CN113337092A - Transparent heat-resistant full-degradable component polylactic acid composite material and preparation method thereof - Google Patents
Transparent heat-resistant full-degradable component polylactic acid composite material and preparation method thereof Download PDFInfo
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 138
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 137
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000002667 nucleating agent Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims description 18
- 230000015556 catabolic process Effects 0.000 claims description 8
- 238000006731 degradation reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- LNKJESSHRFPVPE-UHFFFAOYSA-N 5-(diethylamino)pentyl 3,4,5-trimethoxybenzoate;hydrochloride Chemical compound Cl.CCN(CC)CCCCCOC(=O)C1=CC(OC)=C(OC)C(OC)=C1 LNKJESSHRFPVPE-UHFFFAOYSA-N 0.000 claims description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 4
- LNYGCDOWFJXOSW-UHFFFAOYSA-N 1-n,3-n,5-n-tricyclohexylbenzene-1,3,5-tricarboxamide Chemical compound C=1C(C(=O)NC2CCCCC2)=CC(C(=O)NC2CCCCC2)=CC=1C(=O)NC1CCCCC1 LNYGCDOWFJXOSW-UHFFFAOYSA-N 0.000 claims description 3
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 claims description 2
- -1 TMC-210 Chemical compound 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 5
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- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
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- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
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- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
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- 229920002223 polystyrene Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229920001875 Ebonite Polymers 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
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Classifications
-
- 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
- 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
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
- C08L2205/24—Crystallisation aids
Abstract
The invention relates to the technical field of polylactic acid modification, and discloses a transparent heat-resistant full-degradable component polylactic acid composite material and a preparation method thereof, wherein the composite material comprises polylactic acid and nucleating master batches, and the nucleating master batches comprise high-molecular-weight polylactic acid and beta-nucleating agent; the composite material comprises, by weight, 100 parts of polylactic acid, 3-15 parts of high molecular weight polylactic acid and 1-10 parts of beta-nucleating agent; its preparing process is also disclosed. The polylactic acid composite material adopts a simple and easy-to-operate process, can be widely applied to high-performance PLA-based composite materials after the transparency and heat resistance are optimized, and can be used for manufacturing important industrial products such as medical materials, high-temperature sterilization, degradable packages and the like.
Description
Technical Field
The invention relates to the technical field of polylactic acid modification, in particular to a transparent heat-resistant full-degradable component polylactic acid composite material and a preparation method thereof.
Background
Along with the comprehensive implementation of the plastic forbidden command, the development of the degradable plastic industry is greatly promoted, and the market demand of the degradable plastic is greatly increased. Among various degradable high polymer materials, polylactic acid has the advantages of high yield, low price, excellent comprehensive mechanical property and renewable resources, can become a future mainstream product of degradable plastics, and has wide development prospect.
However, polylactic acid (PLA) belongs to polyester, the molecular chain is relatively rigid, the motion capability of the molecular chain segment is limited, and too low molecular chain flexibility can cause slow crystallization process and incomplete crystallization, thereby exhibiting the characteristics of rigidity, brittleness and the like of Polystyrene (PS). The Heat Distortion Temperature (HDT) of pure PLA is 58-60 ℃, and the product is easy to deform or adhere, so that the heat resistance temperature requirement (HDT is more than 100 ℃) of a packaging material is not met, and the application field of PLA products is severely limited. Therefore, at present, PLA is often modified to improve its heat-resistant temperature and mechanical properties, so that it meets the requirements of high-temperature packaging materials.
The current methods for modifying PLA mainly include: regulating and controlling the chemical composition and condensed state structure of molecular chain and adding heat-resisting polymer into PLA matrix. Compared with the method that the crystallinity of the PLA is greatly improved and the heat resistance is further improved by regulating the chemical composition and the condensed structure of the molecular chain, the performance of the PLA is improved by adding the transparent heat-resistant polymer into the PLA matrix, and the method has the advantages of remarkable effect, capability of keeping the transparency and simple process. At present, the preparation method is mainly realized by adding heat-resistant polymers such as Polycarbonate (PC), polymethyl methacrylate (PMMA), PS and the like into a PLA matrix, and the heat-resistant polymers have the characteristics of wide sources, low cost, low molecular chain flexibility and almost no crystallization, show the outstanding advantage of easy blending modification due to wide thermal processing window, but have non-biodegradability.
