CN114395232B - Processing method of degradable packaging film and degradable packaging film - Google Patents
Processing method of degradable packaging film and degradable packaging film Download PDFInfo
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- C08J5/18—Manufacture of films or sheets
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- 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
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- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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- C08J2483/04—Polysiloxanes
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Abstract
The invention provides a processing method of a degradable packaging film, and relates to the technical field of films. Specifically, the degradable packaging film comprises the following raw material components, by weight, 100 parts of polylactic acid, 0.005-0.2 part of sulfhydrylation cage type polysilsesquioxane, 10-25 parts of terminal vinyl compound or side vinyl compound and 0.1-5 parts of photoinitiator; the processing method of the degradable packaging film comprises the steps of mixing the raw material components, evenly mixing the raw material components in a melting way, extruding, casting to form a film, biaxially stretching and irradiating with ultraviolet light for 0.5-10 minutes. The processing method of the degradable packaging film can obviously improve the puncture resistance strength of the film and still maintain relatively high tensile strength.
Description
Technical Field
The invention belongs to the technical field of films, and relates to a processing method of a degradable packaging film and the degradable packaging film.
Background
Polylactic acid film is an environment-friendly film as a packaging film, but has the problem of insufficient toughness and the like. The toughening modification of adding the toughening modifier into the polylactic acid film is an effective method, but the traditional toughening modifier has larger influence on the tensile strength of the film and larger reduction range of the tensile strength. Therefore, a new toughening modification method is still required to be continuously developed so as to accelerate popularization of application of the polylactic acid film and solve the problem of the hard-to-degrade film.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a processing method of a degradable packaging film.
The invention also provides a degradable packaging film.
The technical scheme of the invention is as follows:
the processing method of the degradable packaging film comprises the following raw material components, by weight, 100 parts of polylactic acid, 0.005-0.2 part of sulfhydrylation cage polysilsesquioxane, 10-25 parts of terminal vinyl compound or side vinyl compound and 0.1-5 parts of photoinitiator;
the average relative molecular mass of the vinyl-terminated compound is not less than 200, and each terminal group has a vinyl group;
the average relative molecular mass of the side vinyl compound is not less than 500, and the side group contains at least 1 vinyl group;
the processing method comprises the steps of mixing the raw material components, evenly mixing the raw material components in a melting way, extruding, casting to form a film, biaxially stretching and irradiating with ultraviolet light for 0.5-10 minutes.
Preferably, the polylactic acid has a number average molecular weight of not less than 5 ten thousand.
Preferably, the structural general formula of the sulfhydrylation cage type polysilsesquioxane is R 1 a R 2 b (SiO 1.5 ) n Wherein R is 1 Substituted alkyl selected from C1-C6 alkyl or non-mercapto, R 2 Is 3-mercaptopropyl, 0.ltoreq.a.ltoreq.6, a+b.ltoreq.n, n.ltoreq.6, 8, 10 or 12.
Preferably, a is more than or equal to 0 and less than or equal to 5, and n=8.
Preferably, the terminal vinyl compound is selected from the group consisting of a double-ended allyloxy polyether or a double-ended allyloxy polyester.
Preferably, the pendant vinyl compound is selected from vinyl silicone oils, having the general structural formula R 3 SiMe 2 O(SiOMe 2 ) e (SiOMeR 4 ) f (SiOMeVi) g SiMe 2 R 3 Wherein R is 3 Selected from methyl, vinyl or hydroxy, R 4 Selected from C1-C18 alkyl or substituted alkyl or phenyl, me represents methyl, vi represents vinyl, g is 1-10, e is 0, and f is 0;
the viscosity of the vinyl silicone oil at 25 ℃ is 200-5000 Pa.s.
Preferably, the extrusion temperature is 180-230 ℃.
Preferably, the multiple of the longitudinal stretching in the biaxial stretching is 2-6 times, and the multiple of the transverse stretching is 2-6 times.
Preferably, the degradable packaging film further comprises at least one of an antioxidant, a processing aid, a filler, and a pigment.
A degradable packaging film obtained by the processing method of any one of the embodiments described above.
