 65 ℃ for 6 hours for later use;
(2) after drying, taking 75 parts of PLA-4032D and 25 parts of PBS-TH801 (in parts by weight), and then weighing a chain extender: ADR-4368 (1.5 parts by weight), a compatilizer: EsunBio5004K (3 parts by weight), hydrolysis resistant agent: sequentially adding carbodiimide with the brand number of UN-150 (1 part by weight) into a high-speed mixer, stirring for 5-8 minutes, and discharging for later use;
(3) adding the mixture obtained in the step (2) into a double-screw extruder for melt blending extrusion, and extruding the mixture through micro-nano laminated co-extrusion equipment to obtain the product;
wherein the rotating speed of the high-speed mixer is 1500 revolutions per minute; the temperature range of the double-screw extruder is 150-190 ℃.
The tensile strength of the obtained PLA/PBS composite material is 12.5MPa, and the impact strength is 16.5 MPa.
Example 3
(1) Drying PLA-4032D and PBS-TH801 at 65 ℃ for 6 hours for later use;
(2) after drying, taking 80 parts of PLA-4032D and 20 parts of PBS-TH801 (in parts by weight), and then weighing a chain extender: ADR-4368 (1.5 parts by weight), a compatilizer: EsunBio5004K (2 parts by weight), hydrolysis resistant agent: sequentially adding carbodiimide with the brand number of UN-150 (1 part by weight) into a high-speed mixer, stirring for 5-8 minutes, and discharging for later use;
(3) adding the mixture obtained in the step (2) into a double-screw extruder for melt blending extrusion, and extruding the mixture through micro-nano laminated co-extrusion equipment to obtain the product;
wherein the rotating speed of the high-speed mixer is 1500 revolutions per minute; the temperature range of the double-screw extruder is 150-190 ℃.
The tensile strength of the obtained PLA/PBS composite material is 14.6MPa, and the impact strength is 12.5 MPa.
Example 4
(1) Drying PLA-4032D and PBS-TH801 at 65 ℃ for 6 hours for later use;
(2) after drying, taking PLA-4032D (85 parts by weight) and PBS-TH801 (15 parts by weight), and then weighing a chain extender: ADR-4368 (1.5 parts by weight), a compatilizer: EsunBio5004K (1.5 parts by weight), hydrolysis resistant agent: sequentially adding carbodiimide with the brand number of UN-150 (1 part by weight) into a high-speed mixer, stirring for 5-8 minutes, and discharging for later use;
(3) adding the mixture obtained in the step (2) into a double-screw extruder for melt blending extrusion, and extruding the mixture through micro-nano laminated co-extrusion equipment to obtain the product;
wherein the rotating speed of the high-speed mixer is 1500 revolutions per minute; the temperature range of the double-screw extruder is 150-190 ℃.
The tensile strength of the obtained PLA/PBS composite material is 18.7MPa, and the impact strength is 11.5 MPa.
Example 5
(1) Drying PLA-4032D and PBS-TH801 at 65 ℃ for 6 hours for later use;
(2) after drying, taking 90 parts by weight of PLA-4032D and 10 parts by weight of PBS-TH801, and then weighing a chain extender: ADR-4368 (1.5 parts by weight), a compatilizer: EsunBio5004K (1 part by weight), hydrolysis resistant agent: sequentially adding carbodiimide with the brand number of UN-150 (1 part by weight) into a high-speed mixer, stirring for 5-8 minutes, and discharging for later use;
(3) adding the mixture obtained in the step (2) into a double-screw extruder for melt blending extrusion, and extruding the mixture through micro-nano laminated co-extrusion equipment to obtain the product;
wherein the rotating speed of the high-speed mixer is 1500 revolutions per minute; the temperature range of the double-screw extruder is 150-190 ℃.
The tensile strength of the obtained PLA/PBS composite material is 26.6MPa, and the impact strength is 10.3 MPa.
Comparative example 1
In the same manner as in example 5, but without the addition of PBS-TH801, the resulting material had an impact strength of 15MPa and a tensile strength of 22.5 MPa.
Comparative example 2
The same as example 5, but without the addition of the compatibilizer EsunBio5004K, the impact strength of the resulting material was 14.6MPa and the tensile strength was 15.5 MPa.
In the specific embodiment, in the PLA matrix, the PBS is subjected to in-situ fiber formation in the processing process by using the micro-nano laminated co-extrusion equipment, so that the crystallinity and the melting temperature of the PBS are improved, and the mechanical strength of the PLA/PBS composite material is improved. In the extrusion granulation process of PLA/PBS, the two-phase interfacial tension is greatly reduced through the action of the compatilizer, and the fibers of the PBS better provide heterogeneous nucleation sites for the PLA, so that the cold crystallization temperature of the PLA is reduced to a certain extent, the processing window of the PLA/PBS composite material is widened, and the forming processing is easy.
