CN111363327A - High-strength polylactic acid packaging bag and preparation method thereof - Google Patents
High-strength polylactic acid packaging bag and preparation method thereof Download PDFInfo
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- CN111363327A CN111363327A CN202010375614.3A CN202010375614A CN111363327A CN 111363327 A CN111363327 A CN 111363327A CN 202010375614 A CN202010375614 A CN 202010375614A CN 111363327 A CN111363327 A CN 111363327A
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 116
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 116
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 146
- 238000002156 mixing Methods 0.000 claims abstract description 85
- -1 polysiloxane Polymers 0.000 claims abstract description 65
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 56
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229940045870 sodium palmitate Drugs 0.000 claims abstract description 23
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 claims abstract description 23
- 229920002472 Starch Polymers 0.000 claims abstract description 20
- 239000008107 starch Substances 0.000 claims abstract description 20
- 235000019698 starch Nutrition 0.000 claims abstract description 20
- JNYUEHVKLOZOHU-UHFFFAOYSA-N diethoxy-[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(O[SiH](OCC)OCC)C JNYUEHVKLOZOHU-UHFFFAOYSA-N 0.000 claims abstract description 19
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 17
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 20
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000012065 filter cake Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 229920002261 Corn starch Polymers 0.000 claims description 8
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 239000008120 corn starch Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 4
- ZFSFDELZPURLKD-UHFFFAOYSA-N azanium;hydroxide;hydrate Chemical compound N.O.O ZFSFDELZPURLKD-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- 238000005457 optimization Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Abstract
The invention discloses a high-strength polylactic acid packaging bag and a preparation method thereof, and relates to the technical field of high polymer materials. The preparation method comprises the steps of preparing modified polysiloxane from dimethyl triethoxysilane and gamma-methacryloxypropyl methyldimethoxysilane under the catalysis of tetramethylammonium hydroxide, coating calcium carbonate whiskers by using gelatinized starch and sodium palmitate, esterifying under the action of acrylic acid to prepare modified calcium carbonate whiskers, mixing the modified polysiloxane with polylactic acid, adding the modified calcium carbonate whiskers, a silane coupling agent KH-550 and nano silicon dioxide to prepare a film forming solution, drying the film forming solution under the condition of ultraviolet light to form a film, removing the film to obtain a blank, and making the blank into a bag in a bag making machine to prepare the high-strength polylactic acid packaging bag. The polylactic acid packaging bag prepared by the invention has excellent mechanical properties.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high-strength polylactic acid packaging bag and a preparation method thereof.
Background
The packing bag is also called as flexible container, and is one kind of flexible transport and packing container widely used in transporting and packing powdered, granular and lumpy food, grain, medicine, chemical, mineral product, etc.
With the entrance of society, people pay more attention to the concept of environmental protection, and nowadays, the white pollution of the environment is serious due to the use of a large amount of non-degradable packaging bags, so the development of degradable packaging bags is particularly important.
Polylactic acid is as novel macromolecular material, because its better degradability has now been used for the preparation of wrapping bag widely, but the polylactic acid wrapping bag mechanical properties that exists on the market at present has certain defect, leads to the practicality of polylactic acid wrapping bag to reduce, therefore how when guaranteeing polylactic acid degradability, improves the mechanical properties of polylactic acid wrapping bag and is a problem that awaits solution urgently.
Disclosure of Invention
The present invention aims to provide a high-strength polylactic acid packaging bag and a preparation method thereof, so as to solve the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme:
a high-strength polylactic acid packaging bag is characterized by mainly comprising the following raw material components in parts by weight: 60-100 parts of polylactic acid, 1-3 parts of modified calcium carbonate whiskers, 4-6 parts of nano silicon dioxide and 3-4 parts of a silane coupling agent KH-550.
The high-strength polylactic acid packaging bag is characterized by further comprising the following raw material components in parts by weight: 2-6 parts of modified polysiloxane and 0.1-1.5 parts of 2-hydroxy-2-methyl-1-phenyl acetone.