The heat-resistant temperature of the interface layer can be improved by using heterogeneous nucleation to induce the epitaxial crystallization on the surface of the PLA heat-resistant polymer and form an interface crystal structure, but most of the reported crystal structures are randomly distributed in a matrix phase and a dispersed phase, so that the designability is lacked, and the improvement effect on the interface compatibility and HDT is limited.
Patent publication No. CN108752888B discloses a heat-resistant PLA composition and a preparation method thereof, the composition formed by PLA resin, starch graft copolymer and nucleating agent is adopted, although the degradability and heat resistance of PLA can be improved, starch is granular substance, the dispersity of the starch and PLA matrix is poor, the improvement of heat resistance is limited, and a product formed after adding the starch is non-transparent, so that the application of the product is greatly limited.
Patent publication No. CN106916422A discloses a method for preparing a highly transparent heat-resistant polylactic acid-based composite material, which uses polylactic acid, transparent resin and nucleating agent to form a composite material, and although the transparency and heat resistance of the polylactic acid product can be improved, the transparent resin is not degradable and the nucleating agent is difficult to be uniformly dispersed in the polylactic acid resin, so that the degradability is poor and the heat resistance is improved to a limited extent.
Therefore, research and development of a transparent heat-resistant fully-degradable polylactic acid material are urgently needed.
Disclosure of Invention
< problems to be solved by the present invention >
The current polylactic acid composite material is difficult to simultaneously combine the characteristics of high transparency, degradability and heat resistance.
< technical solution adopted in the present invention >
In view of the above technical problems, the present invention aims to provide a transparent heat-resistant fully degradable component polylactic acid composite material and a preparation method thereof.
The specific contents are as follows:
the invention provides a transparent heat-resistant full-degradable component polylactic acid composite material, which comprises polylactic acid and nucleating master batches, wherein the nucleating master batches comprise high-molecular-weight polylactic acid and beta-nucleating agent; the polylactic acid-beta-nucleating agent comprises, by weight, 100 parts of polylactic acid, 3-15 parts of high-molecular-weight polylactic acid and 1-10 parts of beta-nucleating agent.
Secondly, the invention provides a preparation method of a transparent heat-resistant full-degradable component polylactic acid composite material, which comprises the following steps,
s1 drying the polylactic acid and the high molecular weight polylactic acid for later use;
s2, sequentially premixing and melting the high molecular weight polylactic acid and the beta-nucleating agent, extruding and granulating, and drying to obtain nucleating master batches;
and (3) sequentially premixing and melting the S3 nucleating master batch and polylactic acid, then extruding and granulating, and drying to obtain the polylactic acid composite material.
< technical mechanism adopted in the present invention >
The polylactic acid has five crystal forms of stereocomplex (SC-PLA), alpha', beta and gamma, generally, the beta-type polylactic acid is thought to have interpenetration of lamella crystals, has no obvious crystal boundary, and can improve the heat distortion temperature of the polylactic acid while ensuring the transparency of the polylactic acid. Therefore, by introducing the beta-nucleating agent into the polylactic acid matrix, the problem of opacity of the interface layer caused by compatibility can be effectively avoided. Although the addition of the beta-nucleating agent can improve the interfacial property, the beta-nucleating agent is a granular/powdery material and is added into a PLA matrix, so that the condition of uneven dispersion is easily caused, and the improvement of the heat resistance is limited. In order to solve the problem, heat-resistant polymers (such as PC, PMMA, PS) are often added to further improve the heat resistance, but the addition of the heat-resistant polymers can improve the heat resistance and obtain a high transparency effect, but the degradability is poor, so that the environment-friendly development situation is difficult to be followed, and the application of the polymer is limited.
