CN114395232A - Processing method of degradable packaging film and degradable packaging film - Google Patents

Processing method of degradable packaging film and degradable packaging film Download PDF

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CN114395232A
CN114395232A CN202210088217.7A CN202210088217A CN114395232A CN 114395232 A CN114395232 A CN 114395232A CN 202210088217 A CN202210088217 A CN 202210088217A CN 114395232 A CN114395232 A CN 114395232A
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vinyl
parts
packaging film
degradable packaging
vinyl compound
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CN114395232B (en
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高国惠
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Guangdong Yinger Industrial Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/06—Unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J2483/04—Polysiloxanes
    • C08J2483/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J2483/04—Polysiloxanes
    • C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

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, melting and uniformly mixing, extruding, casting to form a film, stretching in a bidirectional mode, and irradiating for 0.5-10 minutes by ultraviolet light. The processing method of the degradable packaging film can obviously improve the puncture resistance of the film and still maintain relatively high tensile strength.

Description

Processing method of degradable packaging film and degradable packaging film
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 films are an environmentally friendly film as a packaging film, but have problems such as insufficient toughness. The toughening modification by adding the toughening modifier into the polylactic acid film is an effective method, but the existing toughening modifier has great influence on the tensile strength of the film, and the reduction range of the tensile strength is large. Therefore, there is still a need to develop a new toughening modification method to accelerate the popularization of the application of the polylactic acid film and solve the problem of the film which is difficult to degrade.
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 type 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 terminal vinyl 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, melting and uniformly mixing, extruding, casting to form a film, stretching in two directions, and irradiating for 0.5-10 minutes by ultraviolet light.
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 R1 aR2 b(SiO1.5)nWherein R is1Selected from C1-C6 alkyl or non-mercapto substituted alkyl, R2Is 3-mercaptopropyl, 0 ≤ a ≤ 6, a + b ═ n, n ═ 6, 8, 10, or 12.
Preferably, a is 0 ≦ 5 and n is 8.
Preferably, the terminal vinyl compound is selected from a terminal allyloxy polyether or a terminal allyloxy polyester.
Preferably, the side vinyl compound is selected from vinyl silicone oil and has a structural general formula R3SiMe2O(SiOMe2)e(SiOMeR4)f(SiOMeVi)gSiMe2R3Wherein R is3Selected from methyl, vinyl or hydroxy, R4Selected from C1-C18 alkyl or substituted alkyl or phenyl, Me represents methyl, Vi represents vinyl, g is more than or equal to 1 and less than or equal to 10, e is more than or equal to 0, and f is more than or equal to 0;
the viscosity of the vinyl silicone oil at 25 ℃ is 200-5000mPa.
Preferably, the temperature of the extrusion is 180-.
Preferably, the ratio of longitudinal stretching in the biaxial stretching is 2 to 6 times, and the ratio of transverse stretching is 2 to 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 process of any one of the embodiments above.
The invention adopts the terminal vinyl compound or the side vinyl compound as the toughening component of the polylactic acid, so as to improve the toughness of the polylactic acid film, namely the puncture resistance; meanwhile, the sulfhydrylation cage type polysilsesquioxane has the function of a nucleating agent, and can be crosslinked with a terminal vinyl compound or a side vinyl compound, so that the tensile strength of the packaging film is improved. Therefore, the packaging film has better puncture resistance, and can avoid the great reduction of the tensile strength of the film, so that the packaging film has better comprehensive performance.
The invention has the beneficial effects that:
(1) the degradable packaging film has better puncture resistance and better tensile strength than the conventional toughened polylactic acid.
(2) The heat resistance of the packaging film is improved by the crosslinking structure formed by the sulfhydrylation cage-type polysilsesquioxane and the terminal vinyl compound or the side vinyl compound.
(3) The nucleation effect of the cage-type polysilsesquioxane is beneficial to improving the crystallinity of the polylactic acid and improving the tensile strength of the polylactic acid.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
The invention provides a processing method of a degradable packaging film, which comprises the following raw material components in parts 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;
in the present invention, the weight of the thiolated cage-type polysilsesquioxane may be determined by a number of factors, such as the weight of the terminal vinyl compound or the side vinyl compound, the vinyl contents thereof, and the number of mercapto groups in the molecular structure of the thiolated cage-type polysilsesquioxane. For example, under the same conditions, the number of mercapto groups in the molecular structure of the thiolated cage-type polysilsesquioxane is small, and the weight of the thiolated cage-type polysilsesquioxane required is correspondingly large.