Preferably, the modified calcium carbonate crystal whisker is prepared by coating calcium carbonate crystal whisker with starch and sodium palmitate and then performing acrylic esterification
Preferably, the modified polysiloxane is prepared from dimethyl triethoxysilane, gamma-methacryloxypropyl methyldimethoxysilane under the catalysis of tetramethylammonium hydroxide.
As optimization, the high-strength polylactic acid packaging bag mainly comprises the following raw material components in parts by weight: 80 parts of polylactic acid, 3 parts of modified calcium carbonate whiskers, 4 parts of nano silicon dioxide, 4 parts of silane coupling agent KH-550, 3 parts of modified polysiloxane and 0.8 part of 2-hydroxy-2-methyl-1-phenyl acetone.
As optimization, the preparation method of the high-strength polylactic acid packaging bag mainly comprises the following preparation steps:
(1) mixing dimethyl triethoxysilane and gamma-methacryloxypropyl methyldimethoxysilane, adding water and tetramethylammonium hydroxide, performing reflux reaction to obtain a modified polysiloxane blank, and heating the modified polysiloxane blank to obtain modified polysiloxane;
(2) gelatinizing corn starch at high temperature to obtain gelatinized starch dispersion liquid, mixing the gelatinized starch dispersion liquid with sodium palmitate, adding calcium carbonate whiskers, stirring and mixing to obtain a calcium carbonate mixture, pouring the calcium carbonate mixture into an ammonium sulfate solution, and filtering to obtain a filter cake;
(3) mixing acrylic acid and a sodium hydroxide solution, adding the filter cake obtained in the step (2), and stirring for reaction to obtain modified calcium carbonate whiskers;
(4) mixing polylactic acid and dichloromethane, adding nano silicon dioxide, a silane coupling agent KH-550, the modified polysiloxane obtained in the step (1), the modified calcium carbonate whisker obtained in the step (3) and a photoinitiator, and stirring and mixing to obtain a film forming solution;
(5) transferring the film forming solution obtained in the step (4) into a polytetrafluoroethylene template, drying under the condition of ultraviolet light, removing the film to obtain a blank, and making a bag from the blank in a bag making machine to obtain a high-strength polylactic acid packaging bag;
(6) and (5) carrying out index analysis on the high-strength polylactic acid packaging bag obtained in the step (5).
As optimization, the preparation method of the high-strength polylactic acid packaging bag mainly comprises the following preparation steps:
(1) mixing dimethyl triethoxysilane and gamma-methacryloxypropyl methyldimethoxysilane in a mass ratio of 30: 1, mixing the raw materials in a three-neck flask, adding water with the mass of 0.25 time of that of dimethyl triethoxysilane and tetramethyl ammonium hydroxide with the mass of 0.02-0.08 time of that of the dimethyl triethoxysilane into the three-neck flask, performing reflux reaction to obtain a modified polysiloxane blank, heating the modified polysiloxane blank to 150 ℃, and keeping the temperature for 10min to obtain modified polysiloxane;
(2) mixing corn starch and water according to a mass ratio of 3: 100, carrying out high-temperature gelatinization for 1h at the temperature of 95 ℃, adjusting the pH value to 11 to obtain a gelatinized starch dispersion liquid, and mixing the gelatinized starch dispersion liquid and sodium palmitate according to the mass ratio of 30: 1, mixing the calcium carbonate crystal whisker and the sodium palmitate in an amount which is 0.3-0.6 times the mass of the calcium carbonate crystal whisker in the beaker, stirring and mixing the calcium carbonate crystal whisker and the sodium palmitate crystal whisker to obtain a calcium carbonate mixture, pouring the calcium carbonate mixture into an ammonium sulfate solution which is 3-5 times the mass of the calcium carbonate mixture and has a mass fraction of 40%, and filtering the mixture to obtain a filter cake;
