CN111187495A - Preparation method of high-toughness high-heat-resistance transparent polylactic acid composite material - Google Patents
Preparation method of high-toughness high-heat-resistance transparent polylactic acid composite material Download PDFInfo
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- CN111187495A CN111187495A CN202010017134.XA CN202010017134A CN111187495A CN 111187495 A CN111187495 A CN 111187495A CN 202010017134 A CN202010017134 A CN 202010017134A CN 111187495 A CN111187495 A CN 111187495A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Abstract
The invention discloses a preparation method of a high-toughness high-heat-resistance transparent polylactic acid (PLA) composite material. The core-shell toughening agent S-2001 takes organic silicon and acrylate copolymer as a core and polymethyl methacrylate as a shell; methyl Methacrylate (MMA) and Glycidyl Methacrylate (GMA) copolymer (MG) are used as heat-resistant modifier and compatibilizer. The composite material comprises the following components in percentage by mass: 50-80% of polylactic acid (PLA), 20% of core-shell toughening agent S-2001 and 5-30% of copolymer (MG) of Methyl Methacrylate (MMA) and Glycidyl Methacrylate (GMA). The high-toughness high-heat-resistance transparent polylactic acid composite material provided by the invention has the shock resistance as high as 1015J/m, the glass transition temperature is increased to 80.8 ℃, and when the thickness of a sample is 0.5mm and the wavelength is 800nm, the light transmittance is 84%. The prepared PLA composite material has great application prospects in the aspects of packaging, automobile interior decoration, 3D printing and the like.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a preparation method of a high-toughness high-heat-resistance transparent polylactic acid composite material. The toughness, heat resistance and transparency of the polylactic acid product are improved.
Background
In order to solve the problem of "white pollution" caused by conventional plastic products, the use of completely biodegradable polymers, which are environmentally friendly, instead of conventional petroleum-based plastics has become a hot spot of current research and development. Polylactic acid (PLA) is a new biodegradable material made using starch feedstock proposed by renewable plant resources such as corn and the like. The starch is fermented to prepare lactic acid, and then is converted into polylactic acid through chemical synthesis. PLA has excellent biodegradability and biocompatibility, is finally decomposed into carbon dioxide and water in the environment, has no pollution to the environment, and is one of the research hotspots of degradable materials. The synthesis and application of polylactic acid have been studied as early as fifty years, high molecular weight optically active D-type and L-type PLA have been synthesized from seventy years, and are used for research in pharmaceutical preparations, medical surgery and the like, and various copolymers mainly comprising PLA have been synthesized in order to overcome the limitation that the degradation speed of PLA is regulated by the molecular weight and the distribution thereof. After the eighties, with the continuous expansion of the application field of PLA and the copolymer thereof, the research on the synthesis mechanism, the synthesis and the application of the copolymer with different structures and compositions is increasingly expanded.
The synthetic technology developed by the research institute of applied chemistry of Changchun, national academy of sciences, followed by Nature Works, USA, has also realized the large-scale production of PLA. As PLA enters the industrial production stage, PLA is applied to various fields of national economic construction like other general plastics. Polylactic acid is a high molecular material with good biocompatibility and biodegradability, and compared with polyolefin, the polylactic acid has incomparable characteristics in the aspect of environmental protection. PLA has higher strength, certain biocompatibility and heat resistance, and can be modified to obtain a material with antibacterial and flame retardant properties; and the PLA can be processed and molded by methods such as blow molding, injection molding and the like, and is simple and convenient to process, so that the PLA is considered to be a green biodegradable material which can completely or partially replace petroleum-based high polymer materials and has a relatively prospect. At present, PLA materials are widely applied to various fields (such as disposable products, biomedicine, packaging, automobile interior trim and the like), but the defects of brittleness, poor toughness and low heat distortion temperature limit the wide application of the PLA materials in production and life.
Chinese patent CN1304471C discloses that polylactic acid, glyceryl triacetate, lubricant and other components are blended to prepare polylactic resin for preparing tear-resistant and high-transparency polylactic acid films. But the heat resistance of the product is reduced.
