CN117866246A - Biaxially oriented polyglycolic acid film material and preparation method and application thereof - Google Patents
Biaxially oriented polyglycolic acid film material and preparation method and application thereof Download PDFInfo
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- 229920000954 Polyglycolide Polymers 0.000 title claims abstract description 168
- 239000004633 polyglycolic acid Substances 0.000 title claims abstract description 168
- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000005266 casting Methods 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 23
- 238000003490 calendering Methods 0.000 claims description 10
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- 238000001035 drying Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000005022 packaging material Substances 0.000 claims description 2
- 230000004927 fusion Effects 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 7
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000004698 Polyethylene Substances 0.000 abstract 1
- 229920000180 alkyd Polymers 0.000 abstract 1
- -1 polyethylene Polymers 0.000 abstract 1
- 229920000573 polyethylene Polymers 0.000 abstract 1
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- 238000005096 rolling process Methods 0.000 description 11
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- 241001315609 Pittosporum crassifolium Species 0.000 description 9
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- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- 229920001896 polybutyrate Polymers 0.000 description 5
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
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- 229910052760 oxygen Inorganic materials 0.000 description 3
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- 238000012643 polycondensation polymerization Methods 0.000 description 3
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- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 230000003078 antioxidant effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
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- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention belongs to the field of high polymer materials, and provides a biaxially oriented polyethylene alkyd film and a preparation method thereof. According to the invention, through a synchronous biaxial stretching process, the movement capability of polyglycolic acid molecular chains is properly improved, the relaxation time is reduced, the glassy polyglycolic acid film is forced to deform in a high elastic mode under test conditions, extremely high strain is obtained, and the obtained polyglycolic acid film material has excellent mechanical properties.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a biaxially oriented polyglycolic acid film material, and a preparation method and application thereof.
Background
Polyglycolic acid (PGA), which is the simplest linear aliphatic polyester, is a typical high crystallinity polymer that is lattice stable and has a relatively high melting point. In recent years, PGA has been widely focused and used in the fields of medical sutures, controlled drug release carriers, fracture fixation materials, tissue engineering scaffolds, reinforcing materials, oil fields, etc. because of its excellent biodegradability, high degradation speed, good biocompatibility, good bioresorbability, high mechanical strength, etc., and its ability to enter the circulatory system of the human body for in vivo degradation and release from outside the body, and its ability to degrade in the environment outside the body. However, PGA has a serious problem in processing and material application, such as high melting point, narrow processing temperature, high crystallinity, and too high degradation rate.
Many publications on the preparation of polyglycolic acid films have reported that mainly improve the tensile toughness of films. The conventional idea is to compound polyglycolic acid with high performance with other flexible biodegradable polyester by blending modification means so as to obtain a film product with toughness and strength meeting the requirements. Chinese patent application CN107304285A adds antioxidant, stabilizer and other functional assistants into polyglycolic acid and flexible degradable polyester PBAT to realize blow molding of PGA/PBAT film material. However, the PGA loading content in the blend film is limited due to the structural differences and large amounts of PGA and PBAT. Meanwhile, the high oxygen barrier property of the PGA film conforming to the PBAT is greatly reduced due to the poor oxygen barrier property of the PBAT. Although blending methods can achieve PGA in film product applications, they are still limited by the nature of the material itself and the differences in compatibility between the different components.
PGA is a material with extremely high oxygen barrier properties, and has a very wide application potential in the field of barrier such as food packaging. In addition to blowing films by blending with other materials, PGA may also be produced into film materials by casting methods. However, the tensile toughness of PGA cast films still cannot meet practical use due to high crystallinity caused by large structural regularity of PGA molecular chains.
Disclosure of Invention
The invention provides a polyglycolic acid film material with excellent mechanical properties and a preparation method thereof, which are used for solving the problem of poor tensile toughness of the polyglycolic acid film material in the prior art.
The invention aims to provide a biaxially oriented polyglycolic acid film material which is obtained by melt extrusion, casting or calendaring of polyglycolic acid and biaxially oriented.