(3) mixing acrylic acid with a sodium hydroxide solution with the mass fraction of 5% according to the mass ratio of 1: 20, mixing and mixing, adding a filter cake obtained in the step (2) with the mass of 0.5-1.5 times that of acrylic acid into a mixture of acrylic acid and a sodium hydroxide solution, stirring and reacting for 150min at the temperature of 110 ℃ and the rotating speed of 300r/min, filtering to obtain a modified calcium carbonate whisker blank, and drying the modified calcium carbonate whisker blank for 2h at the temperature of 70 ℃ to obtain the modified calcium carbonate whisker;
(4) mixing polylactic acid and dichloromethane according to a mass ratio of 1: 25, mixing the mixture in a stirrer, adding nano silicon dioxide with the weight of 0.05 time that of the polylactic acid, a silane coupling agent KH-550 with the weight of 0.05 time that of the polylactic acid, modified polysiloxane obtained in the step (1) with the weight of 0.037 time that of the polylactic acid, modified calcium carbonate whiskers obtained in the step (3) with the weight of 0.037 time that of the polylactic acid and a photoinitiator with the weight of 0.01 time that of the polylactic acid into the stirrer, and stirring and mixing to obtain a film forming solution;
(5) transferring the film forming solution obtained in the step (4) into a polytetrafluoroethylene template, placing the polytetrafluoroethylene template under ultraviolet illumination, drying the polytetrafluoroethylene template for 30 hours at the temperature of 40 ℃, removing the film to obtain a blank, and making the blank into a bag in a bag making machine to obtain a high-strength polylactic acid packaging bag;
(6) and (5) carrying out index analysis on the high-strength polylactic acid packaging bag obtained in the step (5).
As an optimization, the reflux reaction condition in the step (1) is firstly to react for 2 hours under the condition of the temperature of 60 ℃, and then to react for 1.5 hours under the condition of the temperature of 95 ℃ and the pressure of-0.8 MPa.
Compared with the prior art, the invention has the beneficial effects that:
the modified polysiloxane and the modified calcium carbonate crystal whisker are added when the high-strength polylactic acid packaging bag is prepared; firstly, polysiloxane is grafted with ester bonds after being modified, and the modified polysiloxane can effectively improve the dispersibility of polysiloxane in polylactic acid after being added into the polylactic acid, secondly, the molecular chain of the modified polysiloxane contains flexible chain segments and can be crosslinked under the action of a photocatalyst, therefore, after the modified polysiloxane is added into the polylactic acid, a crosslinking network can be uniformly formed in a polylactic acid system in the ultraviolet drying process, so as to improve the mechanical property of the product, furthermore, the modified calcium carbonate whisker is also added in the preparation of the polylactic acid packaging bag, the outer side of the calcium carbonate whisker is coated by acrylated starch after being modified, therefore, after being added into the polylactic acid system, the modified calcium carbonate whisker can show good dispersibility, the uniformly dispersed calcium carbonate whisker can promote the good crystallization of the polylactic acid, and, the calcium carbonate whisker can be used as the winding site of polylactic acid macromolecular chains and modified polysiloxane crosslinking networks, thereby further improving the mechanical property of the product.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method of the present invention, the following examples are given, and the method of testing the high-strength polylactic acid packaging bag manufactured in the following examples is as follows:
mechanical properties: the tensile strength of the high-strength polylactic acid packaging bags obtained in the examples and the tensile strength of the comparative products are tested by using a universal tensile testing machine.
Example 1
A high-strength polylactic acid packaging bag mainly comprises the following components in parts by weight: 80 parts of polylactic acid, 3 parts of modified calcium carbonate whiskers, 4 parts of nano silicon dioxide, 4 parts of silane coupling agent KH-550, 3 parts of modified polysiloxane and 0.8 part of 2-hydroxy-2-methyl-1-phenyl acetone.
