TW202332565A - Preparation method of cellulose bio-based material and high-barrier full-biodegradable packaging bottle containing cellulose bio-based material - Google Patents

Abstract

The invention belongs to the technical field of degradable packaging bottle processing. The invention provides a preparation method of a cellulose bio-based material, and the cellulose bio-based material is prepared from the following raw material components in parts by weight: 50 to 100 parts of nitrided lignocellulose, 60 to 90 parts of nano cellulose, 20 to 30 parts of polyvinyl alcohol, 5 to 10 parts of chitosan, 3 to 5 parts of methyl cellulose, 0.5 to 1.0 part of a de-foaming agent, 2 to 3 parts of a plasticizer, 10 to 15 parts of glycerol, 0.1 to 0.2 part of a heat stabilizer and 0.1 to 1 part of a mildew preventive. And 0-30 parts of water. The invention also comprises a preparation method of the cellulose bio-based material and a packaging bottle prepared from the material. The packaging bottle prepared by the invention has mildew-proof, antibacterial, heat-resistant, high-barrier and full-degradable properties.

Description

Preparation method of cellulose bio-based material and high-barrier fully biodegradable packaging bottle containing the material

The invention belongs to the technical field of degradable packaging bottle processing, and specifically relates to a preparation method of cellulose bio-based material and a high-barrier fully biodegradable packaging bottle containing the material.

Most of the current packaging bottles use polyethylene and polyester as raw materials. These packaging bottles have differences in gas permeability barrier properties and humidity barrier properties, and the barrier properties of air permeability and oxygen permeability need to be further improved. ; However, when people are studying how to reduce air permeability and oxygen permeability, they use a large amount of non-degradable biological materials. If people throw them away randomly, it will cause environmental pollution and affect the urban landscape. Random disposal and difficulty in degradation are the main causes of white pollution. White pollution is not only visual, but also puts pressure on the environment and the high cost of its treatment, which is not conducive to sustainable development.

Biodegradable plastic refers to the use of temperature, humidity, minerals and microorganisms (such as bacteria, fungi, algae, etc.) in the environment to hydrolyze or enzymatically decompose polymer materials into low molecular substances, which are then completely decomposed by microorganisms. and residues do no harm to the environment, which has attracted great attention. Countries around the world are competing to develop biodegradable plastics. There are many biodegradable plastics discovered so far, but all of them have more or less defects that greatly limit their large-scale application as single materials. Blending and modifying biodegradable materials, selecting biodegradable material components with suitable properties, adjusting the ratio of biodegradable material components, improving the compatibility between biodegradable materials and adopting appropriate material processing methods, between various biodegradable materials Learning from each other's strengths and compensating for weaknesses to develop high-performance packaging bottles is currently a hot research issue in the field of packaging bottles.

The object of the present invention is to provide a method for preparing a cellulose-based bio-based material and a high-barrier fully biodegradable packaging bottle containing the material. The main components of the cellulose-based bio-based material can all be fully biodegraded. The prepared packaging bottle , has the advantages of being mildew-proof, antibacterial, heat-resistant, high-barrier, and basically fully biodegradable.

In order to achieve the above purpose, the present invention provides a method for preparing a cellulose-based bio-based material. The raw material components of the cellulose-based bio-based material are composed of the following proportions in parts by weight: 50 to 100 parts of nitrogenated lignocellulose, 60~90 parts of cellulose, 20~30 parts of polyvinyl alcohol, 5~10 parts of chitosan, 3~5 parts of methylcellulose, 0.5~1.0 parts of defoaming agent, 2~3 parts of plasticizer, 10 parts of glycerin ~15 parts, heat stabilizer 0.1~0.2 parts, antifungal agent 0.1~1 part, water 0~30 parts. The preparation method of the above-mentioned cellulose bio-based material includes the following steps:

(1) Add the above weight portions of nitrogenated lignocellulose, nanocellulose, polyvinyl alcohol and chitosan to a high-speed mixer in sequence and stir for 1 to 3 hours until evenly mixed;

(2) Add the above weight portions of methylcellulose, defoaming agent, plasticizer, glycerin, heat stabilizer, antifungal agent and water to a high-speed mixer in turn and stir for 1 to 3 hours until evenly mixed;

(3) After decolorizing and vacuum dehydrating the mixture obtained in steps (1) and (2), add it to a high-speed mixer and stir for 1 to 2 hours. After mixing evenly, heat press it with a flat plate at 80 to 130°C for 2 to After 6 hours, cellulosic bio-based materials were obtained.