According to an embodiment of the invention, the polyglycolic acid has a weight average molecular weight of 100000 ～ 1000000, preferably 100000 ～ 300000, thousand g/mol; the polyglycolic acid can be prepared by ring-opening polymerization or polycondensation polymerization, and can be specifically prepared by direct condensation polymerization of glycolic acid/ester, or by ring-opening polymerization of glycolide or polycondensation polymerization of glycolic acid or methyl glycolate.
According to an embodiment of the invention, the biaxially oriented polyglycolic acid film material has a crystallinity of less than 40%, preferably a crystallinity of less than 30%; the thickness of the polyglycolic acid film material is 5 to 50. Mu.m, preferably 5 to 30. Mu.m.
The second object of the invention is to provide a preparation method of the biaxially oriented polyglycolic acid film material, which comprises the steps of carrying out melt extrusion, tape casting or calendaring on polyglycolic acid to form a film, and then carrying out biaxially oriented and cooling to obtain the biaxially oriented polyglycolic acid film material. The longitudinal direction and the transverse direction of the biaxial stretching are synchronously stretched by adopting the same stretching multiple and the same stretching rate.
According to a preferred embodiment of the present invention, the preparation method specifically comprises the following steps:
(1) Drying polyglycolic acid;
(2) Casting or calendaring the dried polyglycolic acid to form a film or sheet;
(3) Preheating the obtained film or sheet, stretching and cooling the film or sheet along the longitudinal direction and the transverse direction of the film at the same time, and obtaining the biaxially oriented polyglycolic acid film material.
According to an embodiment of the present invention, the drying in the step (1) may employ a drying apparatus and drying conditions commonly used in the art, such as vacuum drying, hot air drying, etc., preferably the drying temperature is 10 to 90 ℃, preferably 20 to 60 ℃, and the moisture content of the dried polyglycolic acid is less than 50ppm.
According to a specific embodiment of the present invention, the casting or calendering operation in step (2) may be carried out using casting or calendering extrusion conditions commonly used in the art, in particular extrusion temperatures ranging from 190 to 260 ℃, preferably from 190 to 240 ℃; the rotation speed of the extruder during extrusion is 50-500 rpm, preferably 60-250 rpm; the temperature of casting or calendaring is 10 to 60 ℃, preferably 10 to 50 ℃.
According to a specific embodiment of the present invention, in the step (3):
when the weight average molecular weight of the polyglycolic acid is less than or equal to 200000g/mol, the temperature of preheating and biaxial stretching is 20-70 ℃, preferably 25-50 ℃; the stretching ratio is 1.1 to 5 times, preferably 1.1 to 3 times; the stretching rate is 1 to 500mm/s, preferably 1 to 70mm/s; the cooling rate is 10-400 ℃/min, preferably 20-200 ℃/min; the cooling time is 1 to 30s, preferably 1 to 10s; or alternatively, the first and second heat exchangers may be,
when the weight average molecular weight of the polyglycolic acid is more than 200000g/mol, the temperature of preheating and biaxial stretching is 30-80 ℃, preferably 35-75 ℃; the stretching ratio is 1.1 to 7 times, preferably 1.5 to 5 times; the stretching rate is 1 to 500mm/s, preferably 7 to 70mm/s; the cooling rate is 10-400 ℃/min, preferably 7-100 ℃/min, and the cooling time is 10-60 s, preferably 10-35 s.
The third object of the present invention is to use the biaxially oriented polyglycolic acid film material or the biaxially oriented polyglycolic acid film material obtained by the above-mentioned production method for packaging materials. Specific applications are not particularly limited, and include, but are not limited to, applications in medicine, commodity products, oil recovery, and the like.