Chinese patent CN102942772B discloses that the impact strength of the obtained toughened polylactic acid resin is up to 66.8KJ/m by using a core-shell structure copolymer with butadiene-styrene copolymer as a core and methyl methacrylate and glycidyl methacrylate copolymer as a shell as a toughening agent to toughen polylactic acid2The elongation at break is about 200 percent, and the tensile strength reaches 56.4 MPa. But the transparency of the polylactic acid blend is reduced and the thermal performance is not improved.
Chinese patent CN107090165A discloses a method for preparing polylactic acid modified material with high strength, good heat resistance and controllable degradability, which adopts green light catalytic material nano TiO2And the nano calcium lactate and the polylactic acid material are blended to prepare the composite material, so that the heat resistance and the strength of the polylactic acid are improved, and the degradation performance of the material can be selectively changed. Although the above patent improves the strength and heat resistance of polylactic acid products, the transparency is reduced and the toughness is not improved significantly.
Chinese patent CN105733216A discloses a method for toughening a polylactic acid material by blending a nylon 6 and epoxy composite material with polylactic acid, which effectively improves the impact strength and tensile strength of the polylactic acid. But the heat resistance and transparency of the polylactic acid copolymer are lowered.
Although the blending modification method partially improves the performance of the polylactic acid, the high toughness, the high heat resistance and the high transparency of the polylactic acid composite material are not realized, which is a key problem to be solved by the patent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a high-toughness high-heat-resistance transparent polylactic acid composite material to solve the problems of brittleness, poor toughness, poor heat-resistance stability after modification, poor transparency and the like of polylactic acid. The high-toughness high-heat-resistance transparent polylactic acid composite material prepared by the invention improves the toughness and heat resistance of polylactic acid matrix resin and keeps higher transparency of the material.
The invention provides a high-toughness high-heat-resistance transparent polylactic acid composite material, which comprises the following components in percentage by mass:
50-80 parts by mass of polylactic acid;
20 parts by mass of a core-shell toughening agent S-2001;
5-30 parts by mass of a copolymer of Methyl Methacrylate (MMA) and Glycidyl Methacrylate (GMA) (abbreviated as MG).
The polylactic acid is plastic particles, the molecular weight of PLA is 207000, and the polydispersity is 1.7;
the core-shell toughening agent takes an organic silicon and acrylate copolymer as a core and polymethyl methacrylate as a shell (S-2001 for short);
the copolymer MG is a copolymer of Methyl Methacrylate (MMA) and Glycidyl Methacrylate (GMA), and the mass fractions of MMA and GMA in the copolymer MG are 95% and 5%, respectively. The MG copolymer synthesis method is disclosed in patent CN 102030861B;
compared with the prior art, the invention provides the high-toughness high-heat-resistance transparent polylactic acid composite material. The technical innovation is that the copolymer MG of Methyl Methacrylate (MMA) and Glycidyl Methacrylate (GMA) is synthesized by utilizing the self-contained technology, and the MG plays multiple roles in a blending system. The MG copolymer is compatible with polylactic acid in thermodynamics, is completely compatible with a shell layer of a core-shell toughener S-2001, improves the dispersibility of S-2001 particles in a PLA matrix, enhances the interface strength between PLA and S-2001 particles, and is beneficial to improving the mechanical property of materials; (II) the MG copolymer and the PLA are subjected to chain extension reaction, so that the molecular weight of the PLA is increased, and the tensile strength is improved; thirdly, the MG copolymer has higher glass transition temperature (110-120 ℃), the glass transition temperature of the material after being blended with the PLA is increased, and the heat resistance of the material is enhanced; the (tetra) MG copolymer has high transparency, so that the PLA blend toughened by the S-2001 keeps higher transparency.
The high-toughness high-heat-resistance transparent polylactic acid composite material obtained by the invention has wide application fields, and especially has great application prospects in the aspects of packaging, automobile interior decoration, 3D printing and the like. And the blending modification method for preparing the high-toughness high-heat-resistance transparent polylactic acid composite material is simple in equipment, easy in process realization and suitable for various processing requirements.
