CN115850930A - Polyglycolic acid composition with special microstructure and preparation method and application thereof - Google Patents
Polyglycolic acid composition with special microstructure and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a polyvinyl alcohol acid composition with a special microstructure, a preparation method and application thereof, belonging to the field of modification and preparation of high polymer materials. The polyglycolic acid composition comprises the following components in parts by weight: (1) 85 to 99 parts polyglycolic acid; and (2) 1 to 15 parts of polylactic acid. Because polyglycolic acid and polylactic acid are in special proportion and under the processing technological conditions, the polyglycolic acid composition with a special microstructure is obtained, and the structure has obvious effect on delaying the degradation of the polyglycolic acid composition.
Description
Technical Field
The invention relates to the field of high molecular materials, in particular to a polyglycolic acid composition with a special microstructure and a preparation method and application thereof.
Background
Polyglycolic acid (PGA), which is the simplest linear aliphatic polyester, is a typical high-crystallinity polymer, which has a stable crystal lattice and a high melting point. In recent years, PGA has received wide attention and applications in the fields of medical sutures, drug controlled-release carriers, fracture fixation materials, tissue engineering scaffolds, reinforcing materials, oil fields, and the like, because PGA has the advantages of excellent biodegradability, high degradation rate, good biocompatibility, good bioresorbability, high mechanical strength (certain indexes are higher than those of engineering plastics), and the like. However, PGA has a serious problem in that it has a high melting point, a narrow processing temperature, a large crystallinity, and an excessively fast degradation rate, which has a serious influence on its processing and material applications.
Polylactic acid (PLA) is a biodegradable polyester material mainly prepared from bio-based materials, and has the advantages of high rigidity and strength, good biocompatibility, complete biodegradation and the like. The PLA structure comprises chiral carbon atoms, and has two structures of levorotatory structure and dextrorotatory structure, and the current most used is levorotatory polylactic acid-PLLA. PLA is a preferred choice for reinforcing soft biodegradable materials because of its good performance and relatively low cost.
Since PLA and PGA have excellent biocompatibility, degradability and mechanical rigidity, a great number of researchers in recent years use composite metal-substituted materials of PLA and PGA in the biomedical fields of artificial bones, scaffolds and the like. Although PGA and PLA have similar structures, gekko et al (engineering plastics application, 2020,48 (1): 8-12.) find that the blending of PGA and PLA belongs to a thermodynamically incompatible system, and the compatibility can be improved to a certain extent after the chain extender is added, but obvious phase separation still exists. Therefore, there are certain problems in the application of PGA/PLA blends. It has now been found that the degradation rate of PLA is much smaller than PGA, i.e. PLA has better stability. Thus, in PGA/PLA blends and articles made therefrom, long shelf life and stability are often still achieved with PLA as the major phase. But this brings an upper limit to the amount of PGA added to the blend.
Disclosure of Invention
The invention aims to solve the technical problems that polyglycolic acid is easy to degrade and has poor stability in long-term storage in the prior art.
The second technical problem to be solved by the invention is to provide a preparation method for preparing the polyglycolic acid composition having the special microstructure.
The invention also provides a polyglycolic acid composition with a special microstructure, which is prepared by the preparation method suitable for the polyglycolic acid composition with the special microstructure.
The fourth technical problem to be solved by the present invention is to provide an application of polyglycolic acid composition having a specific microstructure corresponding to one or three of the technical problems.
In order to solve the above technical problems, the present invention proposes to prepare PGA and PGA with a special microstructure based on the physical characteristics and processes of PGA, and it is expected to improve the aging stability of PGA/PLA blends with high PGA contents.
The first aspect of the present invention is to provide a polyglycolic acid composition having a specific microstructure, which includes polyglycolic acid and polylactic acid, and in which both of the polyglycolic acid phase and the polylactic acid phase are continuous phases in the microstructure of the polyglycolic acid composition.
According to an embodiment of the present invention, in the polyglycolic acid composition, the length of the polyglycolic acid phase or the polylactic acid phase is greater than the width thereof, preferably, the length of the polyglycolic acid phase or the polylactic acid phase is at least 40 micrometers, preferably 40 to 150 micrometers; the width of the polyglycolic acid phase or polylactic acid phase is 5 to 30 micrometers, preferably 5 to 20 micrometers.