Polyglycolic acid (Polyglycolic acid, PGA), also known as polyglycolic acid, employed in the present invention is the thermoplastic linear aliphatic polyester of the simplest structure. PGA can be prepared by melt polycondensation of glycolic acid or ring-opening polymerization of glycolide, is a typical polymer with high crystallinity, stable crystal lattice, high melting point and mechanical strength. However, PGA is a type of hydrophilic resin as an aliphatic polyester, and the surface of the main chain ester bond is liable to absorb moisture, undergo hydrolytic aging and accelerate self-degradation, so that the stability of the product is poor. Meanwhile, the film toughness is poor due to the fast crystallization rate of PGA, and the blown film processability is poor, thereby limiting the application thereof. In the preparation method of the polyglycolic acid film material, required amount of dried polyglycolic acid is cast or extruded in a molten state, and the biaxially oriented polyglycolic acid film is obtained after biaxially oriented, cooled and rolled. The entanglement among PGA molecular chains is weakened in the orientation process of biaxial stretching, the motion capability of the PGA molecular chains is improved, and the relaxation time of the PGA chain segments is shortened. According to the invention, polyglycolic acid is biaxially stretched within a specific stretching ratio range, so that the relaxation time of the PGA chain segment is matched with the stretching speed of a stretching strength test, the glassy PGA is subjected to high-elastic deformation, and the synergistic improvement effect of mechanical properties and toughness is realized.
The invention provides a biaxially oriented polyglycolic acid film material and a preparation method thereof, and the obtained polyglycolic acid film material has excellent mechanical properties after biaxially oriented and shaped, and the preparation method of the polyglycolic acid film material is simple, easy to realize industrialization and has wide application prospect.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
Commercially available polyglycolic acid (PGA) was obtained from Bien-Prague, hollaceae, and GMP grade glycolide homopolymer, having an intrinsic viscosity of 1.2dl/g, a weight average molecular weight of 180000g/mol, and a molecular weight distribution index of 1.57.
Polyglycolic acid, intrinsic viscosity 3dl/g, weight average molecular weight 300000g/mol, molecular weight distribution index 2.5, self-made process as follows:
glycolide (GA), anhydrous stannous chloride, ethylene-vinyl alcohol copolymer (EVOH), 1, 4-butanediol, antioxidant 1010 and antioxidant 626 are mixed uniformly according to the mass ratio of 100:0.03:0.015:0.035:0.3:0.6, and then extruded and granulated by a Eurolab parallel co-rotating double screw extruder (screw diameter: 16mm, length-diameter ratio: 40), so as to obtain polyglycolic acid. The extrusion section temperatures were respectively: 160 ℃,200 ℃,220 ℃,220 ℃,220 ℃,220 ℃,230 ℃,235 ℃, and 240 ℃. The feeding speed was 1kg/h and the screw speed was 50rpm.
The invention performs performance measurement according to the following method:
film tensile test: the process software was Bluehill version 2.31, as determined by the ISO 527-3 standard using the INSTRON model 3344 product tester. The pattern was cut into Type 5 of ISO 527-3 standard, and placed in a Bluecard BPS-100CB constant temperature and humidity cabinet (temperature 23 ℃ C., relative humidity 50%) of Shanghai-Hemsl scientific instruments Co., ltd for 24 hours. When testing, the initial clamp interval is 50mm, the test stretching rate is 50mm/min, each sample is tested 5 times, and the average value is obtained.
Crystallinity test: measuring crystallization thermodynamic parameters of the PGA film by using a Differential Scanning Calorimeter (DSC) of the American TA company, adding about 4-8mg of the PGA film sample into a DSC sample cell, heating to 250 ℃ at a speed of 10 ℃/min, and keeping the temperature for 2min to eliminate heat history; then cooling to-50 ℃ at 10 ℃/min, and recording a cooling crystallization DSC spectrum of the film sample; then the temperature is increased to 250 ℃ at the speed of 10 ℃/min, and the crystallization melting DSC spectrum of the sample is recorded. The two DSC curves are processed to obtain crystallization thermodynamic parameters such as the crystallization temperature, the crystallization melting point, the melting heat and the like of the PGA film. Wherein the PGA film has crystallinity (X c ) Calculated according to the following formula:
x in the formula c Crystallinity,%; deltaH m Is the heat absorption enthalpy of melting, J/g; deltaH m100 The melting heat absorption enthalpy at the time of complete crystallization of PGA was 191.32J/g.
Thickness test: the biaxially stretched PGA film was subjected to thickness measurement using a Labthink C640 thickness gauge. Selecting 10×10cm 2 Area films were tested, 5 points per sample, and then the average was taken as the film thickness for that sample.
