AU2019206096B2 - Polylactic acid film modified by organic-inorganic hybrid particles and method for producing same - Google Patents

Polylactic acid film modified by organic-inorganic hybrid particles and method for producing same Download PDF

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AU2019206096B2
AU2019206096B2 AU2019206096A AU2019206096A AU2019206096B2 AU 2019206096 B2 AU2019206096 B2 AU 2019206096B2 AU 2019206096 A AU2019206096 A AU 2019206096A AU 2019206096 A AU2019206096 A AU 2019206096A AU 2019206096 B2 AU2019206096 B2 AU 2019206096B2
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poe
pla
active
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Ligui CHEN
Lei Fu
Shikui JIA
Zhong Wang
Yan Zhu
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Shaanxi University of Technology
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    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • C08J2451/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides

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Abstract

Disclosed is a modified polylactic acid film, including a POE-g-MA/GO hybrid functional masterbatch and PLA, where the PLA has a mass fraction of 80-95%, the POE-g-MA/GO hybrid functional masterbatch has a mass fraction of 5-20%, and the sum of 5 the mass fractions of the above components is 100%. Moreover, the present invention also provides a method for producing a PLA material modified with the POE-g-MA/GO hybrid functional masterbatch, in which the PLA film material can be modified to obtain an improved hygrothermal aging resistance, thus further expanding the development of organic-inorganic hybrid functional materials and promoting the application of PLA materials. ~Mixing Highly-active aqueous GO solution Grinding Low-temperature drying) Highly- active POE-g-MA GO powder organic elastomer Extruding and mixing) POE-g-MA/GO functional master batch PLA (Extruding and film-blowing PA film with hybrid POE g-MA/GO Performance test and application analysis

Description

POLYLACTIC ACID FILM MODIFIED BY ORGANIC-INORGANIC HYBRID PARTICLES AND METHOD FOR PRODUCING SAME
TECHNICAL FIELD
The present application relates to the preparation of composite materials, and more 5 particularly to a polylactic acid film modified by organic-inorganic hybrid particles and a method for producing the same.
BACKGROUND OF THE INVENTION
With the depletion of petroleum resources and the increase of environmental pollution, the development of polymers through petrochemical method will further worsen the 0 environmental pollution due to the shortcomings of high energy and resource consumption, serious pollution and difficulty in the degradation. Therefore, the development and application of an environmentally-friendly bio-based biodegradable polymer are of great interest for the academic and industrial circles around the world.
In recent decades, dozens of biodegradable polyester materials have been developed, of .5 which polylactic acid (PLA) has attracted the most attention due to its good mechanical properties, biocompatibility and processability. At present, about half of the bio-based plastics with an annual yield of about 7.Ox 105-8.0x 105 tons in the world is PLA. At the same time, since the PLA can be basically prepared from some renewable plant resources such as com and grain, the product after use can be decomposed or degraded into non-toxic and harmless carbon 20 dioxide and water under certain conditions, which effectively avoids the environmental pollution.
PLA has been produced in large scale in industry and has shown unique and broad application prospects in frontier science and technology fields such as film, fiber and bioengineering stents. In addition, PLA also has good mechanical properties, transparency,
2019206096 18 Jul 2019 antimicrobial properties and processability, which can be widely used in plastic packaging, biomedicine, daily necessities and other industries. Currently, the biodegradable PLA can be gradually applied in packaging films and agricultural films as the production cost decreases. However, a desired film material must meet the basic requirements of blocking properties (for 5 water vapor, oxygen, carbon dioxide, light, etc.), optical properties (transparency), mechanical properties and molding properties, migration and residue, chemical properties, heat resistance, waste disposal and antistatic properties, since these properties may directly or indirectly affect the use value and safety of the PLA film materials. Moreover, the packaging film materials and agricultural film materials are also required for high hygrothermal aging resistance. However, 0 PLA has inherent drawbacks of low blocking properties and poor hygrothermal aging resistance, which will limit the application. For better application of PLA as film materials, lots of researches have been conducted to develop a method, a technique or a device for improving the hygrothermal aging resistance of PLA. It is worth noting that physical properties of PLA materials can be optimized by proper molecular chain design, composite modification 5 and other processes and methods. Therefore, based on a melting extrusion film-blowing apparatus and an extrusion method, the organic-inorganic hybrid particles resistant to hygrothermal aging can be dispersed into a PLA matrix, thereby effectively improving the hygrothermal aging resistance of the PLA film.