According to an embodiment of the present invention, the polyglycolic acid composition includes 85 to 99 parts of polyglycolic acid and 1 to 15 parts of polylactic acid, based on 100 parts by weight of the total polyglycolic acid composition; for example, polyglycolic acid may be 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99 parts, or a range of values between any two of the foregoing; the polylactic acid can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 parts, or a range of values between any two of the foregoing values; preferably, the polyglycolic acid composition comprises 85 to 95 parts of polyglycolic acid and 5 to 15 parts of polylactic acid, based on 100 parts by weight of the total polyglycolic acid composition.
According to an embodiment of the present invention, the polyglycolic acid may be prepared by ring-opening polymerization of glycolide or polycondensation polymerization of glycolic acid or methyl glycolate; preferably, the polyglycolic acid has a crystallinity of 10 to 60%; for example, the crystallinity can be 10%, 20%, 30%, 40%, 50%, 60%, or a range of values between any two of the foregoing values; the polyglycolic acid may have an intrinsic viscosity of 0.9 to 1.8dl/g, for example, an intrinsic viscosity of 0.9dl/g, 1.0dl/g, 1.1dl/g, 1.2dl/g, 1.3dl/g, 1.4dl/g, 1.5dl/g, 1.6dl/g, 1.7dl/g, 1.8dl/g or a value range between any two of the above values, and more preferably 0.9 to 1.4dl/g.
According to the embodiment of the invention, the polylactic acid is formed by lactide ring-opening polycondensation or by direct polymerization of lactic acid, preferably by lactide ring-opening polycondensation; preferably, the polylactic acid has a melt index of 1 to 50g/10min under the test condition of 2.16kg at 190 ℃, for example, the melt index can be 1g/10min, 5g/10min, 10g/10min, 15g/10min, 20g/10min, 25g/10min, 30g/10min, 35g/10min, 40g/10min, 45g/10min, 50g/10min or a value range between any two of the above values, and further preferably 20 to 40g/10min.
According to an embodiment of the present invention, the polyglycolic acid composition having a specific microstructure is prepared from polyglycolic acid and polylactic acid by melt extrusion. The invention can form a special microstructure by properly proportioning polyglycolic acid and polylactic acid under the action of shearing force under the specific melt extrusion condition. Preferably, the polyglycolic acid composition having a specific microstructure provided by the present invention has a melt flow rate of 1 to 200g/10min, preferably 10 to 140g/10min at 230 ℃ under a test condition of 2.16 kg.
A second aspect of the present invention provides a method for producing the polyglycolic acid composition, comprising: the polyglycolic acid composition is prepared by melt blending and extruding the components including the polyglycolic acid and the polylactic acid.
According to the embodiment of the present invention, the polyglycolic acid and polylactic acid are sufficiently dried before use, and the specific drying operation can be completed by using drying equipment and process conditions commonly used in the art, for example, a blower oven or a vacuum oven, etc., preferably, the drying conditions are as follows: the drying temperature is 40-150 ℃, and preferably 60-110 ℃; the drying time is 1 to 8 hours, preferably 3 to 5 hours. For example, the drying temperature can be selected to be 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or a range between any two of the above values, and the drying time can be 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours or a range between any two of the above values.
According to the embodiment of the present invention, the melt blending may be carried out by using a blending device commonly used in the art, such as an internal mixer, a single screw extruder, a twin screw extruder, and other processing equipment, preferably a twin screw extruder; more preferably still, the first and second liquid crystal compositions are,
the melt blending conditions were: the length-diameter ratio of the screw is more than or equal to 16 and is 1, and the shearing rate is 10-5000 s -1 The shearing temperature is 180-300 ℃; preferably, the length-diameter ratio of the screw is more than or equal to 32, and the shear rate is 1000-2000 s -1 The shearing temperature is 200-230 ℃; for example,
the extrusion conditions were: multi-temperature zone extrusion (e.g., at least 4 temperature zones) is employed, the extrusion temperature is 190-260 ℃ and the temperature of at least two temperature zones is 230 ℃, preferably, the extrusion temperature is 210-250 ℃ and the temperature of at least two temperature zones is 230 ℃; the rotating speed of the extruder is 50-500 rpm, preferably 60-250 rpm; for example, the extrusion temperature can be 200 ℃, 210 ℃,220 ℃,230 ℃, 240 ℃, 250 ℃, 260 ℃, or a range of values between any two of the foregoing; the rotational speed of the extruder may be 50rpm, 60rpm, 70rpm, 80rpm, 90rpm, 100rpm, 120rpm, 150rpm, 170rpm, 180rpm, 200rpm, 220rpm, 240rpm, 250rpm, 260rpm, 270rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, or a range between any two of the foregoing.