A preparation method of a high-strength polylactic acid packaging bag mainly comprises the following preparation steps:
(1) mixing dimethyl triethoxysilane and gamma-methacryloxypropyl methyldimethoxysilane in a mass ratio of 30: 1, mixing the raw materials in a three-neck flask, adding water with the mass of 0.25 time of that of dimethyl triethoxysilane and tetramethyl ammonium hydroxide with the mass of 0.04 time of that of the dimethyl triethoxysilane into the three-neck flask, performing reflux reaction to obtain a modified polysiloxane blank, heating the modified polysiloxane blank to 150 ℃, and keeping the temperature for 10min to obtain modified polysiloxane;
(2) mixing corn starch and water according to a mass ratio of 3: 100, carrying out high-temperature gelatinization for 1h at the temperature of 95 ℃, adjusting the pH value to 11 to obtain a gelatinized starch dispersion liquid, and mixing the gelatinized starch dispersion liquid and sodium palmitate according to the mass ratio of 30: 1, mixing the calcium carbonate crystal whisker and the sodium palmitate in an amount which is 0.3-0.6 times the mass of the calcium carbonate crystal whisker in the beaker, stirring and mixing the calcium carbonate crystal whisker and the sodium palmitate crystal whisker to obtain a calcium carbonate mixture, pouring the calcium carbonate mixture into an ammonium sulfate solution which is 4 times the mass of the calcium carbonate mixture and has a mass fraction of 40%, stirring and mixing the mixture for 30min at the temperature of 30 ℃ and the rotating speed of 400r/min, and filtering the mixture to obtain a filter cake;
(3) mixing acrylic acid with a sodium hydroxide solution with the mass fraction of 5% according to the mass ratio of 1: 20, mixing and mixing, adding a filter cake obtained in the step (2) with the mass of 0.8 time of that of acrylic acid into a mixture of acrylic acid and a sodium hydroxide solution, stirring and reacting for 150min at the temperature of 110 ℃ and the rotating speed of 300r/min, filtering to obtain a modified calcium carbonate whisker blank, and drying the modified calcium carbonate whisker blank for 2h at the temperature of 70 ℃ to obtain the modified calcium carbonate whisker;
(4) mixing polylactic acid and dichloromethane according to a mass ratio of 1: 25, mixing the mixture in a stirrer, adding nano silicon dioxide with the weight of 0.05 time that of the polylactic acid, a silane coupling agent KH-550 with the weight of 0.05 time that of the polylactic acid, modified polysiloxane obtained in the step (1) with the weight of 0.037 time that of the polylactic acid, modified calcium carbonate whiskers obtained in the step (3) with the weight of 0.037 time that of the polylactic acid and a photoinitiator with the weight of 0.01 time that of the polylactic acid into the stirrer, and stirring and mixing the materials for 25 minutes under the condition that the rotating speed is 350r/min to obtain a film forming solution;
(5) transferring the film forming solution obtained in the step (4) into a polytetrafluoroethylene template, placing the polytetrafluoroethylene template under ultraviolet illumination, drying the polytetrafluoroethylene template for 30 hours at the temperature of 40 ℃, removing the film to obtain a blank, and making the blank into a bag in a bag making machine to obtain a high-strength polylactic acid packaging bag;
(6) and (5) carrying out index analysis on the high-strength polylactic acid packaging bag obtained in the step (5).
As an optimization, the reflux reaction condition in the step (1) is firstly to react for 2 hours under the condition of the temperature of 60 ℃, and then to react for 1.5 hours under the condition of the temperature of 95 ℃ and the pressure of-0.8 MPa.
Example 2
A high-strength polylactic acid packaging bag mainly comprises the following components in parts by weight: 80 parts of polylactic acid, 3 parts of calcium carbonate whiskers, 4 parts of nano silicon dioxide, 4 parts of silane coupling agent KH-550, 3 parts of modified polysiloxane and 0.8 part of 2-hydroxy-2-methyl-1-phenyl acetone.