Comparative example 1
Polyglycolic acid (Corbion Purac) having a weight average molecular weight of 180000g/mol was hot air dried at 35.+ -. 2 ℃ for 2 hours with a water content of 30ppm. Subjecting the substantially dried polyglycolic acid to PolyLab HAAKE by Thermo Fisher technology Co., USA TM Rheomix OS PTW16 co-directional single screw extruder (screw diameter 16mm, l/d=40) was cast. The extruder temperatures were respectively: 190 ℃,200 ℃,220 ℃,230 ℃,235 ℃,230 ℃,240 ℃,240 ℃,230 ℃ and 225 ℃, the screw rotation speed is set to 25rpm, and the casting roll temperature is 20 ℃. The torque range is 10-50% during steady operation. And drawing and rolling the polyglycolic acid film material after the polyglycolic acid film material comes out of the die, and finally obtaining the polyglycolic acid casting film with the thickness of 115 mu m.
Comparative example 2
Polyglycolic acid having a weight average molecular weight of 300000g/mol was hot air-dried at 35.+ -. 2 ℃ for 2 hours and at a water content of 40ppm. Subjecting the substantially dried polyglycolic acid to PolyLab HAAKE by Thermo Fisher technology Co., USA TM Rheomix OS PTW16 co-directional single screw extruder (screw diameter 16mm, l/d=40) was cast. The extruder temperatures were respectively: 190 ℃,200 ℃,220 ℃,230 ℃,235 ℃,230 ℃,240 ℃,240 ℃,230 ℃ and 225 ℃, the screw rotation speed is set to 25rpm, and the casting roll temperature is 20 ℃. The torque range is 10-50% during steady operation. And drawing and rolling the polyglycolic acid film material after the polyglycolic acid film material comes out of the die, and finally obtaining the polyglycolic acid casting film with the thickness of 78 mu m.
[ comparative example 3 ]
Hot air drying polyglycolic acid (Corbion Purac) with weight average molecular weight of 180000g/mol at 35Drying time was 2 hours at + -2 deg.C, water content was 30ppm. Subjecting the substantially dried polyglycolic acid to PolyLab HAAKE by Thermo Fisher technology Co., USA TM Rheomix OS PTW16 co-directional single screw extruder (screw diameter 16mm, l/d=40) was cast. The extruder temperatures were respectively: 190 ℃,200 ℃,220 ℃,230 ℃,235 ℃,230 ℃,240 ℃,240 ℃,230 ℃ and 225 ℃, the screw rotation speed is set to 25rpm, and the casting roll temperature is 20 ℃. The torque range is 10-50% during steady operation. And drawing and rolling the polyglycolic acid film material after the polyglycolic acid film material comes out of the die, and finally obtaining the polyglycolic acid casting film.
The cast film was then placed in a KARO type IV laboratory biaxial stretcher (Bruckner Maschinenbau, siegsdorf, germany), preheated at 50 ℃ for 60s, and stretched in the Machine Direction (MD) at a stretch rate of 35mm/s at a stretch temperature of 50 ℃ with a stretch factor of 2; and (3) cooling the film at a speed of 200 ℃/min in an annealing device with a temperature of 20 ℃ for 9s to obtain the unidirectional stretching polyglycolic acid film.
[ comparative example 4 ]
Polyglycolic acid (Corbion Purac) having a weight average molecular weight of 180000g/mol was hot air dried at 35.+ -. 2 ℃ for 2 hours with a water content of 30ppm. Subjecting the substantially dried polyglycolic acid to PolyLab HAAKE by Thermo Fisher technology Co., USA TM Rheomix OS PTW16 co-directional single screw extruder (screw diameter 16mm, l/d=40) was cast. The extruder temperatures were respectively: 190 ℃,200 ℃,220 ℃,230 ℃,235 ℃,230 ℃,240 ℃,240 ℃,230 ℃ and 225 ℃, the screw rotation speed is set to 25rpm, and the casting roll temperature is 20 ℃. The torque range is 10-50% during steady operation. And drawing and rolling the polyglycolic acid film material after the polyglycolic acid film material comes out of the die, and finally obtaining the polyglycolic acid casting film.