A third aspect of the present invention is to provide a polyglycolic acid composition extrusion material including the above polyglycolic acid composition having a specific microstructure or the polyglycolic acid composition having a specific microstructure obtained by the above production method.
According to an embodiment of the present invention, the polyglycolic acid composition extrusion material may be obtained by an extrusion process commonly used in the art. Preferably, the polyglycolic acid composition extruded material provided by the present invention has a retention of tensile strength of at least 14% after 21 days of ultraviolet radiation accelerated aging.
The fourth aspect of the present invention is to provide the use of the polyglycolic acid composition having a specific microstructure or the polyglycolic acid composition extrusion material for producing injection-molded articles, films, and filaments. The applications are not particularly limited, and include but are not limited to wide applications in medicine, daily necessities, oil recovery, and the like.
The materials and preparation methods used in the present invention are briefly described below:
1. polyglycolic acid
Polyglycolic acid (PGA), also known as Polyglycolic acid, is the simplest-structured thermoplastic linear aliphatic polyester. PGA can be produced by a melt polycondensation method of glycolic acid, a ring-opening polymerization method of glycolide, or the like. Polyglycolic acid is a typical high crystallinity polymer that is lattice stable and has a relatively high melting point. PGA is a hydrophilic resin, and its surface tends to absorb moisture and undergo hydrolytic aging, so that its product stability is poor, thereby limiting its applications.
Polyglycolic acid has excellent biodegradability, can enter a human body circulatory system for in vivo degradation and discharge out of the body, can also degrade in an in vitro environment, and is mainly applied to the fields of medical sutures, drug controlled release carriers, fracture fixation materials, tissue engineering scaffolds, reinforcing materials and the like. Through solution spinning and melt spinning, the polyglycolic acid can be processed into a surgical suture line, has strong tensile strength and can be maintained for a sufficient time, and is suitable for wound suturing of deep tissues.
2. Polylactic acid
Polylactic acid (PLA) is an important lactic acid derivative product, is a polyester material which is nontoxic and harmless to a human body, and is a biodegradable high polymer material chemically synthesized by a lactic acid monomer. Currently, PLA is obtained by direct polycondensation of lactic acid (PC method) or ring-opening polymerization of lactide (ROP method). The PC method includes melt polycondensation, melt polycondensation-solid phase polymerization, and solution polycondensation. In contrast, the ROP method can obtain polylactic acid having a relatively high molecular weight. The polylactic acid has good biocompatibility, biodegradability and no toxicity, and is commonly used as a suture line for a surgical operation, a bone repair material, a drug controlled release material, an artificial bone and the like without taking out stitches in medicine.
Polylactic acid as a biodegradable high molecular polymer has the characteristic of good toughness, can be directly processed and formed by extrusion, injection molding, spinning blow molding and the like through general plastic processing equipment, and is widely applied to the fields of agricultural mulching films, agricultural and sideline product packaging bags, snack boxes, disposable knives and forks and the like at present.
3. Composition of polyglycolic acid and polylactic acid
In the method for preparing the polyglycolic acid/polylactic acid composition, melt blending reaction extrusion is adopted, and required amounts of the components are uniformly mixed in a molten state to obtain the polyglycolic acid/polylactic acid composition with high toughness.
One concrete embodiment is that polyglycolic acid and polylactic acid are respectively metered into a double-screw extruder according to a certain feeding proportion to be subjected to melt blending extrusion granulation. Another embodiment is that polyglycolic acid and polylactic acid are blended according to the required proportion and then added into a double-screw extruder for melt blending extrusion granulation.
In the step of preparing the polyglycolic acid/polylactic acid composition, the extrusion temperature suitable for the present invention may be 200 to 260 c, preferably 220 to 250 c. The rotation speed of the extruder is preferably 50rpm to 500rpm, more preferably 60rpm to 250rpm.