A preparation method of a high-strength polylactic acid packaging bag mainly comprises the following preparation steps:
(1) mixing dimethyl triethoxysilane and gamma-methacryloxypropyl methyldimethoxysilane in a mass ratio of 30: 1, mixing the raw materials in a three-neck flask, adding water with the mass of 0.25 time of that of dimethyl triethoxysilane and tetramethyl ammonium hydroxide with the mass of 0.04 time of that of the dimethyl triethoxysilane into the three-neck flask, performing reflux reaction to obtain a modified polysiloxane blank, heating the modified polysiloxane blank to 150 ℃, and keeping the temperature for 10min to obtain modified polysiloxane;
(2) mixing corn starch and water according to a mass ratio of 3: 100, carrying out high-temperature gelatinization for 1h at the temperature of 95 ℃, adjusting the pH value to 11 to obtain a gelatinized starch dispersion liquid, and mixing the gelatinized starch dispersion liquid and sodium palmitate according to the mass ratio of 30: 1, mixing the calcium carbonate whisker and the sodium palmitate in an amount which is 0.3-0.6 times the mass of the calcium carbonate whisker in the beaker, stirring and mixing the calcium carbonate whisker and the sodium palmitate to obtain a calcium carbonate mixture, pouring the calcium carbonate mixture into an ammonium sulfate solution which is 4 times the mass of the calcium carbonate mixture and has a mass fraction of 40%, stirring and mixing the mixture for 30min at the temperature of 30 ℃ and the rotating speed of 400r/min, and filtering the mixture to obtain the calcium carbonate whisker;
(3) mixing polylactic acid and dichloromethane according to a mass ratio of 1: 25, mixing the mixture in a stirrer, adding nano silicon dioxide which is 0.05 time of the mass of the polylactic acid, a silane coupling agent KH-550 which is 0.05 time of the mass of the polylactic acid, modified polysiloxane which is 0.037 times of the mass of the polylactic acid and is obtained in the step (1), calcium carbonate whiskers which are 0.037 times of the mass of the polylactic acid and is obtained in the step (2) and a photoinitiator which is 0.01 time of the mass of the polylactic acid into the stirrer, and stirring and mixing the materials for 25 minutes under the condition that the rotating speed is 350r/min to obtain a film forming solution;
(4) transferring the film forming solution obtained in the step (3) into a polytetrafluoroethylene template, placing the polytetrafluoroethylene template under ultraviolet illumination, drying the polytetrafluoroethylene template for 30 hours at the temperature of 40 ℃, removing the film to obtain a blank, and making the blank into a bag in a bag making machine to obtain a high-strength polylactic acid packaging bag;
(5) and (4) carrying out index analysis on the high-strength polylactic acid packaging bag obtained in the step (4).
As an optimization, the reflux reaction condition in the step (1) is firstly to react for 2 hours under the condition of the temperature of 60 ℃, and then to react for 1.5 hours under the condition of the temperature of 95 ℃ and the pressure of-0.8 MPa.
Example 3
A high-strength polylactic acid packaging bag mainly comprises the following components in parts by weight: 80 parts of polylactic acid, 3 parts of modified calcium carbonate whiskers, 4 parts of nano silicon dioxide, 4 parts of silane coupling agent KH-550, 3 parts of mixed siloxane and 0.8 part of 2-hydroxy-2-methyl-1-phenyl acetone.
A preparation method of a high-strength polylactic acid packaging bag mainly comprises the following preparation steps:
(1) mixing dimethyl triethoxysilane and gamma-methacryloxypropyl methyldimethoxysilane in a mass ratio of 30: 1, mixing the mixture in a three-neck flask, stirring and mixing for 40min under the conditions that the temperature is 60 ℃ and the rotating speed is 350r/min, and obtaining modified polysiloxane;
(2) mixing corn starch and water according to a mass ratio of 3: 100, carrying out high-temperature gelatinization for 1h at the temperature of 95 ℃, adjusting the pH value to 11 to obtain a gelatinized starch dispersion liquid, and mixing the gelatinized starch dispersion liquid and sodium palmitate according to the mass ratio of 30: 1, mixing the calcium carbonate crystal whisker and the sodium palmitate in an amount which is 0.3-0.6 times the mass of the calcium carbonate crystal whisker in the beaker, stirring and mixing the calcium carbonate crystal whisker and the sodium palmitate crystal whisker to obtain a calcium carbonate mixture, pouring the calcium carbonate mixture into an ammonium sulfate solution which is 4 times the mass of the calcium carbonate mixture and has a mass fraction of 40%, stirring and mixing the mixture for 30min at the temperature of 30 ℃ and the rotating speed of 400r/min, and filtering the mixture to obtain a filter cake;