Further, the preparation method of the above-mentioned nitrogenated lignocellulose includes the following steps:

(1) Select cotton or corn stalks, cut them, remove impurities, crush them, and sift to obtain 210~280 mesh wood powder;

(2) Add 210~280 mesh wood powder into a mixed solution of water and ethanol with a mass ratio of 100:5, keep the temperature between 25℃~40℃, and then stir and grind for 1h-5h to obtain Lignocellulose dispersions;

(3) Add urea to the lignocellulose dispersion, heat to 65-74°C, stir evenly, then add peracetic acid or amide percarbonate, continue stirring for 2 hours, then filter, wash, and dry to constant temperature. Heavy to obtain nitrogenated lignocellulose.

Further, the above-mentioned antifungal agent is at least one of citric acid, camphor essential oil and Mengzong bamboo extract.

Further, the above-mentioned antifungal agent is an extract of Mengzong bamboo.

Further, the preparation method of the above-mentioned nanocellulose includes the following steps:

(1) Select cotton or corn stems to cut, remove impurities, crush and sieve to obtain 210~280 mesh wood powder;

(2) Mix wood powder with sulfuric acid with a mass percentage of 62~65%, stir evenly, and obtain a wood powder sulfuric acid mixture;

(3) Pretreat the mixed solution obtained in step (2) in a light wave reactor at a reaction temperature of 60°C and a treatment time of 30 minutes;

(4) Add 5% calcium chloride solution to the reaction mixed liquid pretreated by light waves at 65~70°C, and hydrolyze it for 2 hours;

(5) Centrifuge, filter and wash the hydrolyzed mixed liquid;

(6) After vacuum drying the washed solid, use ultrasonic pulverization and sieving to obtain nanocellulose.

Further, the above-mentioned defoaming agent is polydimethylsiloxane, the plasticizer is epoxidized soybean oil, and the heat stabilizer is triphenyl phosphate.

By using the above-mentioned raw material optimization, the main components of the cellulose bio-based material of the present invention are a specific proportion of nitrogenated lignocellulose, nanocellulose, polyvinyl alcohol and chitosan, which are basically fully biodegradable. The unique preparation process is invented to induce the rearrangement of cellulose molecular chains, making the combination of each component closer, promoting the formation of dense nanofibers between the cellulose grid structures, and blocking the penetration of air and moisture; and the products prepared by the invention Cellulosic bio-based materials can basically be completely biodegraded, and their green and environmental protection properties are significantly improved. By adding heat stabilizers, the heat-resistant temperature of the packaging bottles of the present invention can be increased to above 120°C; by adding antifungal agents, the heat-resistant temperature of the packaging bottles of the present invention can be improved. The anti-mildew and anti-bacterial performance is significantly improved, and the anti-mildew levels are all 0 or 1.

The invention also provides a high-barrier fully biodegradable packaging bottle prepared by using the above-mentioned cellulose bio-based material, and its preparation method includes the following steps:

(1) The above-mentioned cellulosic bio-based materials are decompressed and degassed in a storage silo for 1-2 hours, and then extruded using extrusion equipment to obtain masterbatch;

(2) After extruding or injection molding the masterbatch obtained in step (1), a tubular parison is obtained, which is heated or heated to a softened state, and then blow molded and placed in a closed mold;

(3) The mold is closed and cooled to shape. After the mold is opened, the finished product enters the auxiliary mold, and the edges are cut in the auxiliary mold to produce a packaging bottle.

Due to the excellent properties of the raw materials and the advanced preparation process, the packaging bottles prepared by the present invention have the properties of mildew-proof, antibacterial, heat-resistant and high barrier properties, and the packaging bottles after use can be almost completely degraded to form Small molecules, and decompose to form carbon dioxide and water under the combined action of light, oxygen and microorganisms, which greatly reduces the pollution to the environment and is beneficial to Improve biocompatibility.

The packaging bottle of the present invention can be widely used in chemical industry, cosmetics, food, medicine and other fields.

The technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention. It should be understood that the specific embodiments described here are only used to explain the present invention and are not intended to limit the present invention.