The invention provides a polyglycolic acid composition with a special microstructure and a preparation method thereof. The structure is a special microstructure, i.e. PGA and PLA do not form a conventional sea-island phase-marine phase microstructure (marine phase is abundant), but a special microstructure forming a bicontinuous phase has been unexpectedly found. Thus, the problem that the PGA (with high content) is degraded by too fast aging to have negative effect on the overall mechanical property of the PGL/PLA composite material and the shelf life is too short to meet the use requirement is creatively solved. According to the invention, with high PGA content, PLA unexpectedly forms a continuous phase structure, namely the surface of the product contains PLA coating with slow degradation speed, so that the aging stability of the product can be better relieved and improved, and the shelf life and the application period of the product are prolonged. After 3 weeks of xenon lamp accelerated aging, the tensile strength retention rate of a sample strip prepared by the injection molding composition is more than 35 percent, and the problems that polyglycolic acid is easy to degrade and has poor long-term storage stability can be solved.
Drawings
FIGS. 1 to 6 are sectional SEM micrographs of PGA/PLA compositions obtained in example 1 and comparative examples 1 to 5, respectively.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Source of raw materials
The starting materials used in the examples and comparative examples are, if not particularly limited, those disclosed in the prior art, and may be, for example, obtained as they are or prepared according to the production methods disclosed in the prior art.
The raw materials used in the examples and comparative examples are commercially available.
Polyglycolic acid (PGA) produced by Corbion Purac having an intrinsic viscosity of 1.0 to 1.4dl/g; the melt flow rate was 41g/10min at 230 ℃ under 2.16kg test conditions; when the temperature rise/reduction rate is tested at 10 ℃/min, the melting range is 200-230 ℃, and the crystallinity is 41 percent;
polylactic acid (PLA), manufactured by NatureWorks under the trade name of 3251D, and the melting range is 150-170 ℃ when tested at the temperature rise/decrease rate of 10 ℃/min; the melt index at 190 ℃ under 2.16kg was 35g/10min.
The invention carries out performance measurement according to the following method:
and (3) phase structure characterization: the cross-section of the PGA/PLA blend strand after quenching with liquid nitrogen was observed using a Scanning Electron Microscope (SEM) of the German ZEISS MERLIN model.
Xenon lamp aging performance test: the test was carried out in a Q-Sun Xe-3-HS xenon lamp accelerated aging test chamber of the company Q-Lab, USA. The light intensity at the wavelength of 340nm under a sunlight filter is 0.51W/(m) by adopting the ISO 4892-2 standard 2 Nm) at a test temperature of 65 ℃ for the black board, 38 ℃ for the cabinet and 50% relative humidity, a test cycle of 120 minutes was carried out, wherein 102 minutes was dry illumination and 18 minutes was illumination plus a spray of pure water.
Comparative example 1
After fully mixing 8 parts by mass of polylactic acid (NatureWorks, 3251D) and 92 parts by mass of PGA (Corbion Purac, melt flow rate 41g/10 min) after fully drying, polyLab HAAKE from Thermo Fisher science, USA was added through a feeder TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was pelletized by extrusion. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,200 ℃,225 ℃,235 ℃,235 ℃,235 ℃,230 ℃,225 ℃ and 215 ℃, and the screw speed was set at 67rpm. In steady operation, the torque ranges from 30 to 50%. The extruder is provided with a circular mouth mold with the diameter of 3mm, and a sample strip is extruded from the mouth mold, is air-cooled and then is cut into cylindrical particles with the diameter of about 3mm by a granulator. Collecting particles, vacuumizing in a vacuum drying oven at 60 ℃ for 4h, and packaging for later use.
Comparative example 2
Thoroughly premixing 5 parts by mass of polylactic acid (NatureWorks, 3251D) and 95 parts by mass of PGA (Corbion Purac, melt flow 41g/10 min), and feeding into PolyLab HAAKE (PolyLab HAAKE) of Thermo Fisher science, USA TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was extruded for pelletization. The extruder has 11 sections from a feeding port to a die, and is numbered from 1 to 11, whereinThe 1 st stage only serves as a feed and cannot be heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,200 ℃,225 ℃,235 ℃,235 ℃,235 ℃,230 ℃,225 ℃ and 215 ℃, and the screw speed was set at 67rpm. In steady operation, the torque ranges from 25 to 35%. The extruder is provided with a circular neck ring with the diameter of 3mm, and a sample strip is extruded from the neck ring, cooled by air and cut into cylindrical particles with the diameter of about 3mm by a granulator. Collecting particles, vacuumizing in a vacuum drying oven at 60 ℃ for 4h, and packaging for later use.