The specific implementation mode is as follows:
the invention provides a high-toughness high-heat-resistance transparent polylactic acid composite material, which comprises the following components in percentage by mass:
50-80 parts by mass of polylactic acid
20 parts by mass of core-shell toughening agent S-2001
5 to 30 parts by mass of a copolymer MG
The polylactic acid is 4032D type plastic particles of the American Nature Works company, the molecular weight of PLA is 207000, and the polydispersity is 1.7;
the core-shell toughening agent takes an organic silicon and acrylate copolymer as a core, and polymethyl methacrylate as a shell (S-2001 for short), and is produced by Mitsubishi Yang corporation of Japan;
the copolymer MG is a copolymer of Methyl Methacrylate (MMA) and Glycidyl Methacrylate (GMA), and the mass fractions of MMA and GMA in the copolymer MG are 95% and 5%, respectively. The synthesis method of MG copolymer is disclosed in patent CN 102030861B
In the invention, the high-toughness high-heat-resistance transparent polylactic acid composite material is prepared by the following method: a copolymer (MG) of Methyl Methacrylate (MMA) and Glycidyl Methacrylate (GMA) was prepared according to the method of patent CN 102030861B. And weighing the polylactic acid, the core-shell toughening agent S-2001 and the copolymer MG according to different mass ratios, and then preparing the high-toughness, high-heat-resistance and high-transparency polylactic acid type composite material by adopting HAAKE rheometer for melt blending. The mixing mode of the polylactic acid, the toughening agent and the copolymer MG is not particularly limited, and can be a mixing mode well known by a person skilled in the art; the HAAKE rheometer is not particularly limited, and can be a HAAKE rheometer well known to those skilled in the art, and the HAAKE rheometer is preferably a HAAKE rheometer of TYP557-9301, manufactured by Haake, Germany; the invention has no special requirements on the process for preparing the high-toughness high-heat-resistance transparent polylactic acid composite material by mixing, can be a mixing preparation process well known by the technical personnel in the field, and preferably has the rotor rotating speed of 60r/min, the blending time of 6min and the blending temperature of 190 ℃. After blending, the samples are respectively hot-pressed for 3min in a flat vulcanizing machine, then cold-pressed for 3min, pressed into 2.4mm, 1mm and 0.5mm thin plates and to be tested.
The performance test of the obtained polylactic acid composite material shows that the impact resistance of the high-toughness high-heat-resistance transparent polylactic acid composite material provided by the invention is up to 1015J/m, the glass transition temperature is increased to 80.8 ℃, and the light transmittance is 84% when the sample thickness is 0.5mm and the wavelength is 800 nm.
In order to further illustrate the present invention, the following will describe the transparent polylactic acid composite material with high toughness and high heat resistance in detail with reference to the examples.
Comparative example
The PLA raw material is dried for 4 hours in a vacuum oven at 60 ℃, and the core-shell toughener S-2001 and the MG copolymer are dried for 8 hours in the vacuum oven at 80 ℃.
Weighing 80 parts by mass of PLA
Toughening agent S-200120 parts by mass
And (3) melting and blending the polylactic acid and the toughening agent S-2001 in a HAAKE rheometer. The blending temperature is 190 ℃, the rotor speed is 60r/min, and the blending time is 5 min. After blending, the sample is hot-pressed for 3min in a flat vulcanizing machine, then cold-pressed for 3min, and pressed into 2.4mm, 1mm and 0.5mm thin plates to be tested.
The polylactic acid blend samples obtained were subjected to performance tests, the results of which are shown in table 1.
Example one
The PLA raw material is dried for 4 hours in a vacuum oven at 60 ℃, and the core-shell toughener S-2001 and the MG copolymer are dried for 8 hours in the vacuum oven at 80 ℃.