The cast film was then placed in a KARO type IV laboratory biaxial stretcher (Bruckner Maschinenbau, siegsdorf, germany), preheated at 50 ℃ for 60s, and subjected to Transverse Direction (TD) stretching at a stretching rate of 35mm/s, at a stretching temperature of 50 ℃ and a stretching multiple of 2; and (3) cooling the film at a speed of 200 ℃/min in an annealing device with a temperature of 20 ℃ for 9s to obtain the unidirectional stretching polyglycolic acid film.
[ example 1 ]
Polyglycolic acid (Corbion Purac) having a weight average molecular weight of 180000g/mol was hot air dried at 35.+ -. 2 ℃ for 2 hours with a water content of 30ppm. Subjecting the substantially dried polyglycolic acid to PolyLab HAAKE by Thermo Fisher technology Co., USA TM Rheomix OS PTW16 co-directional single screw extruder (screw diameter 16mm, l/d=40) was cast. The extruder temperatures were respectively: 190 ℃,200 ℃,220 ℃,230 ℃,235 ℃,230 ℃,240 ℃,240 ℃,230 ℃ and 225 ℃, the screw rotation speed is set to 25rpm, and the casting roll temperature is 20 ℃. The torque range is 10-50% during steady operation. And drawing and rolling the polyglycolic acid film material after the polyglycolic acid film material comes out of the die, and finally obtaining the polyglycolic acid casting film.
Subsequently, the cast film was placed in a KARO type IV laboratory biaxial stretcher (Bruckner Maschinenbau, siegsdorf, germany) and preheated at 50 ℃ for 60s, and simultaneously stretched in the Machine Direction (MD) and Transverse Direction (TD) at a stretching rate of 35mm/s at 50 ℃ at a stretching ratio of md×td=2×2; and (3) cooling the film at a speed of 200 ℃/min in an annealing device with a temperature of 20 ℃ for 9s to obtain the biaxially oriented polyglycolic acid film.
[ example 2 ]
Polyglycolic acid (Corbion Purac) having a weight average molecular weight of 180000g/mol was hot air dried at 35.+ -. 2 ℃ for 2 hours with a water content of 30ppm. Subjecting the substantially dried polyglycolic acid to PolyLab HAAKE by Thermo Fisher technology Co., USA TM Rheomix OS PTW16 co-directional single screw extruder (screw diameter 16mm, l/d=40) was cast. The extruder temperatures were respectively: 190 ℃,200 ℃,220 ℃,230 ℃,235 ℃,230 ℃,240 ℃,240 ℃,230 ℃ and 225 ℃, the screw rotation speed is set to 25rpm, and the casting roll temperature is 20 ℃. The torque range is 10-50% during steady operation. And drawing and rolling the polyglycolic acid film material after the polyglycolic acid film material comes out of the die, and finally obtaining the polyglycolic acid casting film.
Subsequently, the cast film was placed in a KARO type IV laboratory biaxial stretcher (Bruckner Maschinenbau, siegsdorf, germany)) and preheated at 50 ℃ for 60s, and subjected to simultaneous Machine Direction (MD) and Transverse Direction (TD) stretching at a stretching rate of 35mm/s at a stretching temperature of 50 ℃ and a stretching ratio of md×td=2.5×2.5; and (3) cooling the film at a speed of 200 ℃/min in an annealing device with the temperature of 20 ℃ for 18 seconds to obtain the biaxially oriented polyglycolic acid film.
[ example 3 ]
Polyglycolic acid (Corbion Purac) having a weight average molecular weight of 180000g/mol was hot air dried at 35.+ -. 2 ℃ for 2 hours with a water content of 30ppm. Subjecting the substantially dried polyglycolic acid to PolyLab HAAKE by Thermo Fisher technology Co., USA TM Rheomix OS PTW16 co-directional single screw extruder (screw diameter 16mm, l/d=40) was cast. The extruder temperatures were respectively: 190 ℃,200 ℃,220 ℃,230 ℃,235 ℃,230 ℃,240 ℃,240 ℃,230 ℃ and 225 ℃, the screw rotation speed is set to 25rpm, and the casting roll temperature is 20 ℃. The torque range is 10-50% during steady operation. And drawing and rolling the polyglycolic acid film material after the polyglycolic acid film material comes out of the die, and finally obtaining the polyglycolic acid casting film.