Based on the above statements, the applicant has creatively found that the addition of high molecular weight PLA as a heat-resistant dispersed phase to a polylactic acid matrix can ensure the degradability of the composite, but the improvement in heat resistance is limited; meanwhile, the beta-nucleating agent is combined to be the problem that the heat resistance is poor in improvement due to the fact that the granular/powdery material is difficult to uniformly disperse in the PLA matrix, high-molecular-weight PLA and the beta-nucleating agent are creatively mixed to form the nucleating master batch, and then the nucleating master batch is added into the PLA matrix.
Firstly, the PLA composite material formed by the method can overcome the problem that a beta-nucleating agent is not easy to disperse, and meanwhile, the polylactic acid composite material formed by the PLA composite material has multiple effects of high transparency, degradability and improvement of heat resistance due to the fact that the high molecular weight PLA is similar to the PLA molecular chain structure and has the characteristics of transparency and full degradation.
Secondly, the beta-nucleating agent is heated, melted and dispersed in the high molecular weight PLA, so that the high molecular weight PLA is loaded with the beta-nucleating agent, and a melt viscoelasticity coating effect of a physical entanglement network of the high molecular weight polymer is utilized to form a beta-nucleating agent enriched master batch; and then the self-assembly capability and the interface stress induction effect of the beta-nucleating agent and the diffusion effect brought by the concentration difference of two phases of the nucleating agent are utilized to control the release and migration of the beta-nucleating agent in the PLA matrix, so that the surface of the high molecular weight PLA is induced to form a beta-type crystal structure which is deep into the PLA matrix.
Finally, the high molecular weight PLA and the PLA belong to homogeneous matrixes, so that the high molecular weight PLA induces interface nucleation, the interface compatibility is improved, a transparent micro-area is formed, and the beta-nucleating agent is combined to refine the crystallization, so that the transparency and the heat resistance of the composite material can be improved.
< advantageous effects achieved by the present invention >
(1) The polylactic acid composite material adopts a process which is simple and easy to operate, can be widely applied to high-performance PLA-based composite materials after the transparency and heat resistance are optimized, and can be used for manufacturing important industrial products such as medical materials, high-temperature sterilization, degradable packages and the like;
(2) the polylactic acid composite material has improved strength, toughness and transparency, and simultaneously has degradability.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides a transparent heat-resistant full-degradable component polylactic acid composite material, which comprises polylactic acid and nucleating master batches, wherein the nucleating master batches comprise high-molecular-weight polylactic acid and beta-nucleating agent; the polylactic acid-beta-nucleating agent comprises, by weight, 100 parts of polylactic acid, 3-15 parts of high-molecular-weight polylactic acid and 1-10 parts of beta-nucleating agent.
In the present invention, the high molecular weight polylactic acid has a relative molecular weight of 1.5 x 106～5*106g/mol。
In the present invention, the polylactic acid has a relative molecular weight of 1 x 105g/mol。
In the present invention, the beta-nucleating agent comprises at least one of TMC-300, TMC-328, TMC-210, or TMB-5.
The invention also comprises 0.2-0.5 part of antioxidant.
In the present invention, the antioxidant includes antioxidant 245 and/or antioxidant 1010.
In the present invention, the polylactic acid is a poly (L-lactic acid), and the polymer polylactic acid is a polymer poly (L-lactic acid). The polylactic acid is preferably L-polylactic acid, which is cheap and easily available.
The invention provides a preparation method of a transparent heat-resistant full-degradable component polylactic acid composite material, which comprises the following steps:
s1 drying the polylactic acid and the high molecular weight polylactic acid for later use;
s2, sequentially premixing and melting the high molecular weight polylactic acid and the beta-nucleating agent, extruding and granulating, and drying to obtain nucleating master batches;
and (3) sequentially premixing and melting the S3 nucleating master batch and polylactic acid, then extruding and granulating, and drying to obtain the polylactic acid composite material.
In the invention, in S1, the drying temperature is 60-80 ℃, and the drying time is 4-8 h.
In the invention, in S2, the temperature of melt blending is 160-180 ℃.
In the invention, the temperature of melt blending in S3 is 155-175 ℃.