Example 1

A method for preparing cellulose-based bio-based materials. The raw material components of the cellulose-based bio-based materials are composed of the following proportions in parts by weight: 50 parts of nitrogenated lignocellulose, 60 parts of nanocellulose, and 20 parts of polyvinyl alcohol. 5 parts of chitosan, 3 parts of methylcellulose, 0.5 parts of polydimethylsiloxane, 2 parts of epoxidized soybean oil, 10 parts of glycerin, 0.1 part of triphenyl phosphate, and 0.1 part of citric acid.

The preparation method of the above-mentioned cellulose bio-based material includes the following steps:

(1) Add the above weight portions of nitrogenated lignocellulose, nanocellulose, polyvinyl alcohol and chitosan to a high-speed mixer in sequence and stir for 1 hour until evenly mixed;

(2) Add the above weight parts of methylcellulose, defoaming agent, plasticizer, glycerin, heat stabilizer and antifungal agent to a high-speed mixer in sequence and stir for 1 hour until evenly mixed;

(3) After decolorizing and vacuum dehydrating the mixture obtained in steps (1) and (2), add it to a high-speed mixer and stir for 1 to 2 hours. After mixing evenly, heat press it with a flat plate at 80 to 130°C for 2 to After 6 hours, cellulosic bio-based materials were obtained.

The preparation method of the above-mentioned nitrogenated lignocellulose includes the following steps:

(1) Select cotton or corn stems to cut, remove impurities, crush and sieve to obtain 210~280 mesh wood powder;

(2) Add 210~280 mesh wood powder to a mixed solution of water and ethanol with a mass ratio of 100:5, keep the temperature between 25~30°C, and then stir and grind for 1 hour to obtain lignocellulose Dispersions;

(3) Add urea to the lignocellulose dispersion, heat to 65-70°C, stir evenly, then add peracetic acid, continue stirring for 2 hours, then filter, wash, and dry to constant weight to obtain nitrided Lignocellulose.

The preparation method of the above-mentioned nanocellulose includes the following steps:

(1) Select cotton or corn stems to cut, remove impurities, crush and sieve to obtain 210~280 mesh wood powder;

(2) Mix wood powder with sulfuric acid with a mass percentage of 62~65%, stir evenly, and obtain a wood powder sulfuric acid mixture;

(3) Pretreat the mixed solution obtained in step (2) in a light wave reactor at a reaction temperature of 60°C and a treatment time of 30 minutes;

(4) Add 5% calcium chloride solution to the reaction mixed liquid pretreated by light waves at 65~70°C, and hydrolyze it for 2 hours;

(5) Centrifuge, filter and wash the hydrolyzed mixed liquid;

(6) After vacuum drying the washed solid, use ultrasonic pulverization and sieving to obtain nanocellulose.

Packaging bottles prepared using the above-mentioned cellulosic bio-based materials, the preparation method includes Includes the following steps:

(1) The above-mentioned cellulosic bio-based materials are decompressed and degassed in a storage silo for 1-2 hours, and then extruded using extrusion equipment to obtain masterbatch;

(2) After extruding or injection molding the masterbatch obtained in step (1), a tubular parison is obtained, which is heated or heated to a softened state, and then blow molded and placed in a closed mold;

(3) The mold is closed and cooled to shape. After the mold is opened, the finished product enters the auxiliary mold, and the edges are cut in the auxiliary mold to produce a packaging bottle.

Example 2

A method for preparing cellulose-based bio-based materials. The raw materials of the cellulose-based bio-based materials are composed of the following proportions in parts by weight: 90 parts of nitrogenated lignocellulose, 90 parts of nanocellulose, and 30 parts of polyvinyl alcohol. 10 parts of chitosan, 4 parts of methylcellulose, 1 part of polydimethylsiloxane, 3 parts of epoxidized soybean oil, 15 parts of glycerin, 0.2 parts of triphenyl phosphate, a mixture of camphor essential oil and Mengzong bamboo extract 1 part, 25 parts water.

The preparation method of the above-mentioned cellulose bio-based material includes the following steps:

(1) Add the above weight portions of nitrogenated lignocellulose, nanocellulose, polyvinyl alcohol and chitosan to a high-speed mixer in turn and stir for 3 hours until evenly mixed;

(2) Add the above weight parts of methylcellulose, defoaming agent, plasticizer, glycerin, heat stabilizer, antifungal agent and water to a high-speed mixer in sequence and stir for 3 hours until evenly mixed;

(3) After decolorizing and vacuum dehydrating the mixture obtained in steps (1) and (2), add it to a high-speed mixer and stir for 1 to 2 hours. After mixing evenly, heat press it with a flat plate at 80 to 130°C for 2 to After 6 hours, cellulosic bio-based materials were obtained.