Subsequently, the cast film was placed in a KARO type IV laboratory biaxial stretcher (Bruckner Maschinenbau, siegsdorf, germany)) and preheated at 50 ℃ for 60s, and subjected to simultaneous Machine Direction (MD) and Transverse Direction (TD) stretching at a stretching rate of 35mm/s at a stretching temperature of 50 ℃ and a stretching ratio of md×td=3×3; and (3) immediately cooling the film in an annealing device with the temperature of 20 ℃ at a speed of 200 ℃/min for 9s to obtain the biaxially oriented polyglycolic acid film.
[ example 4 ]
Polyglycolic acid having a weight average molecular weight of 300000g/mol was hot air-dried at 35.+ -. 2 ℃ for 2 hours and at a water content of 30ppm. Subjecting the substantially dried polyglycolic acid to PolyLab HAAKE by Thermo Fisher technology Co., USA TM Rheomix OS PTW16 co-directional single screw extruder (screw diameter 16mm, l/d=40) was cast. The extruder temperatures were respectively: 190 ℃,200 ℃,220 ℃,230 ℃,235 ℃,230 ℃,240 ℃,240 ℃,230 ℃ and 225 ℃, the screw rotation speed is set to 25rpm, and the casting roll temperature is 20 ℃. The torque range is 10-50% during steady operation. And drawing and rolling the polyglycolic acid film material after the polyglycolic acid film material comes out of the die, and finally obtaining the polyglycolic acid casting film.
Subsequently, the cast film was placed in a KARO type IV laboratory biaxial stretcher (Bruckner Maschinenbau, siegsdorf, germany)) and preheated at 55 ℃ for 60s, and simultaneously stretched in the Machine Direction (MD) and Transverse Direction (TD) at a stretching rate of 35mm/s at a stretching temperature of 55 ℃ and a stretching ratio of md×td=2×2; and (3) rapidly cooling the film in an annealing device with the temperature of 20 ℃ at a speed of 100 ℃/min for 18 seconds to obtain the biaxially oriented polyglycolic acid film.
[ example 5 ]
Polyglycolic acid having a weight average molecular weight of 300000g/mol was hot air-dried at 35.+ -. 2 ℃ for 2 hours and at a water content of 30ppm. Subjecting the substantially dried polyglycolic acid to PolyLab HAAKE by Thermo Fisher technology Co., USA TM Rheomix OS PTW16 co-directional single screw extruder (screw diameter 16mm, l/d=40) was cast. The extruder temperatures were respectively: 190 ℃,200 ℃,220 ℃,230 ℃,235 ℃,230 ℃,240 ℃,240 ℃,230 ℃ and 225 ℃, the screw rotation speed is set to 25rpm, and the casting roll temperature is 30 ℃. The torque range is 10-50% during steady operation. And drawing and rolling the polyglycolic acid film material after the polyglycolic acid film material comes out of the die, and finally obtaining the polyglycolic acid casting film.
Subsequently, the cast film was placed in a KARO type IV laboratory biaxial stretcher (Bruckner Maschinenbau, siegsdorf, germany)) and preheated at 55 ℃ for 60s, and simultaneously stretched in the Machine Direction (MD) and Transverse Direction (TD) at a stretching rate of 35mm/s at a stretching temperature of 55 ℃ and a stretching ratio of md×td=2.5×2.5; and (3) rapidly cooling the film in an annealing device with the temperature of 20 ℃ at a speed of 100 ℃/min for 18 seconds to obtain the biaxially oriented polyglycolic acid film.