Comparative example 3
After fully mixing 8 parts by mass of polylactic acid (NatureWorks, 3251D) and 92 parts by mass of PGA (Corbion Purac, melt flow rate 41g/10 min) after fully drying, polyLab HAAKE from Thermo Fisher science, USA was added through a feeder TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was extruded for pelletization. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, where section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,200 ℃,225 ℃,235 ℃,235 ℃,235 ℃,230 ℃,225 ℃ and 215 ℃, and the screw speed is set to 135rpm. In steady operation, the torque ranges from 20 to 40%. The extruder is provided with a circular mouth mold with the diameter of 3mm, and a sample strip is extruded from the mouth mold, is air-cooled and then is cut into cylindrical particles with the diameter of about 3mm by a granulator. Collecting particles, vacuumizing in a vacuum drying oven at 60 ℃ for 4h, and packaging for later use.
Comparative example 4
Thoroughly pre-mixing 13 parts by mass of fully dried polylactic acid (NatureWorks, 3251D) and 87 parts by mass of PGA (Corbion Purac, melt flow rate 41g/10 min), and feeding into PolyLab HAAKE (PolyLab HAAKE) of Thermo Fisher science and technology, USA TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was extruded for pelletization. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,200 ℃,225 ℃,235 ℃,235 ℃,235 ℃,230 ℃,225 ℃ and 215 ℃, and the screw speed was set at 202rpm. In steady operation, the torque range is 20-50%. The extruder is provided with a circular neck ring with the diameter of 3mm, and a sample strip is extruded from the neck ring, cooled by air and cut into cylindrical particles with the diameter of about 3mm by a granulator. Collecting particles, vacuumizing in a vacuum drying oven at 60 ℃ for 4h, and packaging for later use.
[ COMPARATIVE EXAMPLE 5 ]
After fully mixing 20 parts by mass of polylactic acid (NatureWorks, 3251D) and 80 parts by mass of PGA (Corbion Purac, melt flow rate 41g/10 min) after fully drying, polyLab HAAKE from Thermo Fisher science, USA was added via a feeder TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was extruded for pelletization. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,200 ℃,225 ℃,235 ℃,235 ℃,235 ℃,230 ℃,225 ℃ and 215 ℃, and the screw speed is set at 230rpm. In steady operation, the torque ranges from 20 to 50%. The extruder is provided with a circular neck ring with the diameter of 3mm, and a sample strip is extruded from the neck ring, cooled by air and cut into cylindrical particles with the diameter of about 3mm by a granulator. And collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for later use.
[ example 1 ]
Thoroughly pre-mixing 5 parts by mass of polylactic acid (NatureWorks, 3251D) and 95 parts by mass of PGA (Corbion Purac, melt flow rate 41g/10 min), and feeding into PolyLab HAAKE (PolyLab HAAKE) of Thermo Fisher science and technology, USA TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was extruded for pelletization. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, where section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,230 ℃,225 ℃,220 ℃ and 210 ℃, and the screw rotation speed is set at 67rpm. In steady operation, the torque ranges from 30 to 50%. The extruder is provided with a circular neck ring with the diameter of 3mm, and a sample strip is extruded from the neck ring, cooled by air and cut into cylindrical particles with the diameter of about 3mm by a granulator. And collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for later use.
[ example 2 ]
After fully mixing 6 parts by mass of polylactic acid (NatureWorks, 3251D) and 94 parts by mass of PGA (Corbion Purac, melt flow rate 41g/10 min) after fully drying, polyLab HAAKE from Thermo Fisher science, USA was added via a feeder TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was extruded for pelletization. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,230 ℃,225 ℃,220 ℃ and 210 ℃, and the screw rotation speed is set at 67rpm. In steady operation, the torque ranges from 30 to 50%. The extruder is provided with a circular neck ring with the diameter of 3mm, and a sample strip is extruded from the neck ring, cooled by air and cut into cylindrical particles with the diameter of about 3mm by a granulator. Collecting particles, vacuumizing in a vacuum drying oven at 60 ℃ for 4h, and packaging for later use.