The invention adopts the vinyl-terminated compound or the side vinyl compound as the toughening component of the polylactic acid, so as to improve the toughness, namely the puncture resistance strength, of the polylactic acid film; meanwhile, the mercapto cage polysilsesquioxane is adopted, so that the mercapto cage polysilsesquioxane has the function of a nucleating agent, can be crosslinked with a terminal vinyl compound or a side vinyl compound, and improves the tensile strength of the packaging film. Therefore, the packaging film has better puncture resistance strength, and can avoid the great reduction of the tensile strength of the film, so that the packaging film has better comprehensive performance.
The beneficial effects of the invention are as follows:
(1) The degradable packaging film has better puncture resistance and better tensile strength than the conventional toughened polylactic acid.
(2) The cross-linked structure formed by the mercapto cage polysilsesquioxane and the terminal vinyl compound or the side vinyl compound improves the heat resistance of the packaging film.
(3) The nucleation of the cage polysilsesquioxane is beneficial to improving the crystallinity of the polylactic acid and improving the tensile strength of the polylactic acid.
Detailed Description
The technical scheme of the invention is further illustrated and described through the following specific embodiments.
The invention provides a processing method of a degradable packaging film, which comprises the following raw material components, by weight, 100 parts of polylactic acid, 0.005-0.2 part of sulfhydrylation cage polysilsesquioxane, 10-25 parts of terminal vinyl compound or side vinyl compound and 0.1-5 parts of photoinitiator;
in the present invention, the weight of the mercaptocage polysilsesquioxane can be determined based on the weight of the terminal vinyl compound or the side vinyl compound and their vinyl content, as well as on a number of factors such as the number of mercapto groups in the molecular structure of the mercaptocage polysilsesquioxane. For example, under the same conditions, the number of mercapto groups in the molecular structure of the mercapto-cage polysilsesquioxane is small, and the required weight of the mercapto-cage polysilsesquioxane is correspondingly large.
The average relative molecular mass of the vinyl-terminated compound is not less than 200, and each terminal group has a vinyl group; more preferably, the average relative molecular weight of the terminal vinyl compound is not more than 20000.
The average relative molecular mass of the side vinyl compound is not less than 500, and the side group contains at least 1 vinyl group; more preferably, the average relative molecular weight of the side vinyl compound is not more than 30000.
The processing method comprises the steps of mixing the raw material components, evenly melting and mixing, extruding to form a film, biaxially stretching and irradiating with ultraviolet light for 0.5-10 minutes.
In the present invention, the photoinitiator is not particularly limited, and is a mercapto-ene click chemical reaction addition for generating a radical to initiate a mercapto group and a carbon-carbon double bond under ultraviolet irradiation. In particular, the photoinitiator may be selected from benzoin-type photoinitiators such as benzoin dimethyl ether, benzoin diethyl ether, benzoin butyl ether and the like.
In the invention, during processing, each raw material component is added into an extruder for melting at 180-220 ℃, extruded at 180-230 ℃, cast into a casting film with the thickness of 100 mu m-1mm by using a casting machine, then stretched in one way or two ways by using a stretcher, and finally the packaging film with the thickness of 10-100 mu m is obtained by ultraviolet irradiation. The ultraviolet light in the invention is not particularly limited, the dominant wavelength can be 365nm, and the light intensity is 1-100mW/cm 2 . Generally, the higher the light intensity, the shorter the required ultraviolet irradiation time; the lower the light intensity, the longer the ultraviolet irradiation time required.
In a preferred embodiment of the present invention, the polylactic acid has a number average molecular weight of not less than 5 ten thousand. More preferably, the polylactic acid has a number average molecular weight of not less than 8 ten thousand.
In a preferred embodiment of the present invention, the mercaptocage polysilsesquioxane has the general structural formula R 1 a R 2 b (SiO 1.5 ) n Wherein R is 1 Substituted alkyl selected from C1-C6 alkyl or non-mercapto, R 2 Is 3-mercaptopropyl, 0.ltoreq.a.ltoreq.6, a+b.ltoreq.n, n.ltoreq.6, 8, 10 or 12.
In a preferred embodiment of the present invention, 0.ltoreq.a.ltoreq.5, n=8.
In the present invention, the mercaptocage polysilsesquioxane may be mercaptocage octapolysilsesquioxane, such as octa (3-mercaptopropyl) cage octapolysilsesquioxane, tris (3-mercaptopropyl) pentamethyl cage octapolysilsesquioxane, tris (3-mercaptopropyl) pentapropyl cage octapolysilsesquioxane, penta (3-mercaptopropyl) trimethyl cage octapolysilsesquioxane, penta (3-mercaptopropyl) tripropyl cage octapolysilsesquioxane, penta (3-mercaptopropyl) triphenyl cage octapolysilsesquioxane, and the like.