[ example 6 ]
Polyglycolic acid having a weight average molecular weight of 300000g/mol was hot air-dried at 35.+ -. 2 ℃ for 2 hours and at a water content of 30ppm. Subjecting the substantially dried polyglycolic acid to PolyLab HAAKE by Thermo Fisher technology Co., USA TM Rheomix OS PTW16 co-directional single screw extruder (screw diameter 16mm, l/d=40) was cast. The extruder temperatures were respectively: 190 ℃,200 ℃,220 ℃,230 ℃,235 ℃,230 ℃,240 ℃,240 ℃,230 ℃ and 225 ℃ and the screw rotation speed is set to be25rpm, the casting roll temperature was 20 ℃. The torque range is 10-50% during steady operation. And drawing and rolling the polyglycolic acid film material after the polyglycolic acid film material comes out of the die, and finally obtaining the polyglycolic acid casting film.
Subsequently, the cast film was placed in a KARO type IV laboratory biaxial stretcher (Bruckner Maschinenbau, siegsdorf, germany)) and preheated at 55 ℃ for 60s, and simultaneously stretched in the Machine Direction (MD) and Transverse Direction (TD) at a stretching rate of 35mm/s at a stretching temperature of 55 ℃ and a stretching ratio of md×td=3×3; and (3) rapidly cooling the film in an annealing device with the temperature of 20 ℃ at a speed of 100 ℃/min for 18 seconds to obtain the biaxially oriented polyglycolic acid film.
[ example 7 ]
Polyglycolic acid having a weight average molecular weight of 300000g/mol was hot air-dried at 35.+ -. 2 ℃ for 2 hours and at a water content of 30ppm. Subjecting the substantially dried polyglycolic acid to PolyLab HAAKE by Thermo Fisher technology Co., USA TM Rheomix OS PTW16 co-directional single screw extruder (screw diameter 16mm, l/d=40) was cast. The extruder temperatures were respectively: 190 ℃,200 ℃,220 ℃,230 ℃,235 ℃,230 ℃,240 ℃,240 ℃,230 ℃ and 225 ℃, the screw rotation speed is set to 25rpm, and the casting roll temperature is 20 ℃. The torque range is 10-50% during steady operation. And drawing and rolling the polyglycolic acid film material after the polyglycolic acid film material comes out of the die, and finally obtaining the polyglycolic acid casting film.
Subsequently, the cast film was placed in a KARO type IV laboratory biaxial stretcher (Bruckner Maschinenbau, siegsdorf, germany)) and preheated at 55 ℃ for 60s, and simultaneously stretched in the Machine Direction (MD) and Transverse Direction (TD) at a stretching rate of 35mm/s at a stretching temperature of 55 ℃ and a stretching ratio of md×td=1.5×1.5; and (3) rapidly cooling the film in an annealing device with the temperature of 20 ℃ at a speed of 100 ℃/min for 18 seconds to obtain the biaxially oriented polyglycolic acid film.
[ example 8 ]
Polyglycolic acid films prepared in comparative examples 1 to 4 and examples 1 to 7 were tested according to the film stretching method described above, and the mechanical properties were as shown in the following table.
TABLE 1 mechanical Properties of films of different polyglycolic acid compositions
( And (3) injection: the above table "-" indicates that the film did not undergo biaxial stretching )
As can be seen from the results of table 1, the two molecular weight PGA films were subjected to a biaxial stretching process, and the mechanical strength, elongation at break and elastic modulus were significantly changed from those of the unstretched PGA films. From comparative examples 3, 4 and example 2, it was found that the biaxially oriented film was better in overall mechanical properties at the same draw ratio, rate and temperature. As is evident from comparative example 1, examples 1-3 and comparative example 2, examples 4-6, the modulus of the PGA film was significantly improved after double drawing. And unexpectedly, when the draw ratio r=2.5, the strength and the elastic modulus of the PGA film each obtained the highest value. For a PGA film with a molecular weight of 180000g/mol, the mechanical tensile strength, elongation at break and elastic modulus after 2.5 times double drawing were improved by 9%, 1657% and 38%, respectively. For 300000g/mol of high molecular weight PGA film, the mechanical elongation at break and the elastic modulus after 2.5 times double pulling were improved by 2085% and 10%, respectively. Unexpectedly high elongation is obtained for the PGA film with poor toughness, and the elongation at break of the film is greatly reduced after biaxial stretching. The reason why the PGA film of the present invention is obtained to have an increased elongation at break may be that: the entanglement among PGA molecular chains is weakened in the orientation process of biaxial stretching, the movement capacity of the PGA molecular chains is improved after sizing, and the relaxation time of the PGA chain segments is shortened. The inventors hypothesize that it is possible that the PGA segment relaxation time at a draw ratio r=2.5 matches the tensile strength test draw speed (50 mm/min) at which the glassy PGA undergoes forced high elastic deformation, thus yielding maximum strain.