[ example 3 ]
Thoroughly pre-mixing 7 parts by mass of polylactic acid (NatureWorks, 3251D) and 93 parts by mass of PGA (Corbion Purac, melt flow rate 41g/10 min), and feeding into PolyLab HAAKE (PolyLab HAAKE, inc., thermo Fisher science and technology, USA) via a feeder TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was extruded for pelletization. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, where section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,230 ℃,225 ℃,220 ℃ and 210 ℃, and the screw rotation speed is set at 67rpm. In steady operation, the torque ranges from 30 to 50%. The extruder is provided with a circular neck ring with the diameter of 3mm, and a sample strip is extruded from the neck ring, cooled by air and cut into cylindrical particles with the diameter of about 3mm by a granulator. And collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for later use.
[ example 4 ]
After sufficiently drying, 9 parts by mass of polylactic acid (NatureWorks, 3251D) and 91 parts by mass of PGA (Corbion Purac, melt flow rate 41g/10 min) were sufficiently premixed, and then fedThe material feeder is added with PolyLab HAAKE of Thermo Fisher science and technology company of America TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was extruded for pelletization. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,230 ℃,225 ℃,220 ℃ and 210 ℃, and the screw rotation speed is set to 135rpm. In steady operation, the torque ranges from 30 to 50%. The extruder is provided with a circular neck ring with the diameter of 3mm, and a sample strip is extruded from the neck ring, cooled by air and cut into cylindrical particles with the diameter of about 3mm by a granulator. And collecting particles, pumping in a vacuum drying oven at 60 ℃ for 4 hours, and packaging for later use.
[ example 5 ] A method for producing a polycarbonate
After 15 parts by mass of polylactic acid (NatureWorks, 3251D) and 85 parts by mass of PGA (Corbion Purac, 41g/10min melt flow rate) which had been sufficiently dried were sufficiently premixed, polyLab HAAKE (PolyLab HAAKE) from Thermo Fisher technologies, USA, was added through a feeder TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was extruded for pelletization. The extruder has a total of 11 sections from the feed port to the die, numbered 1-11, wherein section 1 serves only as a feed and is not heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,230 ℃,225 ℃,220 ℃ and 210 ℃, and the screw rotation speed is set to 202rpm. In steady operation, the torque ranges from 30 to 50%. The extruder is provided with a circular neck ring with the diameter of 3mm, and a sample strip is extruded from the neck ring, cooled by air and cut into cylindrical particles with the diameter of about 3mm by a granulator. Collecting particles, vacuumizing in a vacuum drying oven at 60 ℃ for 4h, and packaging for later use.
[ example 6 ] A method for producing a polycarbonate
Thoroughly pre-mixing 13 parts by mass of fully dried polylactic acid (NatureWorks, 3251D) and 87 parts by mass of PGA (Corbion Purac, melt flow rate 41g/10 min), and feeding into PolyLab HAAKE (PolyLab HAAKE) of Thermo Fisher science and technology, USA TM Rheomex OS PTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was extruded for pelletization. The extruder has a total of 11 segments from the feed port to the die, numbered from 1 to 11, wherein the first segmentThe 1 section only plays a role of feeding and can not be heated. The temperatures of 2-11 sections of the extruder are respectively as follows: 200 ℃,200 ℃,220 ℃,230 ℃,230 ℃,230 ℃,230 ℃,225 ℃,220 ℃ and 210 ℃, and the screw rotation speed is set to 202rpm. In steady operation, the torque ranges from 30 to 50%. The extruder is provided with a circular neck ring with the diameter of 3mm, and a sample strip is extruded from the neck ring, cooled by air and cut into cylindrical particles with the diameter of about 3mm by a granulator. Collecting particles, vacuumizing in a vacuum drying oven at 60 ℃ for 4h, and packaging for later use.
After quenching the 6 PGA/PLA blends of example 1 and comparative examples 1-5 in liquid nitrogen, the sections were sprayed with gold and observed on a Scanning Electron Microscope (SEM) of ZEISS MERLIN model, germany, and the microscopic morphologies of the sections were as shown in FIGS. 1-6 and Table 1.