In the invention, in S2 and S3, the drying temperature is 60-80 ℃, and the drying time is 6-8 h.
In the present invention, the extrusion step may be performed according to a conventional process. The rotation speed of the extruder is controlled according to the diameter and the length-diameter ratio of the extruder.
< example >
Example 1
A transparent heat-resistant full-degradable component polylactic acid composite material comprises the following components in parts by weight,
100 parts of levorotatory polylactic acid, 10 parts of high molecular weight levorotatory polylactic acid, TMB-51 parts and 10100.3 parts of antioxidant. The molecular weight of the L-polylactic acid is 1 x 105g/mol, the molecular weight of the high molecular weight L-polylactic acid is 2 x 106g/mol。
The preparation method comprises the following steps of,
s1, drying the L-polylactic acid and the high molecular weight L-polylactic acid at 60-80 ℃ for 6-8 h for later use;
s2, physically blending high molecular weight levorotatory polylactic acid and beta-nucleating agent, adding the mixture into extrusion to perform melt extrusion granulation after physical blending, wherein the melt blending temperature is 160-180 ℃, and performing drying treatment at 60-80 ℃ for 6-8 h to obtain nucleation master batches;
the S3 nucleating master batch is physically blended with the levorotatory polylactic acid and the antioxidant 1010, and then is subjected to melt extrusion granulation after physical blending, wherein the melt blending temperature is 160-180 ℃, and the polylactic acid composite material is obtained after drying treatment at 60-80 ℃ for 6-8 hours.
Among them, in S2 and S3, the treatment may be carried out in accordance with a conventional extrusion process.
Example 2
This example is different from example 1 in the component ratio.
A transparent heat-resistant full-degradable component polylactic acid composite material comprises the following components in parts by weight,
100 parts of levorotatory polylactic acid, 15 parts of high molecular weight levorotatory polylactic acid, 51.5 parts of TMB and 10100.3 parts of antioxidant.
Example 3
This example is different from example 1 in the component ratio.
A transparent heat-resistant full-degradable component polylactic acid composite material comprises the following components in parts by weight,
100 parts of levorotatory polylactic acid, 5 parts of high molecular weight levorotatory polylactic acid, 50.5 parts of TMB and 10100.3 parts of antioxidant.
Example 4
This example differs from example 1 in that the β -nucleating agent is different.
In this example, the nucleating agent is TMC-300.
Example 5
This example differs from example 1 in that the β -nucleating agent is different.
In this example, the nucleating agent is TMC-328.
Example 6
This example differs from example 1 in that the β -nucleating agent is different.
In this example, the nucleating agent is TMC-210.
Example 7
This example differs from example 1 in the relative molecular mass of the high molecular weight polylactic acid.
In this example, the molecular weight of the high molecular weight poly (L-lactic acid) was 3 x 106g/mol。
Example 8
This example differs from example 1 in the relative molecular mass of the high molecular weight polylactic acid.
In this example, the molecular weight of the high molecular weight poly (L-lactic acid) was 5 x 106g/mol。
< comparative example >
Comparative example 1
The difference between the comparative example and the example 1 is that the levorotatory polylactic acid, the high molecular weight levorotatory polylactic acid, TMB-5 and the antioxidant 1010 are added into an extruder at the same time for melt extrusion and granulation.
Comparative example 2
This comparative example differs from example 1 in that TMB-5 was not added.
Comparative example 3
This comparative example differs from example 1 in that no high molecular weight L-polylactic acid was added.
Comparative example 4
This comparative example differs from example 1 in that the high molecular weight L-polylactic acid was replaced with PC in the same amount.
< test example >
The polylactic acid composite materials prepared in examples 1 to 3, 7 to 8 and comparative examples 1 to 4 were used as samples to measure transparency, heat resistance, mechanical properties and impact properties, respectively.