Claims (10)
1. A biaxially oriented polyglycolic acid film material is prepared from polyglycolic acid through fusion extrusion, casting or calendering.
2. The polyglycolic acid film material according to claim 1, wherein,
the weight average molecular weight of the polyglycolic acid is 100000 ～ 1000000 ten thousand g/mol, preferably 100000 ～ 300000 ten thousand g/mol.
3. The biaxially oriented polyglycolic acid film material according to claim 1,
the biaxially oriented polyglycolic acid film material has a crystallinity of less than 40%, preferably a crystallinity of less than 30%.
4. The biaxially oriented polyglycolic acid film material according to claim 1,
the thickness of the biaxially oriented polyglycolic acid film material is 5 to 50 μm, preferably 5 to 30 μm.
5. A method for preparing a biaxially oriented polyglycolic acid film material according to any one of claims 1 to 4, comprising the steps of carrying out melt extrusion, casting or calendaring on polyglycolic acid to form a film or sheet, and carrying out biaxial stretching and cooling to obtain the biaxially oriented polyglycolic acid film material, wherein the longitudinal direction and the transverse direction of biaxial stretching are synchronously stretched by adopting the same stretching multiple and the same stretching rate.
6. The preparation method according to claim 5, wherein the preparation method specifically comprises the following steps:
(1) Drying polyglycolic acid;
(2) Casting or calendaring the dried polyglycolic acid to form a film or sheet;
(3) Preheating the obtained film or sheet, and simultaneously biaxially stretching and cooling the film or sheet along the longitudinal direction and the transverse direction of the film to obtain the biaxially stretched polyglycolic acid film material.
7. The method according to claim 6, wherein,
the drying temperature in the step (1) is 10-90 ℃, preferably 20-60 ℃; and/or the number of the groups of groups,
the moisture content of the dried polyglycolic acid is less than 50ppm.
8. The method according to claim 6, wherein,
the extrusion conditions in the step (2) are as follows: the extrusion temperature is 190-260 ℃, preferably 190-240 ℃; the rotation speed of the extruder is 50-500 rpm, preferably 60-250 rpm; and/or the number of the groups of groups,
the temperature of casting or calendaring is 10 to 60 ℃, preferably 10 to 50 ℃.
9. The method according to claim 6, wherein in the step (3):
when the weight average molecular weight of the polyglycolic acid is less than or equal to 200000g/mol, the temperature of preheating and biaxial stretching is 20-70 ℃, preferably 25-50 ℃; the stretching ratio is 1.1 to 5 times, preferably 1.1 to 3 times; the stretching rate is 1 to 500mm/s, preferably 1 to 70mm/s; the cooling rate is 10-400 ℃/min, preferably 20-200 ℃/min; the cooling time is 1 to 30s, preferably 1 to 10s; or alternatively, the first and second heat exchangers may be,
when the weight average molecular weight of the polyglycolic acid is more than 200000g/mol, the temperature of preheating and biaxial stretching is 30-80 ℃, preferably 45-75 ℃; the stretching ratio is 1.1 to 7 times, preferably 1.5 to 5 times; the stretching rate is 1 to 500mm/s, preferably 7 to 70mm/s; the cooling rate is 10-200 ℃/min, preferably 7-100 ℃/min, and the cooling time is 10-60 s, preferably 10-35 s.
10. A biaxially oriented polyglycolic acid film material according to any one of claims 1 to 4, or a biaxially oriented polyglycolic acid film material obtained by the production method according to any one of claims 5 to 9, for use in packaging materials.
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