TABLE 1
| Test specimen | PGA/PLA | Screw speed/rpm | Temperature/. Degree.C | Type of microphase structure |
| Example 1 | 95/5 | 67 | 230 | Bicontinuous phase |
| Example 2 | 94/6 | 67 | 230 | Bicontinuous phase |
| Example 3 | 93/7 | 67 | 230 | Bicontinuous phase |
| Example 4 | 91/9 | 135 | 230 | Bicontinuous phase |
| Example 5 | 85/15 | 202 | 230 | Bicontinuous phase |
| Example 6 | 87/13 | 202 | 230 | Bicontinuous phase |
| Comparative example 1 | 94/6 | 67 | 235 | Sea island-sea phase |
| Comparative example 2 | 95/5 | 67 | 235 | Sea island-sea phase |
| Comparative example 3 | 92/8 | 135 | 235 | Sea island-sea phase |
| Comparative example 4 | 87/13 | 202 | 235 | Sea island-sea phase |
| Comparative example 5 | 80/20 | 230 | 235 | Sea island-sea phase |
As can be seen from the results, examples 1-6 formed a more pronounced bicontinuous phase structure (as shown in FIG. 1) in which the polyglycolic acid phase or polylactic acid phase had a length of about 50 microns and the width of the polyglycolic acid phase or polylactic acid phase was about 10 microns. Comparative examples 1 to 5 formed a conventional sea-island phase structure. As can be seen from examples 1 and 2, examples 2 and 1, and examples 6 and 4, the different temperatures are very sensitive to the microstructure of the PGA/PLA composition at the same PGA/PLA composition and screw rotation speed, and the bicontinuous phase can be formed only at 230 ℃. When the screw speed is 67rpm and the screw temperature is 230 ℃, the PLA content in the composition is 5-7 percent, and a bicontinuous phase can be formed. When the screw rotation speed is 202rpm, the screw temperature is 230 ℃, and the PLA content in the composition is 13-15 percent. PGA/PLA composition is extremely sensitive to processing temperature and screw rotation speed, and can form a special microstructure only when specific process and composition conditions are satisfied; under other compositions and process conditions, only a micro-phase structure with PGA marine phase and PLA as the sea island phase can be obtained.
EXAMPLE 7 preparation and testing of polyglycolic acid composition extruded Material
Examples 1 to 6 and comparative examples 1 to 5 were dried at 100 ℃ for 3 hours together with 11 seed particles. HAKKE by Thermo Fisher technologies, USA TM And (3) performing injection molding in a MiniJet II micro injection molding machine. The mold is a model 557-2295-60 × 10 × 1 produced by Thermo Fisher technologies, and the temperature of the cavity and the temperature of the mold during the experiment are respectively set as follows: 230 ℃ and 60 ℃. Setting the pressure at 300bar in the injection molding process for 5s, maintaining the pressure at 100bar for 10s in the subsequent pressure maintaining process, demolding, and collecting injection molded sample bars.
Next, the 6 injection-molded specimens were subjected to xenon accelerated aging test in a Q-Sun Xe-3-HS xenon accelerated aging test chamber of Q-Lab, USA. And sampling on days 0, 7, 14 and 21 respectively, and testing the mechanical properties of the injection-molded sample strips. Obtaining the change relation of the mechanical strength of the PGA/PLA composition sample bars with different compositions along with the aging time.
TABLE 2 tensile Strength Retention (%)
From the aging test results, it was found that only when the PGA/PLA splines exhibited bicontinuous special microstructures (examples 1 to 6) as compared with PGA/PLA splines of ordinary sea-island-marine phase structure (comparative examples), the PGA/PLA splines exhibited the highest retention of tensile strength after accelerated aging for 21 days (39.7 to 40.6%, see Table 2), whereas the tensile strength retention of the comparative examples of sea-island-marine phase structure was only 13.2 to 35.2%. Therefore, the PGA blend with the double-continuous-phase special microstructure has excellent aging stability, and the shelf life of the product is prolonged, which greatly promotes the wide application of the PGA in the field of injection molding products.
Claims (11)
1. A polyglycolic acid composition having a specific microstructure, said polyglycolic acid composition comprising polyglycolic acid and polylactic acid, and both of the polyglycolic acid phase and the polylactic acid phase being continuous phases in the microstructure of said polyglycolic acid composition.
2. Polyglycolic acid composition according to claim 1, where the length of the polyglycolic acid or polylactic acid phase is larger than its width, preferably the length of the polyglycolic acid or polylactic acid phase is at least 40 micrometers, preferably 40 to 150 micrometers; the width of the polyglycolic acid phase or polylactic acid phase is 5 to 30 micrometers, preferably 5 to 20 micrometers.