The average relative molecular mass of the terminal vinyl compound is not less than 200, and each terminal group has a vinyl group; more preferably, the average relative molecular mass of the terminal vinyl compound is not higher 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 mass of the pendant vinyl compound is not more than 30000.
The processing method comprises the steps of mixing, melting and uniformly mixing the raw material components, extruding to form a film, stretching in two directions, and irradiating for 0.5-10 minutes by ultraviolet light.
In the present invention, the photoinitiator is not particularly limited, and is to generate free radicals under the irradiation of ultraviolet light to initiate the mercapto-alkene click chemistry reaction addition of mercapto and carbon-carbon double bond. Specifically, the photoinitiator may be selected from benzoin photoinitiators, such as benzoin dimethyl ether, benzoin ethyl ether, benzoin butyl ether, and the like.
In the invention, during processing, the raw material components are added into an extruder to be melted at 220 ℃ and 180 ℃ and extruded at 230 ℃, then cast into a casting film with the thickness of 100 mu m-1mm by a casting machine, and then are stretched unidirectionally or bidirectionally by a stretcher, and finally are irradiated by ultraviolet light to obtain the packaging film with the thickness of 10-100 mu m. The ultraviolet light in the present invention is not particularly limited, and the dominant wavelength may be 365nm, and the light intensity may be 1-100mW/cm2. In general, the higher the light intensity, the longer the UV exposure time requiredThe shorter; the lower the light intensity, the longer the uv exposure time is 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 invention, the structural general formula of the thiolated cage-type polysilsesquioxane is R1 aR2 b(SiO1.5)nWherein R is1Selected from C1-C6 alkyl or non-mercapto substituted alkyl, R2Is 3-mercaptopropyl, 0 ≤ a ≤ 6, a + b ═ n, n ═ 6, 8, 10, or 12.
In a preferred embodiment of the invention, a is 0 ≦ 5 and n is 8.
In the present invention, the thiolated cage-type polysilsesquioxane may be a thiolated cage-type octapolysilsesquioxane, such as octa (3-mercaptopropyl) cage-type octapolysilsesquioxane, tris (3-mercaptopropyl) pentamethyl cage-type octapolysilsesquioxane, tris (3-mercaptopropyl) pentaphenyl cage-type octapolysilsesquioxane, tris (3-mercaptopropyl) pentapropyl cage-type octapolysilsesquioxane, penta (3-mercaptopropyl) trimethyl cage-type octapolysilsesquioxane, penta (3-mercaptopropyl) tripropyl cage-type octapolysilsesquioxane, penta (3-mercaptopropyl) triphenyl cage-type octapolysilsesquioxane, and the like.
In a preferred embodiment of the invention, the vinyl-terminated compound is selected from a double-terminal allyloxy polyether or a double-terminal allyloxy polyester.
In the invention, the structural general formula of the double-end allyloxy polyether is CH2＝CHCH2O(CH2CH2O)x(CH2CHOCH3)yCH2CH＝CH2X is not less than 0, y is not less than 0, and x + y is not less than 5. More specifically, x + y is ≦ 500. Further, the polyether structure in the double-end allyloxy polyether is a polyethylene glycol or polypropylene glycol or a copolymerization structure of the polyethylene glycol and the polypropylene glycol.
In the invention, the structural general formula of the double-end allyloxy polyester is CH2＝CHCH2O(CH2)qO(CO(CH2)pCOO(CH2)qO)hCH2CH＝CH2P 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, and h is more than or equal to 5. More specifically, h is less than or equal to 200. Furthermore, the polyester structure in the double-end allyloxy polyester can be formed by condensing 1, 6-adipic acid and ethylene glycol, or by condensing 1, 4-succinic acid and ethylene glycol, or by condensing 1, 6-adipic acid and 1, 4-butanediol, or by condensing terephthalic acid and ethylene glycol, or by condensing terephthalic acid and 1, 4-butanediol.
In a preferred embodiment of the invention, the pendant vinyl compounds are selected from vinyl silicone oils having the general structural formula R3SiMe2O(SiOMe2)e(SiOMeR4)f(SiOMeVi)gSiMe2R3Wherein R is3Selected from methyl, vinyl or hydroxy, R4Selected from C1-C18 alkyl or substituted alkyl or phenyl, Me represents methyl, Vi represents vinyl, g is more than or equal to 1 and less than or equal to 10, e is more than or equal to 0, and f is more than or equal to 0;
the viscosity of the vinyl silicone oil at 25 ℃ may be 200-5000 mPa.s.