(3) mixing acrylic acid with a sodium hydroxide solution with the mass fraction of 5% according to the mass ratio of 1: 20, mixing and mixing, adding a filter cake obtained in the step (2) with the mass of 0.8 time of that of acrylic acid into a mixture of acrylic acid and a sodium hydroxide solution, stirring and reacting for 150min at the temperature of 110 ℃ and the rotating speed of 300r/min, filtering to obtain a modified calcium carbonate whisker blank, and drying the modified calcium carbonate whisker blank for 2h at the temperature of 70 ℃ to obtain the modified calcium carbonate whisker;
(4) mixing polylactic acid and dichloromethane according to a mass ratio of 1: 25, mixing the mixture in a stirrer, adding nano silicon dioxide which is 0.05 time of the mass of the polylactic acid, a silane coupling agent KH-550 which is 0.05 time of the mass of the polylactic acid, mixed siloxane which is 0.037 times of the mass of the polylactic acid and is obtained in the step (1), modified calcium carbonate whiskers which are 0.037 times of the mass of the polylactic acid and a photoinitiator which is 0.01 time of the mass of the polylactic acid into the stirrer, and stirring and mixing the materials for 25min under the condition that the rotating speed is 350r/min to obtain a film forming solution;
(5) transferring the film forming solution obtained in the step (4) into a polytetrafluoroethylene template, placing the polytetrafluoroethylene template under ultraviolet illumination, drying the polytetrafluoroethylene template for 30 hours at the temperature of 40 ℃, removing the film to obtain a blank, and making the blank into a bag in a bag making machine to obtain a high-strength polylactic acid packaging bag;
(6) and (5) carrying out index analysis on the high-strength polylactic acid packaging bag obtained in the step (5).
Comparative example
A high-strength polylactic acid packaging bag mainly comprises the following components in parts by weight: 80 parts of polylactic acid, 3 parts of calcium carbonate whiskers, 4 parts of nano silicon dioxide, 4 parts of silane coupling agent KH-550, 3 parts of mixed siloxane and 0.8 part of 2-hydroxy-2-methyl-1-phenyl acetone.
A preparation method of a high-strength polylactic acid packaging bag mainly comprises the following preparation steps:
(1) mixing dimethyl triethoxysilane and gamma-methacryloxypropyl methyldimethoxysilane in a mass ratio of 30: 1, mixing the mixture in a three-neck flask, stirring and mixing for 40min under the conditions that the temperature is 60 ℃ and the rotating speed is 350r/min, and obtaining modified polysiloxane;
(2) mixing corn starch and water according to a mass ratio of 3: 100, carrying out high-temperature gelatinization for 1h at the temperature of 95 ℃, adjusting the pH value to 11 to obtain a gelatinized starch dispersion liquid, and mixing the gelatinized starch dispersion liquid and sodium palmitate according to the mass ratio of 30: 1, mixing the calcium carbonate whisker and the sodium palmitate in an amount which is 0.3-0.6 times the mass of the calcium carbonate whisker in the beaker, stirring and mixing the calcium carbonate whisker and the sodium palmitate to obtain a calcium carbonate mixture, pouring the calcium carbonate mixture into an ammonium sulfate solution which is 4 times the mass of the calcium carbonate mixture and has a mass fraction of 40%, stirring and mixing the mixture for 30min at the temperature of 30 ℃ and the rotating speed of 400r/min, and filtering the mixture to obtain the calcium carbonate whisker;
(3) mixing polylactic acid and dichloromethane according to a mass ratio of 1: 25, mixing the mixture in a stirrer, adding nano silicon dioxide which is 0.05 time of the mass of the polylactic acid, a silane coupling agent KH-550 which is 0.05 time of the mass of the polylactic acid, mixed siloxane which is 0.037 times of the mass of the polylactic acid and is obtained in the step (1), calcium carbonate whiskers which are 0.037 times of the mass of the polylactic acid and is obtained in the step (2) and a photoinitiator which is 0.01 time of the mass of the polylactic acid into the stirrer, and stirring and mixing the materials for 25 minutes under the condition that the rotating speed is 350r/min to obtain a film forming solution;
(4) transferring the film forming solution obtained in the step (3) into a polytetrafluoroethylene template, placing the polytetrafluoroethylene template under ultraviolet illumination, drying the polytetrafluoroethylene template for 30 hours at the temperature of 40 ℃, removing the film to obtain a blank, and making the blank into a bag in a bag making machine to obtain a high-strength polylactic acid packaging bag;
(5) and (4) carrying out index analysis on the high-strength polylactic acid packaging bag obtained in the step (4).