3. The polyglycolic acid composition according to claim 1, which comprises 85 to 99 parts of polyglycolic acid and 1 to 15 parts of polylactic acid; preferably, the polyglycolic acid composition comprises 85 to 95 parts of polyglycolic acid and 5 to 15 parts of polylactic acid, based on 100 parts of the total weight of the polyglycolic acid composition.
4. Polyglycolic acid composition according to claim 1,
the crystallinity of the polyglycolic acid is 10 to 60 percent; and/or the presence of a gas in the atmosphere,
the polyglycolic acid has an intrinsic viscosity of 0.9 to 1.8dl/g, preferably 0.9 to 1.4dl/g; and/or the presence of a gas in the gas,
the polylactic acid has a melt index of 1-50 g/10min, preferably 20-40 g/10min, under the test conditions of 190 ℃ and 2.16 kg.
5. A polyglycolic acid composition according to any one of claims 1 to 4,
the polyglycolic acid composition has a melt flow rate of 1 to 200g/10min, preferably 10 to 140g/10min under a test condition of 2.16kg at 230 ℃.
6. A method of preparing a polyglycolic acid composition having a particular microstructure according to any one of claims 1 to 5, comprising: the polyglycolic acid composition is prepared by melt blending and extruding the components including the polyglycolic acid and the polylactic acid.
7. The production method according to claim 6,
the polyglycolic acid and the polylactic acid are dried before use; and/or the presence of a gas in the atmosphere,
the melt blending employs a twin screw extruder.
8. The production method according to claim 7,
the drying conditions were: the drying temperature is 40-150 ℃, and preferably 60-110 ℃; the drying time is 1 to 8 hours, preferably 2 to 4 hours; and/or the presence of a gas in the gas,
the melt blending conditions were: the length-diameter ratio of the screw is more than or equal to 16 and is 1, and the shearing rate is 10-5000 s -1 The shearing temperature is 180-300 ℃; preferably, the length-diameter ratio of the screw is more than or equal to 32:1, the shear rate is 1000 to 2000s -1 The shearing temperature is 200-230 ℃; and/or the presence of a gas in the gas,
the extrusion conditions were: adopting multi-temperature zone extrusion, wherein the extrusion temperature is 190-260 ℃ and the temperature of at least two temperature zones is 230 ℃, preferably, the extrusion temperature is 210-250 ℃ and the temperature of at least two temperature zones is 230 ℃; the rotational speed of the extruder is 50 to 500rpm, preferably 60 to 250rpm.
9. A polyglycolic acid composition extrusion material comprising the polyglycolic acid composition having a specific microstructure according to any one of claims 1 to 5 or the polyglycolic acid composition having a specific microstructure obtained by the production method according to any one of claims 6 to 8.
10. The polyglycolic acid composition extruded material according to claim 9, wherein said polyglycolic acid composition extruded material has a retention of tensile strength of at least 14% after 21 days of uv radiation accelerated aging.
11. Use of a polyglycolic acid composition according to any one of claims 1 to 5 having a specific microstructure or of an extruded material of the polyglycolic acid composition according to any one of claims 9 to 10 in injection molding, films, spinning.
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| CN101367986A (en) * | 2007-08-14 | 2009-02-18 | 袁明龙 | Coupling and capacity increasing technique for coblended interface of biodegradation polylactic acid/starch composite material |
| CN113429764A (en) * | 2021-06-11 | 2021-09-24 | 杨如麟 | starch/PLA-PGA-PBAT biodegradable and compostable special material and preparation method thereof |
| WO2022037349A1 (en) * | 2020-08-19 | 2022-02-24 | 国家能源投资集团有限责任公司 | Toughening degradable polyglycolic acid composition, and toughening degradable polyglycolic acid material and preparation method therefor and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367986A (en) * | 2007-08-14 | 2009-02-18 | 袁明龙 | Coupling and capacity increasing technique for coblended interface of biodegradation polylactic acid/starch composite material |
| WO2022037349A1 (en) * | 2020-08-19 | 2022-02-24 | 国家能源投资集团有限责任公司 | Toughening degradable polyglycolic acid composition, and toughening degradable polyglycolic acid material and preparation method therefor and use thereof |
| CN113429764A (en) * | 2021-06-11 | 2021-09-24 | 杨如麟 | starch/PLA-PGA-PBAT biodegradable and compostable special material and preparation method thereof |
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