In a preferred embodiment of the present invention, the terminal vinyl compound is selected from the group consisting of a double-ended allyloxy polyether or a double-ended allyloxy polyester.
In the invention, the structural general formula of the double-end allyloxy polyether is CH 2 ＝CHCH 2 O(CH 2 CH 2 O) x (CH 2 CHOCH 3 ) y CH 2 CH＝CH 2 X is greater than or equal to 0, y is greater than or equal to 0, and x+y is greater than or equal to 5. More specifically, x+y is less than or equal to 500. Further, the polyether structure in the double-end allyloxy polyether is polyethylene glycol or polypropylene glycol or a copolymerization structure of polyethylene glycol and polypropylene glycol.
In the invention, the structural general formula of the double-end allyloxy polyester is CH 2 ＝CHCH 2 O(CH 2 ) q O(CO(CH 2 ) p COO(CH 2 ) q O) h CH 2 CH＝CH 2 P and q are positive integers, p is more than or equal to 0 and less than or equal to 4, q is more than or equal to 2 and less than or equal to 4,h and more than or equal to 5. More specifically, h is less than or equal to 200. Further, the polyester structure in the double-end allyloxy polyester can be formed by condensing 1, 6-adipic acid with ethylene glycol, or by condensing 1, 4-succinic acid with ethylene glycol, or by condensing 1, 6-adipic acid with 1, 4-butanediol, or by condensing terephthalic acid with ethylene glycol, or by condensing terephthalic acid with 1, 4-butanediol.
In a preferred embodiment of the present invention, the pendant vinyl compound is selected from vinyl silicone oils, having the general structural formula R 3 SiMe 2 O(SiOMe 2 ) e (SiOMeR 4 ) f (SiOMeVi) g SiMe 2 R 3 Wherein R is 3 Selected from methyl, vinyl or hydroxy, R 4 Selected from C1-C18 alkyl or substituted alkyl or phenyl, me represents methyl, vi represents vinyl, g is 1-10, e is 0, and f is 0;
the viscosity of the vinyl silicone oil may be 200-5000mpa.s at 25 ℃.
In a more preferred embodiment of the present invention, if R 3 Not vinyl, and g is more than or equal to 2.5 and less than or equal to 6; if R is 3 Vinyl, g is more than or equal to 1 and less than or equal to 6; when R is 3 When vinyl, R 3 Can participate in the reaction with sulfhydryl groups, so that the average number of sulfhydryl groups on a pendant group can be relatively small, such as 1 or 2 or more than 2; if R is 3 When not vinyl, R 3 Cannot participate in the reaction with mercapto groups, so that the average number of mercapto groups on the side groups must be 2 or more to achieve a crosslinked structure.
In a preferred embodiment of the invention, the extrusion temperature is 180-230 ℃.
In a preferred embodiment of the present invention, the multiple of the longitudinal stretching in the biaxial stretching is 2 to 6 times and the multiple of the transverse stretching is 2 to 6 times.
One specific extrusion, casting film forming and stretching process is as follows: extruding and casting into a casting sheet with the thickness of about 450 mu m, and carrying out biaxial stretching on the casting sheet on a biaxial stretching tester at the temperature of 50-90 ℃ for 10-20 seconds at the stretching speed of 30-70mm/s at the shaping temperature of 80-130 ℃ for 5-7 seconds at the biaxial stretching multiplying power of (2-6) x (2-6). More specifically, the temperature is 60-80 ℃, the preheating time is 12-17 seconds, the stretching speed is 45-65mm/s, the shaping temperature is 90-120 ℃, the shaping time is 5 seconds, and the biaxial stretching multiplying power can be (3-5) x (3-5).
In a preferred embodiment of the present invention, the degradable packaging film further comprises at least one of an antioxidant, a processing aid, a filler, and a pigment.
The purpose of the antioxidant in the present invention is to improve the antioxidant properties of the degradable material composition, and may be selected from the group consisting of antioxidant 1010, antioxidant 1076, antioxidant 1098, and the like. The addition weight of the antioxidant can be 0.5-2% of the weight of the polylactic acid.