In the present invention, more preferred embodiments are those wherein R is3Not vinyl, 2.5-6 g; if R is3Is vinyl, g is more than or equal to 1 and less than or equal to 6; when R is3When it is vinyl, R3Can participate in the reaction with thiol groups, and thus the average number of thiol groups of the pendant group can be small, such as 1 or 2 or more than 2; if R is3When not vinyl, R3It is not allowed to participate in the reaction with the mercapto group, and therefore the average number of mercapto groups in the pendant group must be 2 or more to form a crosslinked structure.
In a preferred embodiment of the invention, the temperature of the extrusion is 180-230 ℃.
In a preferred embodiment of the present invention, the stretching ratio in the longitudinal direction in the biaxial stretching is 2 to 6 times, and the stretching ratio in the transverse direction is 2 to 6 times.
A specific extrusion, casting film forming and stretching process comprises the following steps: extruding and casting to form a casting sheet with the thickness of about 450 mu m, and biaxially stretching the casting sheet on a biaxial tensile tester at the temperature of 50-90 ℃, the preheating time of 10-20 seconds, the stretching speed of 30-70mm/s, the setting temperature of 80-130 ℃, the setting time of 5-7 seconds, and the biaxial tension ratio of (2-6) × (2-6). More specifically, the temperature is 60-80 ℃, the preheating time is 12-17 seconds, the stretching speed is 45-65mm/s, the setting temperature is 90-120 ℃, the setting time is 5 seconds, and the biaxial stretching magnification can be (3-5) × (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 antioxidant in the present invention is to improve the antioxidant property of the degradable material composition, and may be selected from antioxidant 1010, antioxidant 1076, antioxidant 1098, and the like. The added weight of the antioxidant can be 0.5-2% of the weight of the polylactic acid.
The processing aid of the present invention is to improve the processability of the degradable material composition, and can be selected from polyethylene wax, oxidized polyethylene wax, stearic acid, zinc stearate, calcium stearate, magnesium stearate, etc. The processing aid may be added in an amount of 0.5 to 1.5% by weight based on the weight of the polylactic acid.
The filler of the invention aims to further improve certain properties of the degradable material composition, and can be selected from talcum powder, silicon micropowder, titanium dioxide, silicon dioxide, calcium carbonate, silicon carbide, silicon nitride, nylon fiber, glass microsphere, glass fiber and the like. The added weight of the filler can be 5-60% of the weight of the polylactic acid.
The pigment used in the present invention is intended to improve the apparent color of the degradable material composition and may be selected from inorganic pigments or organic pigments. The added weight of the pigment can be 0.5-5% of the weight of the polylactic acid.
In another aspect, the present invention further provides a degradable packaging film obtained by the processing method according to any one of the above embodiments.
The degradable packaging film of the present invention can be applied to various types of packaging.
The technical solution of the present invention will be further described and illustrated below with reference to various embodiments. Unless otherwise specified, the parts described in the following examples are parts by weight.
Example 1
Polylactic acid: the copolymer of L-lactic acid and D-lactic acid, the proportion of L-lactic acid is 96.1 percent, the proportion of D-lactic acid is 3.9 percent, the number average molecular weight is 9.2 ten thousand, and the molecular weight distribution is 1.68.
Double-terminal allyloxy polyether: structural formula CH2＝CHCH2O(CH2CH2O)37.3(CH2CHOCH3)6.9CH2CH＝CH2；
100 parts of polylactic acid, 0.01 part of octa (3-mercaptopropyl) cage octa-polysilsesquioxane, 12 parts of double-end allyloxy polyether and 2 parts of benzoin butyl ether are added into an extruder, the mixture is melted and mixed uniformly at 195-plus-200 ℃, the mixture is extruded and cast into a casting sheet with the thickness of about 450 mu m at 205 ℃, the casting sheet is stretched bidirectionally on a biaxial stretching tester with 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 and the biaxial stretching magnification of 4 multiplied by 4, and then the dominant wavelength of 365nm and the strength of 20mW/cm2Then, the film was irradiated for 2 minutes to obtain a thin film having a thickness of 25 μm.