The preparation method of the above-mentioned nitrogenated lignocellulose includes the following steps:

(1) Select cotton or corn stems to cut, remove impurities, crush and sieve to obtain 210~280 mesh wood powder;

(2) Add 210~280 mesh wood powder to a mixed solution of water and ethanol with a mass ratio of 100:5, keep the temperature between 35~40°C, and then stir and grind for 5 hours to obtain lignocellulose Dispersions;

(3) Add urea to the lignocellulose dispersion, heat to 69-74°C, stir evenly, then add peracetic acid, continue stirring for 2 hours, then filter, wash, and dry to constant weight to obtain nitrided Lignocellulose.

Among them, the preparation methods of nanocellulose and packaging bottles are the same as in Example 1.

Example 3

A method for preparing cellulose-based bio-based materials. The raw material components of the cellulose-based bio-based materials are composed of the following proportions by weight: 80 parts of nitrogenated lignocellulose, 70 parts of nanocellulose, and 25 parts of polyvinyl alcohol. 8 parts of chitosan, 4 parts of methylcellulose, 1 part of polydimethylsiloxane, 3 parts of epoxidized soybean oil, 15 parts of glycerin, 0.3 parts of triphenyl phosphate, 0.5 parts of Mengzong bamboo extract, 10 parts of water .

The preparation method of the above-mentioned cellulose bio-based material includes the following steps:

(1) Add the above weight portions of nitrogenated lignocellulose, nanocellulose, polyvinyl alcohol and chitosan to a high-speed mixer in sequence and stir for 2 hours until evenly mixed;

(2) Add the above weight parts of methylcellulose, defoaming agent, plasticizer, glycerin, heat stabilizer, antifungal agent and water to a high-speed mixer in sequence and stir for 2 hours until evenly mixed;

(3) After decolorizing and vacuum dehydrating the mixture obtained in steps (1) and (2), add it to a high-speed mixer and stir for 1 to 2 hours. After mixing evenly, heat press it with a flat plate at 80 to 130°C for 2 to After 6 hours, cellulosic bio-based materials were obtained.

The preparation method of the above-mentioned nitrogenated lignocellulose includes the following steps:

(1) Select cotton or corn stems to cut, remove impurities, crush and sieve to obtain 210~280 mesh wood powder;

(2) Add 210~280 mesh wood powder to a mixed solution of water and ethanol with a mass ratio of 100:5, keep the temperature between 35~40°C, and then stir and grind for 3 hours to obtain lignocellulose Dispersions;

(3) Add urea to the lignocellulose dispersion, heat to 69-74°C, stir evenly, then add peracetic acid, continue stirring for 2 hours, then filter, wash, and dry to constant weight to obtain nitrided Lignocellulose.

Among them, the preparation methods of nanocellulose and packaging bottles are the same as in Example 1.

Comparative example 1

A method for preparing a packaging bottle. The raw material components of the packaging bottle are composed of the following proportions in parts by weight: 100 parts of polyethylene, 0.5 to 1.0 parts of defoaming agent, and 2 to 3 parts of plasticizer. The preparation method of the packaging bottle is the same as in the implementation example 1.

Performance testing

Performance tests were performed on the packaging bottles prepared in the above examples and comparative examples. The test results are shown in Table 1.

Table 1 Packaging bottle performance test results

The above data shows that due to the use of unique raw materials and special preparation processes process, so that the oxygen throughput, water vapor permeability, pressure resistance strength and other indicators of the packaging bottle prepared by the present invention are significantly better than those of the comparative example. The present invention uses degradable raw materials, so that the degradation rate of the packaging bottle prepared by the present invention is 98%; after using the heat stabilizer triphenyl phosphate, the thermal stability of the packaging bottle prepared by the present invention is significantly improved, and the heat-resistant temperature is increased to above 120°C, but the added amount does not improve the thermal stability of the packaging bottle as the added amount increases. properties are increased, and the addition amount of 0.2 parts is the most appropriate amount; after adding the antifungal agent Mengzong bamboo extract, the anti-mold levels of the safety bottles of the present invention are all level 0, indicating that the anti-mold effect of the Mengzong bamboo extract in the present invention is better good.