Maleic anhydride grafted ethylene-octene copolymer (POE-g-MA) is an organic polymer 20 elastomer with an octene soft chain curled structure and a crystalline ethylene chain, which has excellent toughness, good processability and excellent hygrothermal aging resistance due to the absence of unsaturated double bonds in the POE molecular structure. Meanwhile, graphene oxide (GO) is an inorganic particle with a unique sheet-like structure and certain reactivity, and it has not been reported on the use of solution intercalation technique and blending technique 25 to develop a hybrid POE-g-MA/GO material.
So far, a publication in Chemical Journal of Chinese Universities (Feng Yulin, 2012,
2019206096 13 Feb 2020
33(2): 400-403) demonstrated the toughening effect of a grafted elastomer structure on polylactic acid by treating the PLA with ethylene-octene copolymer grafted glycidyl methacrylate (POE-g-GMA) toughened PLA. In addition, POE-g-MA and calcium carbonate (CaCCh) were reported to synergistically toughen the PLA materials and the composite material was investigated for rheological and thermal properties (Jia Shikui, 2017, Acta Materiae Compositae Sinica, 34(2): 256-262). However, these two publications both fail to disclose the use of solution intercalation and melt mixing techniques to prepare an organic-inorganic hybrid material and to modify PLA.
SUMMARY OF THE INVENTION
Advantageously, the present invention may provide a polylactic acid film modified by organic-inorganic hybrid particles to solve the problem of poor hygrothermal aging resistance in the existing PLA films.
The present invention may also advantageously provide a method for producing the above polylactic acid film modified by organic-inorganic hybrid particles.
The first technical solution of the invention provides a polylactic acid film modified by organic-inorganic hybrid particles, including an organic-inorganic hybrid functional masterbatch resistant to hygrothermal aging and PLA, wherein PLA has a mass fraction of 80-95%; the organic-inorganic hybrid functional masterbatch has a mass fraction of 5-20%; and the sum of the mass fractions of PLA and the organic-inorganic hybrid functional 20 masterbatch is 100%.
The first technical solution of the invention is described in detail below.
The organic-inorganic hybrid functional masterbatch includes POE-g-MA and highly-active GO powder, wherein POE-g-MA has a mass fraction of 90-95%; the highly-active GO powder has a mass fraction of 5-10%; and the sum of the mass fractions of
2019206096 18 Jul 2019
POE-g-MA and the highly-active GO powder is 100%.
The highly-active GO powder includes GO, DCP and AIBN, wherein GO has a mass fraction of 85-95%; DCP has a mass fraction of 2-5%; AIBN has a mass fraction of 3-10%; and the sum of the mass fractions of GO, DCP and AIBN is 100%.
The second technical solution of the present invention is to provide a method for producing a polylactic acid film modified by organic-inorganic hybrid particles, comprising:
(1) preparing highly-active GO powder by solution intercalation;
(2) after step (1), preparing a POE-g-MA/GO hybrid functional masterbatch resistant to hygrothermal aging by blending; and (3) subjecting the POE-g-MA/GO hybrid functional masterbatch obtained in step (2) and
PLA to melt-extruding and film-blowing.
The second technical solution of the invention is described in detail below.
Further, the step (1) includes the following specific steps:
(1.1) adding dicumyl peroxide (DCP) and azobisisobutyronitrile (AIBN) to an aqueous 15 GO solution at a concentration of 1-8 mg/mL; placing the reaction mixture in a water bath pot at 0-40°C followed by dropwise addition of an acetone/ethanol solution; stirring the reaction mixture under a constant temperature for 4-12 h to obtain an aqueous layered GO solution;
where a mass ratio of GO to DCP to AIBN is 8.5-9.5: 0.2-0.5: 0.3-1;
the acetone/ethanol solution is 10-30% of the total volume of the aqueous GO solution, 20 DCP and AIBN;
a volume ratio of acetone to ethanol in the acetone/ethanol solution is 1:5-10; and
2019206096 18 Jul 2019 (1.2) allowing the aqueous layered GO solution obtained in step (1.1) to stand for filtration and drying in a vacuum drying oven at 10-40°C for 48-96 h to obtain highly-active GO; and grinding the highly-active GO followed by sieving to obtain the highly-active GO powder.
The step (2) specifically includes the following steps: premixing the highly-active GO powder as an inorganic component with POE-g-MA as an organic elastic component in a high-speed mixer; transferring the premixed product to a twin-screw extruder followed by melt-mixing, extruding, granulation and drying in a drying oven at 50-90°C for 4-12 h to obtain the POE-g-MA/GO hybrid functional masterbatch;
where a mass ratio of POE-g-MA to the highly-active GO powder is 9-9.5: 0.5-1;
an extrusion temperature of the twin-screw extruder is 150-200°C and a rotation speed of the twin-screw extruder is 30-90 r/min.