Example 2
100 parts of polylactic acid of example 1, 0.01 part of octa (3-mercaptopropyl) cage-type octapolysilsesquioxane, 20 parts of double-ended allyloxy polyether of example 1 and 2 parts of benzoin butyl ether were fed into an extruder, melt-mixed uniformly at 195 ℃ and 200 ℃, extruded and cast into a cast sheet having a thickness of about 450 μm at 205 ℃, the cast sheet was biaxially stretched in a biaxial tensile tester at 65 ℃, a preheating time of 12 seconds, a stretching speed of 60mm/s, a setting temperature of 110 ℃, a setting time of 5 seconds, a biaxial stretching magnification of 4X 4, and then a dominant wavelength of 365nm and a strength of 20mW/cm2Then, the film was irradiated for 2 minutes to obtain a thin film having a thickness of 25 μm.
Example 3
100 parts of polylactic acid of example 1, 0.03 part of octa (3-mercaptopropyl) cage-type octasilsesquioxane, 20 parts of double-terminal allyloxy polyether of example 1 and 2 parts of benzoin butyl ether were fed into an extruder, melt-mixed uniformly at 195 ℃ and 200 ℃, extruded at 205 ℃ and cast into a cast sheet having a thickness of about 450 μm, which was biaxially stretched in a biaxial tensile tester at 65 ℃ with preheatingThe time is 12 seconds, the stretching speed is 60mm/s, the setting temperature is 110 ℃, the setting time is 5 seconds, the biaxial stretching magnification is 4 multiplied by 4, and then the dominant wavelength is 365nm, and the intensity is 20mW/cm2Then, the film was irradiated for 2 minutes to obtain a thin film having a thickness of 25 μm.
Example 4
Double-ended allyloxy polyester: structural formula CH2＝CHCH2O(CH2)2O(CO(CH2)4COO(CH2)2O)30.5CH2CH＝CH2；
100 parts of the polylactic acid of example 1, 0.08 part of tris (3-mercaptopropyl) pentapropyl cage octasilsesquioxane, 15 parts of double-terminal allyloxy polyester and 3 parts of benzoin dimethyl ether were fed into an extruder, melt-mixed uniformly at 195-plus-200 ℃, extruded and cast at 210 ℃ to form a cast sheet having a thickness of about 450 μm, biaxially stretched in a biaxial tensile tester at a temperature of 70 ℃, a preheating time of 13 seconds, a stretching speed of 65mm/s, a setting temperature of 95 ℃, a setting time of 5 seconds, a biaxial tension ratio of 4X 4, and then a dominant wavelength of 365nm and a strength of 20mW/cm2Then, the film was irradiated for 2 minutes to obtain a thin film having a thickness of 25 μm.
Example 5
100 parts of the polylactic acid of example 1, 0.15 part of tris (3-mercaptopropyl) pentapropyl cage octasilsesquioxane, 15 parts of the double-terminal allyloxy polyester of example 4 and 3 parts of benzoin dimethyl ether were fed into an extruder, melt-mixed uniformly at 195-plus-200 ℃, extruded and cast at 210 ℃ to form a cast sheet having a thickness of about 450 μm, biaxially stretched in a biaxial tensile tester at a temperature of 70 ℃, a preheating time of 13 seconds, a stretching speed of 65mm/s, a setting temperature of 95 ℃, a setting time of 5 seconds, a biaxial stretching ratio of 4X 4, and then a dominant wavelength of 365nm and a strength of 20mW/cm2Then, the film was irradiated for 2 minutes to obtain a thin film having a thickness of 25 μm.
Example 6
100 parts of polylactic acid from example 1, 0.15 part of tris (3-mercaptopropyl) pentapropyl cage octasilsesquioxane, 20 parts of the double-ended allyloxy polyester from example 4 and 3 parts of benzoin bis methyl ether were fed into an extruder, melt-mixed uniformly at 195-Casting into cast sheet with thickness of about 450 μm, biaxially stretching the cast sheet in a biaxial tensile tester at 70 deg.C for 13 s, at 65mm/s, at 95 deg.C for 5 s, at a biaxial stretching magnification of 4 × 4, and at a dominant wavelength of 365nm and a strength of 20mW/cm2Then, the film was irradiated for 2 minutes to obtain a thin film having a thickness of 25 μm.
Example 7
Vinyl silicone oil: structural formula SiMe3O(SiOMe2)80.4(SiOMeR4)10.7(SiOMeVi)4.1SiMe3Me is methyl, Vi is vinyl, R4Is gamma- (2, 3-epoxypropoxy) propyl.