The processing aid in the present invention is aimed at improving the processability of the degradable material composition and may be selected from polyethylene wax, oxidized polyethylene wax, stearic acid, zinc stearate, calcium stearate, magnesium stearate, etc. The addition weight of the processing aid can be 0.5-1.5% of the weight of the polylactic acid.
The filler of the present invention is aimed at further improving certain properties of the degradable material composition and may be selected from talc, silica micropowder, titanium pigment, silica, calcium carbonate, silicon carbide, silicon nitride, nylon fiber, glass microsphere, glass fiber, etc. The addition weight of the filler can be 5-60% of the weight of the polylactic acid.
The purpose of the pigments in the present invention is to enhance the apparent color of the degradable material composition, which may be selected from inorganic pigments or organic pigments. The addition weight of the pigment may be 0.5 to 5% of the weight of the polylactic acid.
In another aspect, the invention also provides a degradable packaging film obtained by the processing method according to any one of the embodiments.
The degradable packaging film of the invention can be applied to various types of packaging.
The technical scheme of the invention is further described and illustrated below according to various embodiments. The parts are by weight in the examples below, unless otherwise indicated.
Example 1
Polylactic acid: l-lactic acid and D-lactic acid copolymer, L-lactic acid accounting for 96.1%, D-lactic acid 3.9%, number average molecular weight 9.2 ten thousand, and molecular weight distribution 1.68.
Double-ended allyloxy polyether: structural CH 2 ＝CHCH 2 O(CH 2 CH 2 O) 37.3 (CH 2 CHOCH 3 ) 6.9 CH 2 CH＝CH 2 ；
100 parts of polylactic acid, 0.01 part of octa (3-mercaptopropyl) cage-type octa polysilsesquioxane, 12 parts of double-end allyloxy polyether and 2 parts of benzoin butyl ether are added into an extruder, are melted and mixed uniformly at 195-200 ℃, are extruded and cast into a casting sheet with the thickness of about 450 mu m at 205 ℃, the casting sheet is biaxially stretched on a biaxial stretching tester at the temperature of 65 ℃ for 12 seconds, the stretching speed of 60mm/s, the shaping temperature of 110 ℃ and the shaping time of 5 seconds, the biaxial stretching multiplying power is 4 multiplied by 4, and the main wavelength of 365nm and the intensity of 20mW/cm are obtained 2 The mixture was irradiated for 2 minutes to obtain a thin film having a thickness of 25. Mu.m.
Example 2
100 parts of polylactic acid in example 1, 0.01 part of octa (3-mercaptopropyl) cage octapolysilsesquioxane, 20 parts of double-end allyloxy polyether in example 1 and 2 parts of benzoin butyl ether are added into an extruder, melted and mixed uniformly at 195-200 ℃, extruded and cast into a casting sheet with the thickness of about 450 mu m at 205 ℃, biaxially stretched on a biaxial stretching tester at the temperature of 65 ℃, the preheating time of 12 seconds, the stretching speed of 60mm/s, the setting temperature of 110 ℃, the setting time of 5 seconds, the biaxial stretching multiplying power of 4 multiplied by 4, and the main wavelength of 365nm and the intensity of 20mW/cm 2 The mixture was irradiated for 2 minutes to obtain a thin film having a thickness of 25. Mu.m.
Example 3
100 parts of polylactic acid in example 1, 0.03 part of octa (3-mercaptopropyl) cage octapolysilsesquioxane, 20 parts of double-end allyloxy polyether in example 1 and 2 parts of benzoin butyl ether are added into an extruder, melted and mixed uniformly at 195-200 ℃, extruded and cast into a casting sheet with the thickness of about 450 mu m at 205 ℃, biaxially stretched on a biaxial stretching tester at the temperature of 65 ℃, the preheating time of 12 seconds, the stretching speed of 60mm/s, the setting temperature of 110 ℃, the setting time of 5 seconds, the biaxial stretching multiplying power of 4 multiplied by 4, and the main wavelength of 365nm and the intensity of 20mW/cm 2 Under irradiation for 2 minutesA film having a film thickness of 25 μm was obtained.