The step (3) specifically includes the following steps: premixing the POE-g-MA/GO hybrid functional masterbatch and the PLA in a high-speed mixer; and processing the premixed 5 product by an extruding and film-blowing device to produce a modified PLA film, that is, the polylactic acid film modified by organic-inorganic hybrid particles;
where a mass ratio of PLA to the POE-g-MA/GO hybrid functional masterbatch is 8-9.5: 0.5-2; and an extrusion temperature is 150-190°C.
The present invention has the following beneficial effects.
The invention first disperses and mixes the graphene oxide (GO) with a sheet-like structure, active DCP and AIBN in a solution to obtain an aqueous solution of highly-active layered GO, which is then filtered, dried at low temperature and ground to produce
2019206096 18 Jul 2019 highly-active GO powder. Then the anti-aging POE-g-MA organic elastomer is melt-mixed with the highly-active GO powder through reaction extrusion followed by granulation and drying to obtain a POE-g-MA/GO hybrid functional masterbatch having good oil-water barrier property and high hygrothermal aging resistance. The POE-g-MA/GO hybrid functional 5 masterbatch and PLA are subjected to the film-blowing molding by controlling the parameters of the extruding and film-blowing to obtain a PLA film resistant to hygrothermal aging. The method improves the hygrothermal aging resistance of the PLA film material by modification, facilitating the further development of organic-inorganic hybrid functional materials and promoting the application of PLA materials.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a flow chart showing a process of the present invention for preparing a polylactic acid film modified by organic-inorganic hybrid particles.
Figs. 2A-B are scanning electron microscope (SEM) images showing the POE-g-MA/GO/PLA before and after hygrothermal aging in an embodiment of the invention;
Figs. 3A-B are wide-angle X-ray diffraction (WAXD) images showing the POE-g-MA/GO/PLA before and after hygrothermal aging in an embodiment of the invention.
Figs. 4A-B are polarized optical microscope (POM) images showing the POE-g-MA/GO/PLA before and after hygrothermal aging in an embodiment of the invention.
Fig. 5 shows the thermal stability of the unmodified or modified PLA before and after 20 hygrothermal aging in an embodiment of the invention.
Fig. 6 shows the tensile strength of various modified PLA materials before and after hygrothermal aging in an embodiment of the invention.
2019206096 18 Jul 2019
DETAILED DESCRIPTION OF EMBODIMENTS
The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
The invention provides a polylactic acid film modified by organic-inorganic hybrid 5 particles, including an organic-inorganic hybrid functional masterbatch resistant to hygrothermal aging and PLA (polylactic acid), where PLA has a mass fraction of 80-95%; the organic-inorganic hybrid functional masterbatch has a mass fraction of 5-20%; and the sum of the mass fractions of PLA and the organic-inorganic hybrid functional masterbatch is 100%.
The organic-inorganic hybrid functional masterbatch (POE-g-MA/GO hybrid functional 0 masterbatch) includes POE-g-MA (maleic anhydride grafted ethylene-octene copolymer) and highly-active GO powder (highly-active graphene oxide powder), where POE-g-MA has a mass fraction of 90-95%; the highly-active GO powder has a mass fraction of 5-10%; and the sum of the mass fractions of POE-g-MA and the highly-active GO powder is 100%.
The highly-active GO powder includes GO (graphene oxide), dicumyl peroxide (DCP) 5 and azobisisobutyronitrile (AIBN), wherein GO has a mass fraction of 85-95%; DCP has a mass fraction of 2-5%; AIBN has a mass fraction of 3-10%; and the sum of the mass fractions of the above components is 100%.