The invention provides a high-strength bio-based degradable PLA/PBS composite material for food packaging boxes and a method for preparing the same, and a plurality of methods and ways for implementing the technical scheme are provided. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. A high-strength bio-based degradable PLA/PBS composite material for food packaging boxes is characterized by being prepared from the following materials in parts by weight: 70-90 parts of polylactic acid, 10-30 parts of polybutylene succinate, 1-3 parts of a chain extender, 1-4 parts of a compatilizer and 0.5-2 parts of an anti-hydrolysis agent.
2. The composite material of claim 1, wherein the chain extender is an epoxy chain extender.
3. The composite material according to claim 2, wherein the epoxy chain extender is ADR-4368 and/or ADR-4370S.
4. The composite material of claim 1, wherein the compatibilizer is EsunBio 5004K.
5. The composite material of claim 1, wherein the hydrolysis resistant agent is a carbodiimide-based hydrolysis resistant agent.
6. The composite material according to claim 5, wherein the carbodiimide-based hydrolysis inhibitor is
1010 and/or UN-150.
7. The preparation method of the composite material according to any one of claims 1 to 6, characterized by weighing the materials according to the formula ratio, dispersing and stirring in a high-speed mixer, then performing melt mixing extrusion granulation by a double-screw extruder, and then performing extrusion by a micro-nano laminated co-extrusion device to obtain the composite material.
8. The method as claimed in claim 7, wherein the rotation speed of the high-speed mixer is 500-2000 r/min.
9. The method according to claim 7, wherein the time for the dispersion stirring is 5 to 6 min.
10. The method as claimed in claim 7, wherein the temperature of the twin-screw extruder is 150 ℃ to 190 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210522852.1A CN114752198A (en) | 2022-05-13 | 2022-05-13 | High-strength bio-based degradable PLA/PBS composite material for food packaging boxes and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210522852.1A CN114752198A (en) | 2022-05-13 | 2022-05-13 | High-strength bio-based degradable PLA/PBS composite material for food packaging boxes and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087488A (en) * | 2013-01-31 | 2013-05-08 | 金发科技股份有限公司 | Biodegradable polylactic acid composite material, and preparation method and application thereof |
| CN105907061A (en) * | 2016-05-06 | 2016-08-31 | 王泽陆 | PBS (Polybuthylenesuccinate) /PLA (Polylactic Acid)/PHA (Polyhydroxyalkanoate) biodegradable composite material and preparation method thereof |
| CN111040400A (en) * | 2019-12-27 | 2020-04-21 | 周锐 | Full-biodegradable sheet and preparation method thereof |
| CN113185821A (en) * | 2021-05-18 | 2021-07-30 | 温州大学 | High-toughness heat-resistant biodegradable composite material for tableware and preparation method thereof |
| CN113429750A (en) * | 2021-06-05 | 2021-09-24 | 贾帅 | Composite toughened high-temperature-resistant polylactic acid modified material and preparation method thereof |
| CN113619241A (en) * | 2021-08-09 | 2021-11-09 | 江苏利特尔绿色包装股份有限公司 | Biodegradable high-barrier paper-plastic packaging composite film and preparation method thereof |
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2022
- 2022-05-13 CN CN202210522852.1A patent/CN114752198A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087488A (en) * | 2013-01-31 | 2013-05-08 | 金发科技股份有限公司 | Biodegradable polylactic acid composite material, and preparation method and application thereof |
| CN105907061A (en) * | 2016-05-06 | 2016-08-31 | 王泽陆 | PBS (Polybuthylenesuccinate) /PLA (Polylactic Acid)/PHA (Polyhydroxyalkanoate) biodegradable composite material and preparation method thereof |
| CN111040400A (en) * | 2019-12-27 | 2020-04-21 | 周锐 | Full-biodegradable sheet and preparation method thereof |
| CN113185821A (en) * | 2021-05-18 | 2021-07-30 | 温州大学 | High-toughness heat-resistant biodegradable composite material for tableware and preparation method thereof |
| CN113429750A (en) * | 2021-06-05 | 2021-09-24 | 贾帅 | Composite toughened high-temperature-resistant polylactic acid modified material and preparation method thereof |
| CN113619241A (en) * | 2021-08-09 | 2021-11-09 | 江苏利特尔绿色包装股份有限公司 | Biodegradable high-barrier paper-plastic packaging composite film and preparation method thereof |
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