Examples of effects
Table 1 below shows the results of performance analysis of the high-strength polylactic acid packaging bags using examples 1 to 3 according to the present invention and a comparative example.
TABLE 1
From the comparison of the experimental data of example 1 and the comparative example in table 1, it can be found that the tensile strength of the product can be effectively improved by adding the modified calcium carbonate whiskers and the modified polysiloxane when preparing the high-strength polylactic acid packaging bag, and from the comparison of the experimental data of example 1 and example 2, when preparing the high-strength polylactic acid packaging bag, the calcium carbonate whiskers are not treated, and cannot be uniformly dispersed after being added into the polylactic acid, so that the calcium carbonate whiskers cannot play a role of winding sites of polylactic acid macromolecular chains and a modified polysiloxane crosslinking network, and therefore, the mechanical properties of the polylactic acid packaging bag are greatly reduced; from the comparison of the experimental data of example 1 and example 3, it can be seen that when only the mixed siloxane is added to prepare the high-strength polylactic acid packaging bag, the mixed siloxane has poor dispersibility in the polylactic acid and cannot form an effective cross-linked network under ultraviolet light, so that the mechanical properties of the polylactic acid packaging bag are seriously reduced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (8)
1. A high-strength polylactic acid packaging bag is characterized by mainly comprising the following raw material components in parts by weight: 60-100 parts of polylactic acid, 1-3 parts of modified calcium carbonate whiskers, 4-6 parts of nano silicon dioxide and 3-4 parts of a silane coupling agent KH-550.
2. The high-strength polylactic acid packaging bag according to claim 1, further comprising the following raw material components in parts by weight: 2-6 parts of modified polysiloxane and 0.1-1.5 parts of 2-hydroxy-2-methyl-1-phenyl acetone.
3. The high-strength polylactic acid packaging bag according to claim 2, wherein the modified calcium carbonate whiskers are prepared by coating calcium carbonate whiskers with starch and sodium palmitate and then performing acrylation.
4. The high-strength polylactic acid packing bag according to claim 3, wherein the modified polysiloxane is prepared from dimethyl triethoxysilane, gamma-methacryloxypropyl methyldimethoxysilane under the catalysis of tetramethyl ammonium hydroxide.
5. The high-strength polylactic acid packaging bag according to claim 4, which is characterized by mainly comprising the following raw material components in parts by weight: 80 parts of polylactic acid, 3 parts of modified calcium carbonate whiskers, 4 parts of nano silicon dioxide, 4 parts of silane coupling agent KH-550, 3 parts of modified polysiloxane and 0.8 part of 2-hydroxy-2-methyl-1-phenyl acetone.
6. A preparation method of a high-strength polylactic acid packaging bag is characterized by mainly comprising the following preparation steps:
(1) mixing dimethyl triethoxysilane and gamma-methacryloxypropyl methyldimethoxysilane, adding water and tetramethylammonium hydroxide, performing reflux reaction to obtain a modified polysiloxane blank, and heating the modified polysiloxane blank to obtain modified polysiloxane;
(2) gelatinizing corn starch at high temperature to obtain gelatinized starch dispersion liquid, mixing the gelatinized starch dispersion liquid with sodium palmitate, adding calcium carbonate whiskers, stirring and mixing to obtain a calcium carbonate mixture, pouring the calcium carbonate mixture into an ammonium sulfate solution, and filtering to obtain a filter cake;
(3) mixing acrylic acid and a sodium hydroxide solution, adding the filter cake obtained in the step (2), and stirring for reaction to obtain modified calcium carbonate whiskers;
(4) mixing polylactic acid and dichloromethane, adding nano silicon dioxide, a silane coupling agent KH-550, the modified polysiloxane obtained in the step (1), the modified calcium carbonate whisker obtained in the step (3) and a photoinitiator, and stirring and mixing to obtain a film forming solution;
(5) transferring the film forming solution obtained in the step (4) into a polytetrafluoroethylene template, drying under the condition of ultraviolet light, removing the film to obtain a blank, and making a bag from the blank in a bag making machine to obtain a high-strength polylactic acid packaging bag;
(6) and (5) carrying out index analysis on the high-strength polylactic acid packaging bag obtained in the step (5).