The invention also discloses a method for producing a polylactic acid film modified by organic-inorganic hybrid particles, including:
(1) preparing highly-active GO powder by solution intercalation; where step (1) specifically includes the following steps:
(1.1) adding dicumyl peroxide (DCP) and azobisisobutyronitrile (AIBN) to an aqueous GO solution; placing the reaction mixture in a water bath pot at 0-40°C followed by dropwise
2019206096 18 Jul 2019 addition of an acetone/ethanol solution; and stirring the reaction mixture under a constant temperature for 4-12 h to obtain an aqueous layered GO solution;
where a mass ratio of GO to DCP to AIBN is 8.5-9.5: 0.2-0.5: 0.3-1;
a concentration of the aqueous GO solution is 1-8 mg/mL;
the acetone/ethanol solution is 10-30% of the total volume of the aqueous GO solution, DCP and AIBN;
a volume ratio of acetone to ethanol in the acetone/ethanol solution is 1:5-10;
(1.2) allowing the aqueous layered GO solution obtained in step (1.1) to stand for filtration and drying in a vacuum drying oven at 10-40°C for 48-96 h to obtain highly-active 0 GO; and grinding the highly-active GO followed by sieving to obtain the highly-active GO powder;
where a sieve having a pore size of 30-100 pm is used for sieving;
(2) after step (1), preparing a POE-g-MA/GO hybrid functional masterbatch (organic-inorganic hybrid functional masterbatch) resistant to hygrothermal aging by blending;
where the step (2) specifically includes the following steps:
premixing the highly-active GO powder as an inorganic component with POE-g-MA as an organic elastic component in a high-speed mixer; and transferring the premixed product to a twin-screw extruder followed by melt-mixing, extruding, granulation and drying in a drying oven at 50-90°C for 4-12 h to obtain the POE-g-MA/GO hybrid functional masterbatch;
where a mass ratio of POE-g-MA to the highly-active GO powder is 9-9.5: 0.5-1;
an extrusion temperature of the twin-screw extruder is 150-200°C and a rotation speed of
2019206096 18 Jul 2019 the twin-screw extruder is 30-90 r/min;
(3) subjecting the POE-g-MA/GO hybrid functional masterbatch obtained in step (2) and the PLA to melt-extruding and film-blowing;
where the step (3) specifically includes the following steps: premixing the 5 POE-g-MA/GO hybrid functional masterbatch with the PLA in a high-speed mixer; processing the premixed product by an extruding and film-blowing device to produce a modified PLA film, that is, the polylactic acid film modified by organic-inorganic hybrid particles;
where a mass ratio of PLA to the POE-g-MA/GO hybrid functional masterbatch is 8-9.5: 0.5-2;
an extrusion temperature of the extruding and film-blowing device is 150-190°C.
Example 1
The present invention provides a method for producing a polylactic acid film modified by organic-inorganic hybrid particles, which is shown in Fig. 1 and includes the following steps.
(1) Highly-active GO powder was prepared by solution intercalation, where the specific 15 steps were as follows.
(1.1) Dicumyl peroxide (DCP) and azobisisobutyronitrile (AIBN) were added to an aqueous GO solution. The reaction mixture was then placed in a water bath pot at 0°C, dropwise added with an acetone/ethanol solution and stirred at a constant temperature for 4 h to obtain an aqueous layered GO solution.
In step (1.1), a mass ratio of GO to DCP to AIBN was 9.5: 0.2: 0.3;
a concentration of the aqueous GO solution was 1 mg/mL;
2019206096 18 Jul 2019 the acetone/ethanol solution was 10% of the total volume of the aqueous GO solution, DCPandAIBN; and a volume ratio of acetone to ethanol in the acetone/ethanol solution was 1:5.
(1.2) The aqueous layered GO solution obtained in step (1.1) was allowed to stand, 5 filtered and dried in a vacuum drying oven at 10°C for 48 h to obtain highly-active GO. The obtained highly-active GO was ground and sieved to obtain the highly-active GO powder.
In step (1.2), a sieve having a pore size of 30 pm was used for sieving.
(2) After step (1), a POE-g-MA/GO hybrid functional masterbatch (organic-inorganic hybrid functional masterbatch) resistant to hygrothermal aging was prepared by blending, where the specific steps were described as follows.
The highly-active GO powder and POE-g-MA were respectively used as an inorganic component and an organic elastic component and premixed in a high-speed mixer and transferred to a twin-screw extruder for melt-mixing and extruding, granulation. The obtained product was dried in a drying oven at 50°C for 4 h to obtain the POE-g-MA /GO hybrid .5 functional masterbatch.
In step (2), a mass ratio of POE-g-MA to the highly-active GO powder was 9: 1; and an extrusion temperature of the twin-screw extruder was 150°C, and a rotation speed of the twin-screw extruder was 30 r/min.
(3) The obtained POE-g-MA/GO hybrid functional masterbatch obtained in step (2) and 20 the PLA were subjected to melt-extruding and film-blowing, where the specific steps were described as follows.
The POE-g-MA/GO hybrid functional masterbatch and the PLA were premixed in a
2019206096 18 Jul 2019 high-speed mixer and processed by an extruding and film-blowing device to produce a modified PLA film, i.e. the polylactic acid film modified by organic-inorganic hybridparticles.
In step (3), a mass ratio of PLA to POE-g-MA/GO hybrid functional masterbatch was 9.5: 0.5; and an extrusion temperature of the extruding and film-blowing device was 150°C.