Weighing 75 parts by mass of PLA
Toughening agent S-200120 parts by mass
Copolymer MG 5 parts by mass
Melt blending the polylactic acid, toughener S-2001 and copolymer MG in a HAAKE rheometer. The blending temperature is 190 ℃, the rotor speed is 60r/min, and the blending time is 5 min. After blending, all samples are respectively hot-pressed for 3min in a flat vulcanizing machine, then cold-pressed for 3min, pressed into 2.4mm, 1mm and 0.5mm thin plates and to be tested.
The resulting polylactic acid blends were subjected to performance tests, the results of which are shown in table 1.
Example two
The PLA raw material is dried for 4 hours in a vacuum oven at 60 ℃, and the core-shell toughener S-2001 and the MG copolymer are dried for 8 hours in the vacuum oven at 80 ℃.
70 parts by mass of PLA is weighed
Toughening agent S-200120 parts by mass
Copolymer MG 10 parts by mass
Melt blending the polylactic acid, toughener S-2001 and copolymer MG in a HAAKE rheometer. The blending temperature is 190 ℃, the rotor speed is 60r/min, and the blending time is 5 min. After blending, all samples are respectively hot-pressed for 3min in a flat vulcanizing machine, then cold-pressed for 3min, pressed into 2.4mm, 1mm and 0.5mm thin plates and to be tested.
The resulting polylactic acid blends were subjected to performance tests, the results of which are shown in table 1.
EXAMPLE III
The PLA raw material is dried for 4 hours in a vacuum oven at 60 ℃, and the core-shell toughener S-2001 and the MG copolymer are dried for 8 hours in the vacuum oven at 80 ℃.
Weighing 65 parts by mass of PLA
Toughening agent S-200120 parts by mass
Copolymer MG 15 parts by mass
Melt blending the polylactic acid, toughener S-2001 and copolymer MG in a HAAKE rheometer. The blending temperature is 190 ℃, the rotor speed is 60r/min, and the blending time is 5 min. After blending, all samples are respectively hot-pressed for 3min in a flat vulcanizing machine, then cold-pressed for 3min, pressed into 2.4mm, 1mm and 0.5mm thin plates and to be tested.
The resulting polylactic acid blends were subjected to performance tests, the results of which are shown in table 1.
Example four
The PLA raw material is dried for 4 hours in a vacuum oven at 60 ℃, and the core-shell toughener S-2001 and the MG copolymer are dried for 8 hours in the vacuum oven at 80 ℃.
60 parts by mass of PLA is weighed
Toughening agent S-200120 parts by mass
Copolymer MG 20 parts by mass
Melt blending the polylactic acid, toughener S-2001 and copolymer MG in a HAAKE rheometer. The blending temperature is 190 ℃, the rotor speed is 60r/min, and the blending time is 5 min. After blending, all samples are respectively hot-pressed for 3min in a flat vulcanizing machine, then cold-pressed for 3min, pressed into 2.4mm, 1mm and 0.5mm thin plates and to be tested.
The resulting polylactic acid blends were subjected to performance tests, the results of which are shown in table 1.
EXAMPLE five
The PLA raw material is dried for 4 hours in a vacuum oven at 60 ℃, and the core-shell toughener S-2001 and the MG copolymer are dried for 8 hours in the vacuum oven at 80 ℃.
Weighing 55 parts by mass of PLA
Toughening agent S-200120 parts by mass
Copolymer MG 25 parts by mass
Melt blending the polylactic acid, toughener S-2001 and copolymer MG in a HAAKE rheometer. The blending temperature is 190 ℃, the rotor speed is 60r/min, and the blending time is 5 min. After blending, all samples are respectively hot-pressed for 3min in a flat vulcanizing machine, then cold-pressed for 3min, pressed into 2.4mm, 1mm and 0.5mm thin plates and to be tested.
The resulting polylactic acid blends were subjected to performance tests, the results of which are shown in table 1.
EXAMPLE six
The PLA raw material is dried for 4 hours in a vacuum oven at 60 ℃, and the core-shell toughener S-2001 and the MG copolymer are dried for 8 hours in the vacuum oven at 80 ℃.