7. The preparation method of the high-strength polylactic acid packaging bag according to claim 6, which is characterized by mainly comprising the following preparation steps:
(1) mixing dimethyl triethoxysilane and gamma-methacryloxypropyl methyldimethoxysilane in a mass ratio of 30: 1, mixing the raw materials in a three-neck flask, adding water with the mass of 0.25 time of that of dimethyl triethoxysilane and tetramethyl ammonium hydroxide with the mass of 0.02-0.08 time of that of the dimethyl triethoxysilane into the three-neck flask, performing reflux reaction to obtain a modified polysiloxane blank, heating the modified polysiloxane blank to 150 ℃, and keeping the temperature for 10min to obtain modified polysiloxane;
(2) mixing corn starch and water according to a mass ratio of 3: 100, carrying out high-temperature gelatinization for 1h at the temperature of 95 ℃, adjusting the pH value to 11 to obtain a gelatinized starch dispersion liquid, and mixing the gelatinized starch dispersion liquid and sodium palmitate according to the mass ratio of 30: 1, mixing the calcium carbonate crystal whisker and the sodium palmitate in an amount which is 0.3-0.6 times the mass of the calcium carbonate crystal whisker in the beaker, stirring and mixing the calcium carbonate crystal whisker and the sodium palmitate crystal whisker to obtain a calcium carbonate mixture, pouring the calcium carbonate mixture into an ammonium sulfate solution which is 3-5 times the mass of the calcium carbonate mixture and has a mass fraction of 40%, and filtering the mixture to obtain a filter cake;
(3) mixing acrylic acid with a sodium hydroxide solution with the mass fraction of 5% according to the mass ratio of 1: 20, mixing and mixing, adding a filter cake obtained in the step (2) with the mass of 0.5-1.5 times that of acrylic acid into a mixture of acrylic acid and a sodium hydroxide solution, stirring and reacting for 150min at the temperature of 110 ℃ and the rotating speed of 300r/min, filtering to obtain a modified calcium carbonate whisker blank, and drying the modified calcium carbonate whisker blank for 2h at the temperature of 70 ℃ to obtain the modified calcium carbonate whisker;
(4) mixing polylactic acid and dichloromethane according to a mass ratio of 1: 25, mixing the mixture in a stirrer, adding nano silicon dioxide with the weight of 0.05 time that of the polylactic acid, a silane coupling agent KH-550 with the weight of 0.05 time that of the polylactic acid, modified polysiloxane obtained in the step (1) with the weight of 0.037 time that of the polylactic acid, modified calcium carbonate whiskers obtained in the step (3) with the weight of 0.037 time that of the polylactic acid and a photoinitiator with the weight of 0.01 time that of the polylactic acid into the stirrer, and stirring and mixing to obtain a film forming solution;
(5) transferring the film forming solution obtained in the step (4) into a polytetrafluoroethylene template, placing the polytetrafluoroethylene template under ultraviolet illumination, drying the polytetrafluoroethylene template for 30 hours at the temperature of 40 ℃, removing the film to obtain a blank, and making the blank into a bag in a bag making machine to obtain a high-strength polylactic acid packaging bag;
(6) and (5) carrying out index analysis on the high-strength polylactic acid packaging bag obtained in the step (5).
8. The method for preparing a fresh-keeping polylactic acid packaging bag according to claim 5, wherein the reflux reaction condition in the step (1) is that the reaction is performed for 2 hours at a temperature of 60 ℃ and for 1.5 hours at a temperature of 95 ℃ and under a pressure of-0.8 MPa.
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| CN113185825A (en) * | 2021-06-05 | 2021-07-30 | 韩群 | Tear-resistant and degradable polylactic acid food packaging film and preparation method thereof |
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