Finally, a series of PLA materials modified with the POE-g-MA/GO hybrid functional masterbatch were subjected to hygrothermal aging in a hygrothermal aging chamber at a temperature of 50°C and a relative humidity (RH) of 90% for 48 h. Then the samples before and after hygrothermal aging were tested for micromorphology, crystalline morphology, crystal 0 morphology, thermal stability and tensile strength. It can be observed from Fig. 2A that the PLA material modified with the POE-g-MA/GO hybrid functional masterbatch before hygrothermal aging presented as fine particles with uniform dispersion, while as shown in Fig. 2B, a flowing cross-linking morphology was observed in the PLA material modified with the POE-g-MA/GO hybrid functional masterbatch after the hygrothermal aging. The wide-angle 5 X-ray diffraction (WAXD) results showed that the active GO or the POE-g-MA/GO hybrid functional masterbatch did not significantly affect the crystalline morphology of PLA (as shown in Fig. 3A), while after the hygrothermal aging, the crystalline diffraction peak of the PLA material modified with the active GO or the POE-g-MA/GO hybrid functional masterbatch became sharp (as shown in Fig. 3B). It can be seen from Figs. 4A-B that the 20 crystal of the PLA material modified with POE-g-MA/GO hybrid functional masterbatch was refined and improved in the perfection degree after the hygrothermal aging. Meanwhile, the thermal stability test showed that a thermal decomposition temperature of the pure PLA was decreased by about 20° C due to the hygrothermal aging, while the thermal decomposition temperature of the PLA material added with active GO or POE-g-MA/GO hybrid functional 25 masterbatch was less affected by the hygrothermal aging (as shown in Fig. 5). In addition, the
2019206096 18 Jul 2019 pure PLA and the PLA material modified with active GO or POE-g-MA/GO hybrid functional masterbatch were respectively tested for tensile strength. As shown in Fig. 6, after processed by a 72-h hygrothermal aging, the tensile strength of the pure PLA was reduced by 19%, while the tensile strength of the PLA material modified with the active GO or POE-g-MA/GO hybrid functional masterbatch was only reduced by 12.1% or 7.3%, respectively.
Example 2
The present invention provides a method for producing a polylactic acid film modified by organic-inorganic hybrid particles, which includes the following steps.
(1) Highly-active GO powder was prepared by solution intercalation, where the specific 0 steps were described as follows.
(1.1) Dicumyl peroxide (DCP) and azobisisobutyronitrile (AIBN) were added to an aqueous GO solution at a concentration of 3 mg/mL. The reaction mixture was placed in a water bath pot at 20°C, dropwise added with an acetone/ethanol solution and stirred at a constant temperature for 8 h to obtain an aqueous layered GO solution.
.5 In step (1.1), a mass ratio of GO to DCP to AIBN was 9.3: 0.2: 0.5;
the acetone/ethanol solution was 15% of the total volume of the aqueous GO solution, DCP and AIBN; and a volume ratio of acetone to ethanol in the acetone/ethanol solution was 1:6.
(1.2) The aqueous layered GO solution obtained in step (1.1) was allowed to stand, 20 filtered and dried in a vacuum drying oven at 20°C for 48 h to obtain highly-active GO. The obtained highly-active GO was ground and sieved to obtain the highly-active GO powder.
In step (1.2), a sieve having a pore size of 50 pm was used for sieving.
2019206096 18 Jul 2019 (2) After step (1), a POE-g-MA/GO hybrid functional masterbatch (organic-inorganic hybrid functional masterbatch) resistant to hygrothermal aging was prepared by blending, where the specific steps were described as follows.
The highly-active GO powder and POE-g-MA were respectively used as an inorganic component and an organic elastic component and premixed in a high-speed mixer and transferred to a twin-screw extruder for melt-mixing and extruding, granulation. The obtained product was dried in a drying oven at 60°C for 8 h to obtain the POE-g-MA /GO hybrid functional masterbatch.
In step (2), a mass ratio of POE-g-MA to the highly-active GO powder was 9.1: 0.9; and an extrusion temperature of the twin-screw extruder was 160°C, and a rotation speed of the twin-screw extruder was 40 r/min.
(3) The obtained POE-g-MA/GO hybrid functional masterbatch obtained in step (2) and the PLA were subjected to melt extruding and film blowing, where the specific steps were described as follows.
.5 The POE-g-MA/GO hybrid functional masterbatch and the PLA were premixed in a high-speed mixer and processed by an extruding and film-blowing device to produce a modified PLA film, that is, the organic-inorganic hybrid polylactic acid film.
In step (3), a mass ratio of PLA to POE-g-MA/GO hybrid functional masterbatch was 9: 1; and an extrusion temperature of the extruding and film-blowing device was 160°C.