100 parts of the polylactic acid of example 1, 0.18 part of octa (3-mercaptopropyl) cage-type octapolysilsesquioxane, 10 parts of the vinyl silicone oil, 0.8 part of antioxidant 1076, 40 parts of glass microspheres with an average particle size of 1.8 mu m, 2 parts of zinc stearate and 4 parts of benzoin butyl ether were fed into an extruder, melt-mixed uniformly at 205 ℃ and 205 ℃, extruded and cast into a cast sheet with a thickness of about 450 mu m at 210 ℃, the cast sheet was biaxially stretched in a biaxial tensile tester at 70 ℃, a preheating time of 15 seconds, a stretching speed of 65mm/s, a setting temperature of 90 ℃, a setting time of 6 seconds and a biaxial stretching ratio of 4X 4, and then the main wavelength of 365nm and a strength of 20mW/cm2Then, the film was irradiated for 3 minutes to obtain a thin film having a thickness of 25 μm.
Example 8
100 parts of the polylactic acid of example 1, 0.18 part of octa (3-mercaptopropyl) cage-type octasilsesquioxane, 16 parts of the vinyl silicone oil of example 7, 0.8 part of antioxidant 1076, 40 parts of glass microspheres with an average particle size of 1.8 μm, 2 parts of zinc stearate and 4 parts of benzoin butyl ether were fed into an extruder, melt-mixed uniformly at 205 ℃ and 205 ℃, extruded and cast into cast sheets with a thickness of about 450 μm at 210 ℃, the cast sheets were biaxially stretched on a biaxial tensile tester at 70 ℃, a preheating time of 15 seconds, a stretching speed of 65mm/s, a setting temperature of 90 ℃, a setting time of 6 seconds, a biaxial stretching magnification of 4 × 4, and then a dominant wavelength of 365nm and a strength of 20mW/cm2Then, the film was irradiated for 3 minutes to obtain a thin film having a thickness of 25 μm.
Example 9
100 parts of the polylactic acid of example 1, 0.18 part of octa (3-mercaptopropyl) cage-type octasilsesquioxane, 23 parts of the vinyl silicone oil of example 7, 0.8 part of antioxidant 1076, 40 parts of glass microspheres with an average particle size of 1.8 μm, 2 parts of zinc stearate and 4 parts of benzoin butyl ether were fed into an extruder, melt-mixed uniformly at 205 ℃ and 205 ℃, extruded and cast into cast sheets with a thickness of about 450 μm at 210 ℃, the cast sheets were biaxially stretched on a biaxial tensile tester at 70 ℃, a preheating time of 15 seconds, a stretching speed of 65mm/s, a setting temperature of 90 ℃, a setting time of 6 seconds, a biaxial stretching magnification of 4 × 4, and then a dominant wavelength of 365nm and a strength of 20mW/cm2Then, the film was irradiated for 3 minutes to obtain a thin film having a thickness of 25 μm.
Comparative example 1
100 parts of the polylactic acid of example 1 and 0.01 part of octa (3-mercaptopropyl) cage-type octasilsesquioxane were fed into an extruder, melt-mixed uniformly at 195-200 ℃ and extruded and cast into a cast sheet having a thickness of about 450 μm at 205 ℃, the cast sheet was biaxially stretched in a biaxial tensile tester at a temperature of 65 ℃, a preheating time of 12 seconds, a stretching speed of 60mm/s, a setting temperature of 110 ℃, a setting time of 5 seconds and a biaxial stretching magnification of 4X 4 to obtain a film having a thickness of 25 μm.
Comparative example 2
In comparative example 1, 0.15 part of octa (3-mercaptopropyl) cage-type octapolysilsesquioxane was changed, and the remaining steps were kept unchanged.
Comparative example 3
100 parts of polylactic acid in example 1 and 20 parts of double-ended allyloxy polyether in example 1 were fed into an extruder, melt-mixed uniformly at 195-plus-200 ℃, extruded and cast into a cast sheet having a thickness of about 450 μm at 205 ℃, the cast sheet was biaxially stretched in a biaxial tensile tester at a temperature of 65 ℃, a preheating time of 12 seconds, a stretching speed of 60mm/s, a setting temperature of 110 ℃, a setting time of 5 seconds and a biaxial stretching magnification of 4X 4, and then the main wavelength of 365nm and the strength of 20mW/cm were applied2Then, the film was irradiated for 2 minutes to obtain a thin film having a thickness of 25 μm.