Wherein the content of the first and second substances,
transparency ofThe determination is carried out according to the method of GB2410-80 transparent plastic light transmittance and haze test method;
heat resistanceThe measurement indexes of (2) are heat distortion temperature and Vicat softening point, and the heat distortion temperature refers to GB/T1634.2-2004' measurement part 2 of plastic load distortion temperature: plastics, hard rubber and long fiber reinforced composites, the Vicat softening point is determined by reference to GB/T1633-;
mechanical propertiesThe measurement indexes of (1) comprise tensile property and bending strength, the tensile property is measured according to a method of ASTM D638-91 Standard test method for tensile property of plastics, and the bending strength is measured according to a method of GB/T9341-2008 measuring method for bending property of plastics;
impact performanceThe determination is carried out with reference to the method of ISO 179-1-2010 "determination of plastics pendulum impact Properties" part 1: non-mechanical impact test ".
The results of the experiment are shown in table 1.
As is clear from the results in Table 1, the polylactic acid composite materials obtained in examples 1 to 3 and 7 to 8 all had excellent effects in transparency, heat resistance, mechanical properties, impact properties, and the like. Comparative example 1 compared with example 1, the transparency, mechanical properties and impact properties of the raw material components directly added to the extruder are significantly reduced. Comparative example 2 shows a significant decrease in mechanical properties and impact strength when compared to example 1 without the addition of a beta-nucleating agent. Comparative example 3 shows a significant decrease in transparency, heat resistance, mechanical properties and impact properties when no high molecular weight PLLA is added, compared to example 1. Compared with example 1, the transparency, heat resistance, mechanical properties and impact properties of the comparative example 4 are significantly improved by adopting high molecular weight PLLA to be compared with PC.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A transparent heat-resistant full-degradable component polylactic acid composite material is characterized by comprising polylactic acid and nucleating master batches, wherein the nucleating master batches comprise high-molecular-weight polylactic acid and beta-nucleating agent; the polylactic acid-beta-nucleating agent comprises, by weight, 100 parts of polylactic acid, 3-15 parts of high-molecular-weight polylactic acid and 1-10 parts of beta-nucleating agent.
2. The polylactic acid composite material with transparent heat-resistant full degradation component according to claim 1, wherein the relative molecular weight of the high molecular weight polylactic acid is 1.5 x 106～5*106g/mol。
3. The polylactic acid composite material with transparent heat-resistant full degradation component according to claim 1, wherein the polylactic acid has a relative molecular weight of 1 x 105g/mol。
4. The transparent heat resistant fully degradable component polylactic acid composite material of claim 1 wherein the β -nucleating agent comprises at least one of TMC-300, TMC-328, TMC-210, or TMB-5.
5. The transparent heat-resistant full degradation component polylactic acid composite material according to any one of claims 1 to 4, wherein the polylactic acid is L-polylactic acid, and the high molecular weight polylactic acid is high molecular weight L-polylactic acid.
6. The polylactic acid composite material with the transparent heat-resistant full degradation component as claimed in any one of claims 1 to 4, further comprising 0.2-0.5 part of antioxidant, wherein the antioxidant comprises antioxidant 245 and/or antioxidant 1010.
7. A method for preparing a transparent heat-resistant fully degradable component polylactic acid composite material according to any one of claims 1 to 6, which comprises the following steps:
s1 drying the polylactic acid and the high molecular weight polylactic acid for later use;
s2, sequentially premixing and melting the high molecular weight polylactic acid and the beta-nucleating agent, extruding and granulating, and drying to obtain nucleating master batches;
and (3) sequentially premixing and melting the S3 nucleating master batch and polylactic acid, then extruding and granulating, and drying to obtain the polylactic acid composite material.
8. The method for preparing the polylactic acid composite material with the transparent heat-resistant full degradation component according to claim 7, wherein the temperature of melt blending in S2 is 160-180 ℃.
9. The method for preparing the polylactic acid composite material with the transparent heat-resistant full degradation component according to claim 7 or 8, wherein the temperature of melt blending in S3 is 155-175 ℃.
10. The method for preparing the polylactic acid composite material with the transparent heat-resistant full degradation component according to claim 7 or 8, wherein the drying temperature in S2 and S3 is 60-80 ℃ and the drying time is 6-8 h.
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