Example 4
Double-ended allyloxy polyesters: structural CH 2 ＝CHCH 2 O(CH 2 ) 2 O(CO(CH 2 ) 4 COO(CH 2 ) 2 O) 30.5 CH 2 CH＝CH 2 ；
100 parts of polylactic acid in example 1, 0.08 part of tris (3-mercaptopropyl) pentapropyl cage octapolysilsesquioxane, 15 parts of double-end allyloxy polyester and 3 parts of benzoin dimethyl ether are added into an extruder, are melted and mixed uniformly at 195-200 ℃, are extruded and cast into a casting sheet with the thickness of about 450 mu m at 210 ℃, the casting sheet is biaxially stretched on a biaxial stretching tester at the temperature of 70 ℃ and the preheating time of 13 seconds, the stretching speed of 65mm/s, the shaping temperature of 95 ℃ and the shaping time of 5 seconds, the biaxial stretching multiplying power is 4 multiplied by 4, and the main wavelength of 365nm and the intensity of 20mW/cm are obtained 2 The mixture was irradiated for 2 minutes to obtain a thin film having a thickness of 25. Mu.m.
Example 5
100 parts of polylactic acid in example 1, 0.15 part of tris (3-mercaptopropyl) pentapropyl cage octapolysilsesquioxane, 15 parts of double-end allyloxy polyester in example 4 and 3 parts of benzoin dimethyl ether are added into an extruder, are melted and mixed uniformly at 195-200 ℃, are extruded and cast into a casting sheet with the thickness of about 450 mu m at 210 ℃, the casting sheet is biaxially stretched on a biaxial stretching tester at the temperature of 70 ℃, the preheating time is 13 seconds, the stretching speed is 65mm/s, the shaping temperature is 95 ℃, the shaping time is 5 seconds, the biaxial stretching multiplying power is 4 multiplied by 4, and the main wavelength is 365nm and the intensity is 20mW/cm 2 The mixture was irradiated for 2 minutes to obtain a thin film having a thickness of 25. Mu.m.
Example 6
100 parts of polylactic acid in example 1, 0.15 part of tris (3-mercaptopropyl) pentapropyl cage octapolysilsesquioxane, 20 parts of double-end allyloxy polyester in example 4 and 3 parts of benzoin dimethyl ether are added into an extruder, are melted and mixed uniformly at 195-200 ℃, are extruded and cast at 210 ℃ to form a casting sheet with the thickness of about 450 mu m, the casting sheet is biaxially stretched on a biaxial stretching tester at the temperature of 70 ℃, the preheating time is 13 seconds, the stretching speed is 65mm/s, the shaping temperature is 95 ℃,setting for 5 seconds, wherein the biaxial stretching multiplying power is 4 multiplied by 4, and the main wavelength is 365nm, and the intensity is 20mW/cm 2 The mixture was irradiated for 2 minutes to obtain a thin film having a thickness of 25. Mu.m.
Example 7
Vinyl silicone oil: structural SiMe 3 O(SiOMe 2 ) 80.4 (SiOMeR 4 ) 10.7 (SiOMeVi) 4.1 SiMe 3 Me is methyl, vi is vinyl, R 4 Is gamma- (2, 3-glycidoxypropyl) propyl.
100 parts of polylactic acid in example 1, 0.18 part of octa (3-mercaptopropyl) cage octapolysilsesquioxane, 10 parts of vinyl silicone oil, 0.8 part of antioxidant 1076, 40 parts of glass microspheres with average particle size of 1.8 mu m, 2 parts of zinc stearate and 4 parts of benzoin butyl ether are added into an extruder, are melted and mixed uniformly at 205-205 ℃, are extruded at 210 ℃ and cast into a casting sheet with thickness of about 450 mu m, the casting sheet is biaxially stretched on a biaxial stretching tester at 70 ℃ for 15 seconds at a preheating speed of 65mm/s and a shaping temperature of 90 ℃ for 6 seconds, the biaxial stretching multiplying power is 4 multiplied by 4, and the casting sheet is further stretched at 365nm of main wavelength and 20mW/cm of intensity 2 The mixture was irradiated for 3 minutes to obtain a thin film having a thickness of 25. Mu.m.