Example 3
The present invention provides a method for producing a polylactic acid film modified by
2019206096 18 Jul 2019 organic-inorganic hybrid particles, which includes the following steps.
(1) Highly-active GO powder was prepared by solution intercalation, where the specific steps were described as follows.
(1.1) Dicumyl peroxide (DCP) and azobisisobutyronitrile (AIBN) were added to an aqueous GO solution at a concentration of 5 mg/mL. The reaction mixture was placed in a water bath pot at 10°C, dropwise added with an acetone/ethanol solution and stirred at a constant temperature for 10 h to obtain an aqueous layered GO solution.
In step (1.1), a mass ratio of GO to DCP to AIBN was 9: 0.3: 0.7;
the acetone/ethanol solution was 20% of the total volume of the aqueous GO solution, 0 DCP and AIBN; and a volume ratio of acetone to ethanol in the acetone/ethanol solution was 1:6.
(1.2) The aqueous layered GO solution obtained in step (1.1) was allowed to stand, filtered and dried in a vacuum drying oven at 25°C for 72 h to obtain highly-active GO. The obtained highly-active GO was ground and sieved to obtain the highly-active GO powder.
In step (1.2), a sieve having a pore size of 60 pm was used for sieving.
(2) After step (1), a POE-g-MA/GO hybrid functional masterbatch (organic-inorganic hybrid functional masterbatch) resistant to hygrothermal aging was prepared by blending, where the specific steps were described as follows.
The highly-active GO powder and POE-g-MA were respectively used as an inorganic component and an organic elastic component and premixed in a high-speed mixer and transferred to a twin-screw extruder for melt-mixing and extruding, granulation. The obtained product was dried in a drying oven at 50°C for 12 h to obtain the POE-g-MA /GO hybrid
2019206096 18 Jul 2019 functional masterbatch.
In step (2), a mass ratio of POE-g-MAto the highly-active GO powder was 9.2: 0.8; and an extrusion temperature of the twin-screw extruder was 170°C, and a rotation speed of the twin-screw extruder was 40 r/min.
(3) The obtained POE-g-MA/GO hybrid functional masterbatch obtained in step (2) and the PLA were subjected to melt extruding and fdm blowing, where the specific steps were described as follows.
The POE-g-MA/GO hybrid functional masterbatch and the PLA were premixed in a high-speed mixer and processed by an extruding and film-blowing device to produce a 0 modified PLA film, i.e., the polylactic acid film modified by organic-inorganic hybrid particles.
In step (3), a mass ratio of PLA to POE-g-MA/GO hybrid functional masterbatch was 8.7: 1.3; and an extrusion temperature of the extruding and film-blowing device was 170°C.
Example 4
The present invention provides a method for producing a polylactic acid film modified by organic-inorganic hybrid particles, which includes the following steps.
(1) Highly-active GO powder was prepared by solution intercalation, where the specific steps were described as follows.
(1-1) Dicumyl peroxide (DCP) and azobisisobutyronitrile (AIBN) were added to an aqueous GO solution at a concentration of 6 mg/mL. The reaction mixture was placed in a
2019206096 18 Jul 2019 water bath pot at 20°C, dropwise added with an acetone/ethanol solution and stirred at a constant temperature for 10 h to obtain an aqueous layered GO solution.
In step (1.1), a mass ratio of GO to DCP to AIBN was 8.7: 0.4: 0.9;
the acetone/ethanol solution was 25% of the total volume of the aqueous GO solution, 5 DCP and AIBN; and a volume ratio of acetone to ethanol in the acetone/ethanol solution was 1:8.
(1.2) The aqueous layered GO solution obtained in step (1.1) was allowed to stand, filtered and dried in a vacuum drying oven at 30°C for 72 h to obtain highly-active GO. The obtained highly-active GO was ground and sieved to obtain the highly-active GO powder.
In step (1.2), a sieve having a pore size of 80 pm was used for sieving.
(2) After step (1), a POE-g-MA/GO hybrid functional masterbatch (organic-inorganic hybrid functional masterbatch) resistant to hygrothermal aging was prepared by blending, where the specific steps were described as follows.
The highly-active GO powder and POE-g-MA were respectively used as an inorganic 15 component and an organic elastic component and premixed in a high-speed mixer and transferred to a twin-screw extruder for melt-mixing and extruding, granulation. The obtained product was dried in a drying oven at 60°C for 12 h to obtain the POE-g-MA /GO hybrid functional masterbatch.