The above are only preferred embodiments of the present invention, and do not limit the patent scope of the present invention. Under the concept of the present invention, equivalent structural transformations made by using the description of the present invention, or directly/indirectly applied to other related technologies All fields are included in the patent protection scope of the present invention.

Claims (5)

A high-barrier fully biodegradable packaging bottle containing cellulose bio-based materials, characterized in that its preparation method includes the following steps: (1) Depressurize the cellulosic bio-based materials in the storage silo for 1-2 hours to degas, and then use extrusion equipment to extrude and process the masterbatch; (2) After extruding or injection molding the masterbatch obtained in step (1), a tubular parison is obtained, which is heated or heated to a softened state, and then blow molded and placed in a closed mold; (3) The mold is closed and cooled to shape. After the mold is opened, the finished product enters the auxiliary mold, and the edges are removed in the auxiliary mold to produce a packaging bottle; The cellulosic bio-based material is prepared from the following raw materials by weight: 50 to 100 parts of nitrogenated lignocellulose, 60 to 90 parts of nanocellulose, 20 to 30 parts of polyvinyl alcohol, and 5 to 10 parts of chitosan. parts, 3~5 parts of methylcellulose, 0.5~1.0 parts of defoaming agent, 2~3 parts of plasticizer, 10~15 parts of glycerin, 0.1~0.2 parts of heat stabilizer, 0.1~1 part of antifungal agent, water 0 to 30 parts, the preparation method of the fiber bio-based material includes the following steps: (1) Add the above weight portions of nitrogenated lignocellulose, nanocellulose, polyvinyl alcohol and chitosan to a high-speed mixer in sequence and stir for 1 to 3 hours until evenly mixed; (2) Add the above weight portions of methylcellulose, defoaming agent, plasticizer, glycerin, heat stabilizer, antifungal agent and water to a high-speed mixer in turn and stir for 1 to 3 hours until evenly mixed; (3) After decolorizing and vacuum dehydrating the mixture obtained in steps (1) and (2), add it to a high-speed mixer and stir for 1 to 2 hours. After mixing evenly, heat press it with a flat plate at 80 to 130°C for 2 to After 6 hours, cellulosic bio-based materials were obtained; The preparation method of nitrogenated lignocellulose includes the following steps: (1) Select cotton or corn stems to cut, remove impurities, crush and sieve to obtain 210~280 mesh wood powder; (2) Add 210~280 mesh wood powder to a mixed solution of water and ethanol with a mass ratio of 100:5, keep the temperature between 25~40°C, and then stir and grind for 1h-5h to obtain wood cellulose dispersion; (3) Add urea to the lignocellulose dispersion, heat to 65-74°C, stir evenly, then add peracetic acid or amide percarbonate, continue stirring for 2 hours, then filter, wash, and dry to constant temperature. Heavy to obtain nitrogenated lignocellulose. The high-barrier fully biodegradable packaging bottle containing cellulose bio-based materials as described in claim 1, wherein the preparation method of nanocellulose includes the following steps: (1) Select cotton or corn stems to cut, remove impurities, crush and sieve to obtain 210~280 mesh wood powder; (2) Mix wood powder with sulfuric acid with a mass percentage of 62~65%, stir evenly, and obtain a wood powder sulfuric acid mixture; (3) Pretreat the mixed solution obtained in step (2) in a light wave reactor at a reaction temperature of 60°C and a treatment time of 30 minutes; (4) Add 5% calcium chloride solution to the reaction mixed liquid pretreated by light waves at 65~70°C, and hydrolyze it for 2 hours; (5) Centrifuge, filter and wash the hydrolyzed mixed liquid; (6) After vacuum drying the washed solid, use ultrasonic pulverization and sieving to obtain nanocellulose. High-barrier biomass containing cellulosic bio-based materials as described in claim 1 Biodegradable packaging bottle, wherein the defoaming agent is polydimethylsiloxane, the plasticizer is epoxidized soybean oil, and the heat stabilizer is triphenyl phosphate. The high-barrier fully biodegradable packaging bottle containing cellulose bio-based materials as claimed in claim 1, wherein the antifungal agent is at least one of citric acid, camphor essential oil and Mengzong bamboo extract. The high-barrier fully biodegradable packaging bottle containing cellulose bio-based materials as described in claim 4 is characterized in that: the antifungal agent is Mengzong bamboo extract.