Example 8
100 parts of polylactic acid in example 1, 0.18 part of octa (3-mercaptopropyl) cage octapolysilsesquioxane, 16 parts of vinyl silicone oil in example 7, 0.8 part of antioxidant 1076, 40 parts of glass microspheres with average particle size of 1.8 mu m, 2 parts of zinc stearate and 4 parts of benzoin butyl ether are added into an extruder, and are melted and mixed uniformly at 205-205 ℃, extruded and cast into a casting sheet with thickness of about 450 mu m at 210 ℃, the casting sheet is biaxially stretched on a biaxial stretching tester at 70 ℃, the preheating time is 15 seconds, the stretching speed is 65mm/s, the shaping temperature is 90 ℃, the shaping time is 6 seconds, the biaxial stretching multiplying power is 4 multiplied by 4, and the casting sheet is further processed at the dominant wavelength of 365nm and the strength of 20mW/cm 2 The mixture was irradiated for 3 minutes to obtain a thin film having a thickness of 25. Mu.m.
Example 9
100 parts of polylactic acid in example 1, 0.18 part of octa (3-mercaptopropyl) cage octa-polysilsesquioxane, 23 parts of vinyl silicone oil in example 7, 0.8 part of antioxidant 1076,Adding 40 parts of glass microspheres with average particle size of 1.8 mu m, 2 parts of zinc stearate and 4 parts of benzoin butyl ether into an extruder, melting and mixing uniformly at 205-205 ℃, extruding at 210 ℃ and casting into a casting sheet with thickness of about 450 mu m, biaxially stretching the casting sheet on a biaxially stretching tester at 70 ℃ for 15 seconds, stretching speed of 65mm/s, shaping temperature of 90 ℃ for 6 seconds, biaxially stretching multiplying power of 4 multiplied by 4, and then obtaining a casting sheet with main wavelength of 365nm and intensity of 20mW/cm 2 The mixture was irradiated for 3 minutes to obtain a thin film having a thickness of 25. Mu.m.
Comparative example 1
100 parts of polylactic acid and 0.01 part of octa (3-mercaptopropyl) cage octa polysilsesquioxane in the example 1 are added into an extruder, melted and mixed uniformly at 195-200 ℃, extruded at 205 ℃ and cast into a casting sheet with the thickness of about 450 mu m, the casting sheet is biaxially stretched on a biaxial stretching tester at 65 ℃ for 12 seconds, the stretching speed is 60mm/s, the shaping temperature is 110 ℃, the shaping time is 5 seconds, the biaxial stretching multiplying power is 4 multiplied by 4, and the film with the thickness of 25 mu m is obtained.
Comparative example 2
The octa (3-mercaptopropyl) cage octa polysilsesquioxane in comparative example 1 was changed to 0.15 parts, and the remaining steps remained unchanged.
Comparative example 3
100 parts of polylactic acid in example 1 and 20 parts of double-end allyloxy polyether in example 1 are added into an extruder, melted and mixed uniformly at 195-200 ℃, extruded at 205 ℃ and cast into a casting sheet with the thickness of about 450 mu m, the casting sheet is biaxially stretched on a biaxial stretching tester at the temperature of 65 ℃, the preheating time of 12 seconds, the stretching speed of 60mm/s, the shaping temperature of 110 ℃, the shaping time of 5 seconds, the biaxial stretching multiplying power of 4 multiplied by 4, and the main wavelength of 365nm and the intensity of 20mW/cm 2 The mixture was irradiated for 2 minutes to obtain a thin film having a thickness of 25. Mu.m.
Comparative example 4
100 parts of polylactic acid in example 1, 0.25 part of octa (3-mercaptopropyl) cage octa-polysilsesquioxane and 20 parts of double-end allyloxy polyether in example 1 are added into an extruder, extruded at 205 ℃ and cast into a casting sheet with the thickness of about 450 mu m, the casting sheet is biaxially stretched on a biaxial stretching tester,the temperature is 65 ℃, the preheating time is 12 seconds, the stretching speed is 60mm/s, the shaping temperature is 110 ℃, the shaping time is 5 seconds, the biaxial stretching multiplying power is 4 multiplied by 4, and then the stretching speed is 20mW/cm at the dominant wavelength of 365nm 2 The mixture was irradiated for 2 minutes to obtain a thin film having a thickness of 25. Mu.m.