In step (2), a mass ratio of POE-g-MA to the highly-active GO powder was 9.3: 0.7; and an extrusion temperature of the twin-screw extruder was 180°C, and a rotation speed of the twin-screw extruder was 50 r/min.
2019206096 18 Jul 2019 (3) The obtained POE-g-MA/GO hybrid functional masterbatch obtained in step (2) and the PLA were subjected to melt extruding and fdm blowing, where the specific steps were described as follows.
The POE-g-MA/GO hybrid functional masterbatch and the PLA were premixed in a 5 high-speed mixer and processed by an extruding and film-blowing device to produce a modified PLA film, i.e., the polylactic acid film modified by organic-inorganic hybrid particles.
In step (3), a mass ratio of PLA to POE-g-MA/GO hybrid functional masterbatch was 8.5: 1.5; and an extrusion temperature of the extruding and film-blowing device was 180°C.
Example 5
The present invention provides a method for producing a polylactic acid film modified by organic-inorganic hybrid particles, which includes the following steps.
(1) Highly-active GO powder was prepared by solution intercalation, where the specific 15 steps were as follows.
(1.1) Dicumyl peroxide (DCP) and azobisisobutyronitrile (AIBN) were added to an aqueous GO solution at a concentration of 8 mg/mL. The reaction mixture was placed in a water bath pot at 40°C, dropwise added with an acetone/ethanol solution and stirred at a constant temperature for 12 h to obtain an aqueous layered GO solution.
In step (1.1), a mass ratio of GO to DCP to AIBN was 8.5: 0.5: 1;
the acetone/ethanol solution was 30% of the total volume of the aqueous GO solution, DCP and AIBN; and
2019206096 18 Jul 2019 a volume ratio of acetone to ethanol in the acetone/ethanol solution was 1:10.
(1.2) The aqueous layered GO solution obtained in step (1.1) was allowed to stand, filtered and dried in a vacuum drying oven at 30°C for 96 h to obtain highly-active GO. The obtained highly-active GO was ground and sieved to obtain the highly-active GO powder.
In step (1.2), a sieve having a pore size of 100 pm was used for sieving;
(2) After step (1), a POE-g-MA/GO hybrid functional masterbatch (organic-inorganic hybrid functional masterbatch) resistant to hygrothermal aging was prepared by blending, where the specific steps were described as follows.
The highly-active GO powder and POE-g-MA were respectively used as an inorganic 0 component and an organic elastic component and premixed in a high-speed mixer and transferred to a twin-screw extruder for melt-mixing and extruding, granulation. The obtained product was dried in a drying oven at 80°C for 12 h to obtain the POE-g-MA /GO hybrid functional masterbatch.
In step (2), a mass ratio of POE-g-MA to the highly-active GO powder was 9.5: 0.5; and an extrusion temperature of the twin-screw extruder was 200°C, and a rotation speed of the twin-screw extruder was 90r/min.
(3) The obtained POE-g-MA/GO hybrid functional masterbatch obtained in step (2) and the PLA were subjected to melt extruding and film blowing, where the specific steps were described as follows.
The POE-g-MA/GO hybrid functional masterbatch and the PLA were premixed in a high-speed mixer and processed by an extruding and film-blowing device to produce a modified PLA film, i.e., the polylactic acid film modified by organic-inorganic hybrid particles.
2019206096 18 Jul 2019
In step (3), a mass ratio of PLA to POE-g-MA/GO hybrid functional masterbatch was 8: 2;
and an extrusion temperature of the extruding and film-blowing device was 190°C.
It is to be understood that, if any prior art publication is referred to herein, such reference 5 does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.
In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word “comprise” or variations such as “comprises” or “comprising” is used in an inclusive sense, i.e.
to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.

Claims (5)

  1. (1.1) adding DCP and AIBN to an aqueous GO solution; placing the reaction mixture in a water bath at 0-40°C followed by dropwise addition of an acetone/ethanol solution; and .5 stirring the reaction mixture under a constant temperature for 4-12 h to obtain an aqueous layered GO solution;
    wherein a mass ratio of GO to DCP to AIBN is 8.5-9.5: 0.2-0.5: 0.3-1;
    a concentration of the aqueous GO solution is 1-8 mg/mL;
    the acetone/ethanol solution is 10-30% of the total volume of the aqueous GO solution, 20 DCP and AIBN;
    a volume ratio of acetone to ethanol in the acetone/ethanol solution is 1:5-10; and
    2019206096 13 Feb 2020 (1.2) allowing the aqueous layered GO solution obtained in step (1.1) to stand for filtration and drying in a vacuum drying oven at 10-40°C for 48-96 h to obtain highly-active GO; and grinding the highly-active GO followed by sieving to obtain the highly-active GO powder.