Comparative example 4
100 parts of polylactic acid in example 1, 0.25 part of octa (3-mercaptopropyl) cage-type octapolysilsesquioxane, and 20 parts of polylactic acidThe double-ended allyloxy polyether of example 1 was fed into an extruder, extruded at 205 ℃ and cast into a cast sheet having a thickness of about 450 μm, the cast sheet was biaxially stretched in a biaxial tensile tester at 65 ℃ for 12 seconds at a stretching speed of 60mm/s, at a setting temperature of 110 ℃ for 5 seconds at a biaxial stretching magnification of 4X 4, and then the dominant wavelength was 365nm and the intensity was 20mW/cm2Then, the film was irradiated for 2 minutes to obtain a thin film having a thickness of 25 μm.
Comparative example 5
100 parts of polylactic acid according to example 1, 0.003 part of octa (3-mercaptopropyl) cage-type octapolysilsesquioxane, 16 parts of vinyl silicone oil according to example 7, 0.8 part of antioxidant 1076, 40 parts of glass microspheres with an average particle size of 1.8 mu m, and 2 parts of zinc stearate are fed into an extruder, melt-mixed uniformly at 205 ℃ and 205 ℃, extruded at 210 ℃ and cast into a cast sheet with a thickness of about 450 mu m, the cast sheet is biaxially stretched on a biaxial tensile tester at a temperature of 70 ℃, a preheating time of 15 seconds, a stretching speed of 65mm/s, a setting temperature of 90 ℃, a setting time of 6 seconds and a biaxial stretching magnification of 4X 4, and then the polylactic acid with a dominant wavelength of 365nm and a strength of 20mW/cm2Then, the film was irradiated for 3 minutes to obtain a thin film having a thickness of 25 μm.
Comparative example 6
In comparative example 5, 0.28 part of octa (3-mercaptopropyl) cage-type octapolysilsesquioxane was changed, and the remaining steps were kept 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 results of performance testing
Figure BDA0003487995510000081
Figure BDA0003487995510000091
Therefore, the data results in table 1 show that the ultraviolet irradiation crosslinking reaction of the thiolated cage polysilsesquioxane and the terminal vinyl compound or the side vinyl compound, such as the terminal allyloxy polyether, the terminal allyloxy polyester and the vinyl silicone oil, improves the puncture resistance of the polylactic acid film, has little influence on the tensile strength, and can maintain the tensile strength at a better performance than that of a simple toughening agent.
The foregoing has shown and described the fundamental principles, principal features and advantages of the invention. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are merely preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and that equivalent changes and modifications made within the scope of the present invention and the specification should be covered thereby. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. The processing method of the degradable packaging film is characterized in that 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 average relative molecular mass of the terminal vinyl 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, melting and uniformly mixing, extruding, casting to form a film, stretching in two directions, and irradiating for 0.5-10 minutes by ultraviolet light.
2. The process of claim 1, wherein the polylactic acid has a number average molecular weight of not less than 5 ten thousand.
3. The method of claim 1, wherein said thiolated cage polysilsesquioxane has the general structural formula R1 aR2 b(SiO1.5)nWherein R is1Selected from C1-C6 alkyl or non-mercapto substituted alkyl, R2Is 3-mercaptopropyl, 0 ≤ a ≤ 6, a + b ═ n, n ═ 6, 8, 10, or 12.
4. The method of claim 1, wherein a is 0. ltoreq. a.ltoreq.5 and n is 8.
5. The process of claim 1, wherein the vinyl-terminated compound is selected from a double-terminal allyloxy polyether or a double-terminal allyloxy polyester.
6. The process of claim 1, said pendant vinyl compound being selected from vinyl silicone oils having the general structural formula R3SiMe2O(SiOMe2)e(SiOMeR4)f(SiOMeVi)gSiMe2R3Wherein R is3Selected from methyl, vinyl or hydroxy, R4Selected from C1-C18 alkyl or substituted alkyl or phenyl, Me represents methyl, Vi represents vinyl, g is more than or equal to 1 and less than or equal to 10, e is more than or equal to 0, and f is more than or equal to 0;
the viscosity of the vinyl silicone oil at 25 ℃ is 200-5000mPa.
7. The process of claim 1 wherein the temperature of said extrusion is 180-230 ℃.
8. The process of claim 1, wherein the biaxial stretching is carried out at a ratio of 2 to 6 times in the longitudinal direction and 2 to 6 times in the transverse direction.
9. The process of claim 1, said degradable packaging film further comprising at least one of an antioxidant, a processing aid, a filler and a pigment.
10. A degradable packaging film obtained by the process according to any one of claims 1 to 9.
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