50 parts by mass of PLA is weighed
Toughening agent S-200120 parts by mass
Copolymer MG 30 parts by mass
Melt blending the polylactic acid, toughener S-2001 and copolymer MG in a HAAKE rheometer. The blending temperature is 190 ℃, the rotor speed is 60r/min, and the blending time is 5 min. After blending, all samples are respectively hot-pressed for 3min in a flat vulcanizing machine, then cold-pressed for 3min, pressed into 2.4mm, 1mm and 0.5mm thin plates and to be tested.
The resulting polylactic acid blends were subjected to performance tests, the results of which are shown in table 1.
TABLE 1 high toughness, high heat resistance and transparent polylactic acid composite material performance test results
| Test items | Comparative example | Example one | Example two | EXAMPLE III | Example four | EXAMPLE five | EXAMPLE six |
| Notched impact strength (J/m) | 770 | 1015 | 721 | 719 | 640 | 585 | 547 |
| Glass transition temperature (. degree. C.) | 60.1 | 61.5 | 65.8 | 68.7 | 71.5 | 76.5 | 80.8 |
| Light transmittance (%) | 76 | 81 | 84 | 79 | 78 | 78 | 76 |
From the above examples, it can be seen that the polylactic acid composite material modified by the core-shell toughener S-2001 and the MG copolymer has high notched impact strength, glass transition temperature and light transmittance.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall into the protection scope of the claims of the present invention.
Claims (8)
1. A high-toughness high-heat-resistance transparent polylactic acid composite material comprises polylactic acid and a toughening agent, and is characterized by also comprising a copolymer of methyl methacrylate and glycidyl methacrylate (MG for short).
2. The polylactic acid composite material according to claim 1, wherein the mass fraction of the polylactic acid is 50% to 80%.
3. The polylactic acid composite material according to claim 1, wherein the mass fraction of the toughening agent is 20%.
4. The polylactic acid composite material according to claim 1, wherein the polylactic acid has a number average molecular weight of 5 to 20 ten thousand.
5. The polylactic acid composite material according to claim 1, wherein the MG is present in an amount of 5 to 30% by mass.
6. The polylactic acid composite material as claimed in claim 1, wherein the toughening agent is a core-shell structure toughening agent, the core phase is an organosilicon and acrylate copolymer, and the shell layer is polymethyl methacrylate.
7. A polylactic acid composite according to claim 1, wherein MG is 5% by mass of glycidyl methacrylate in methyl.
8. The polylactic acid composite material as claimed in claim 1, wherein the preparation method of the polylactic acid composite material comprises the steps of drying PLA, core-shell toughening agent and MG copolymer before mixing, wherein the drying temperature is PLA60 ℃, and the drying time is 4 hours; the core-shell toughening agent and the MG copolymer are 80 ℃ for 8 hours, the dried PLA, the core-shell toughening agent and the MG copolymer are weighed according to a certain proportion, then are melted and blended in a HAAKE rheometer, the blending temperature is 190 ℃, the rotor speed is 60r/min, the blending time is 5min, after blending, all samples are respectively hot-pressed for 3min in a flat vulcanizing machine, and then are cold-pressed for 3min, and the standard sample strip testing performance is prepared.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112094488A (en) * | 2020-09-25 | 2020-12-18 | 长春工业大学 | High-toughness high-heat-resistance polylactic acid composite material and preparation method thereof |
| CN113416396A (en) * | 2021-05-14 | 2021-09-21 | 中船重工鹏力（南京）塑造科技有限公司 | High-permeability and high-toughness polylactic acid and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112094488A (en) * | 2020-09-25 | 2020-12-18 | 长春工业大学 | High-toughness high-heat-resistance polylactic acid composite material and preparation method thereof |
| CN113416396A (en) * | 2021-05-14 | 2021-09-21 | 中船重工鹏力（南京）塑造科技有限公司 | High-permeability and high-toughness polylactic acid and preparation method thereof |
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