Comparative example 5
100 parts of polylactic acid in example 1, 0.003 part of octa (3-mercaptopropyl) cage octapolysilsesquioxane, 16 parts of vinyl silicone oil in example 7, 0.8 part of antioxidant 1076, 40 parts of glass microspheres with average particle size of 1.8 mu m and 2 parts of zinc stearate are added into an extruder, are evenly mixed by melting at 205-205 ℃, are extruded at 210 ℃ and cast into a casting sheet with thickness of about 450 mu m, the casting sheet is biaxially stretched on a biaxial stretching tester at the temperature of 70 ℃, the preheating time is 15 seconds, the stretching speed is 65mm/s, the shaping temperature is 90 ℃, the shaping time is 6 seconds, the biaxial stretching multiplying power is 4 multiplied by 4, and the casting sheet is further stretched at the dominant wavelength of 365nm and the intensity of 20mW/cm 2 The mixture was irradiated for 3 minutes to obtain a thin film having a thickness of 25. Mu.m.
Comparative example 6
The octa (3-mercaptopropyl) cage octa-polysilsesquioxane in comparative example 5 was changed to 0.28 parts, and the remaining steps remained unchanged.
Performance testing
The results of the performance test of the films of examples 1 to 9 and comparative examples 1 to 6 are shown in Table 1.
TABLE 1 Performance test results
Therefore, the data in table 1 shows that the ultraviolet irradiation crosslinking reaction is performed by using the mercapto cage polysilsesquioxane and the terminal vinyl compound or the side vinyl compound, such as the double-end allyloxy polyether, the double-end allyloxy polyester and the vinyl silicone oil, so that the puncture resistance strength of the polylactic acid film is improved, the influence on the tensile strength is small, and the tensile strength can be maintained to be better than that of a pure toughening agent.
As described above, the basic principles, main features and advantages of the present invention are shown and described. It will be appreciated by persons skilled in the art that the present invention is not limited to the embodiments described above, which are preferred embodiments of the present invention, and the scope of the invention is not limited thereto, i.e. equivalent changes and modifications as defined by the claims and the description herein should be made while remaining within the scope of the invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The processing method of the degradable packaging film is characterized by comprising the following raw material components, by weight, 100 parts of polylactic acid, 0.005-0.2 part of sulfhydrylation cage-type polysilsesquioxane, 10-25 parts of terminal vinyl compound or side vinyl compound and 0.1-5 parts of photoinitiator;
the vinyl-terminated compound is selected from double-end allyloxy polyether or double-end allyloxy polyester, and the average relative molecular weight of the vinyl-terminated compound is not less than 200;
the side vinyl compound is selected from vinyl silicone oil and has a structural general formula R 3 SiMe 2 O(SiOMe 2 ) e (SiOMeR 4 ) f (SiOMeVi) g SiMe 2 R 3 Wherein R is 3 Selected from methyl, vinyl or hydroxy, R 4 Selected from C1-C18 alkyl or substituted alkyl or phenyl, me represents methyl, vi represents vinyl, 1.ltoreq.g.ltoreq.10, e.gtoreq.0, f.gtoreq.0, the average relative molecular mass of the side vinyl compound being not less than 500;
the processing method comprises the steps of mixing the raw material components, evenly mixing the raw material components in a melting way, extruding, casting to form a film, biaxially stretching and irradiating with ultraviolet light for 0.5-10 minutes.
2. The processing method according to claim 1, wherein the polylactic acid has a number average molecular weight of not less than 5 ten thousand.
3. The process of claim 1, wherein the mercaptocage polysilsesquioxane has the general structural formula R 1 a R 2 b (SiO 1.5 ) n Wherein R is 1 Substituted alkyl selected from C1-C6 alkyl or non-mercapto, R 2 Is 3-mercaptopropyl, 0.ltoreq.a.ltoreq.6, a+b.ltoreq.n, n.ltoreq.6, 8, 10 or 12.
4. A processing method according to claim 3, wherein 0.ltoreq.a.ltoreq.5, and n=8.
5. The process according to claim 1, wherein the viscosity of the vinyl silicone oil is 200-5000mpa.s at 25 ℃.
6. The process of claim 1, wherein the extrusion temperature is 180-230 ℃.
7. The processing method according to claim 1, wherein the multiple of the longitudinal stretching in the biaxial stretching is 2 to 6 times and the multiple of the transverse stretching is 2 to 6 times.
8. The process of claim 1, the degradable packaging film further comprising at least one of an antioxidant, a processing aid, a filler, and a pigment;
the processing aid is selected from polyethylene wax, oxidized polyethylene wax, stearic acid, zinc stearate, calcium stearate or magnesium stearate.
9. A degradable packaging film, characterized in that it is obtained by the processing method according to any one of claims 1-8.
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