    5 5. The method according to claim 3 or claim 4, characterized in that an extrusion temperature of the twin-screw extruder is 150-200°C and a rotation speed of the twin-screw extruder is 30-90 r/min.
    6. The method according to any one of claims 3 to 5, characterized in that the step (3) comprises the following steps: pre-mixing the POE-g-MA/GO hybrid functional masterbatch 0 with the PLA in the high-speed mixer; and processing the premixed product by an extruding and film-blowing device to produce a modified PLA film such that the polylactic acid film modified by organic-inorganic hybrid particles is obtained;
    wherein a mass ratio of the PLA to the POE-g-MA/GO hybrid functional masterbatch is 8-9.5: 0.5-2.
    (1) preparing highly-active GO powder by solution intercalation;
    20 (2) after step (1), preparing a POE-g-MA/GO hybrid functional masterbatch resistant to hygrothermal aging by blending; and
    2019206096 13 Feb 2020 (3) subjecting the POE-g-MA/GO hybrid functional masterbatch obtained in step (2) and the PLA to melt extrusion and film blowing, wherein the operation of preparing a POE-g-MA/GO hybrid functional masterbatch resistant to hygrothermal aging by blending further comprises:
    5 premixing the highly-active GO powder as an inorganic component with POE-g-MA as an organic elastic component in a high-speed mixer; and transferring the premixed product to a twin-screw extruder followed by melt-mixing, extruding, granulation and drying in a drying oven at 50-90°C for 4-12 h to obtain the POE-g-MA/GO hybrid functional masterbatch;
    0 wherein a mass ratio of POE-g-MA to the highly-active GO powder is 9-9.5:0.5-1.
    1. A polylactic acid film modified by organic-inorganic hybrid particles, comprising:
    an organic-inorganic hybrid functional masterbatch resistant to hygrothermal aging; and 5 PLA;
    wherein the PLA has a mass fraction of 80-95%;
    the organic-inorganic hybrid functional masterbatch has a mass fraction of 5-20% wherein the organic-inorganic hybrid functional masterbatch comprises POE-g-MA and highly-active GO powder with a mass ratio of POE-g-MA to the highly-active GO powder being 9-9.5:0.5-1; 0 and the sum of the mass fractions of the PLA and the organic-inorganic hybrid functional masterbatch is 100%.
  2. 2. The polylactic acid film modified by organic-inorganic hybrid particles according to claim 1, characterized in that the highly-active GO powder comprises GO, DCP and AIBN;
    15 wherein GO has a mass fraction of 85-95%; DCP has a mass fraction of 2-5%; and AIBN has a mass fraction of 3-10%; and the sum of the mass fractions of GO, DCP and AIBN is 100%.
  3. 3. A method for preparing a polylactic acid film modified by organic-inorganic hybrid particles, comprising:
  4. 4. The method according to claim 3, characterized in that the step (1) comprises the following steps:
  5. 5 7. The method according to claim 6, characterized in that an extrusion temperature of the extruding and film-blowing device is 150-190°.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110190437A1 (en) * 2010-02-01 2011-08-04 Hyundai Motor Company Polylactic acid composites
US20110189452A1 (en) * 2009-07-31 2011-08-04 Vorbeck Materials Corp. Crosslinked Graphene and Graphite Oxide
US20160177050A1 (en) * 2014-12-22 2016-06-23 Samsung Electronics Co., Ltd. Thermoplastic resin composition, molded article made of the thermoplastic resin composition, and method of preparing the thermoplastic resin composition

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130103154A (en) * 2012-03-09 2013-09-23 충남대학교산학협력단 Polypropylene-polylactic acid mixed resin/graphene/natural fiber bionanocomposite and manufacturing method of thereof
CN103319864A (en) * 2013-06-01 2013-09-25 青岛中科昊泰新材料科技有限公司 Biaxially stretched polylactic acid/graphene composite membrane
CN105504469B (en) * 2015-12-11 2018-08-07 余姚中国塑料城塑料研究院有限公司 A kind of graphene/polyolefin elastomer masterbatch, graphene anti-static composite material and preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110189452A1 (en) * 2009-07-31 2011-08-04 Vorbeck Materials Corp. Crosslinked Graphene and Graphite Oxide
US20110190437A1 (en) * 2010-02-01 2011-08-04 Hyundai Motor Company Polylactic acid composites
US20160177050A1 (en) * 2014-12-22 2016-06-23 Samsung Electronics Co., Ltd. Thermoplastic resin composition, molded article made of the thermoplastic resin composition, and method of preparing the thermoplastic resin composition

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