CN114196216B - Full-biodegradable thermoplastic water-soluble film based on vinasse waste and preparation method and application thereof - Google Patents
Full-biodegradable thermoplastic water-soluble film based on vinasse waste and preparation method and application thereof Download PDFInfo
- Publication number
- CN114196216B CN114196216B CN202111609843.8A CN202111609843A CN114196216B CN 114196216 B CN114196216 B CN 114196216B CN 202111609843 A CN202111609843 A CN 202111609843A CN 114196216 B CN114196216 B CN 114196216B
- Authority
- CN
- China
- Prior art keywords
- water
- vinasse
- soluble film
- protein
- biodegradable thermoplastic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
-
- 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
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
-
- 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
-
- 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
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Wrappers (AREA)
Abstract
The invention discloses a full-biodegradable thermoplastic water-soluble film based on vinasse waste and a preparation method and application thereof, and belongs to the technical field of full-biodegradable composite material forming and processing. Compared with the existing petroleum-based polyvinyl alcohol (PVA) water-soluble film in the market, the vinasse protein-based fully-biodegradable thermoplastic water-soluble film has the advantages of meeting the basic performance requirement of a water-soluble film, along with lower preparation cost and higher industrial operability, can be adapted to the existing high polymer plastic processing system, and also has lower carbon dioxide emission.
Description
Technical Field
The invention relates to the technical field of forming and processing of full-biodegradable composite materials, in particular to a full-biodegradable thermoplastic water-soluble film based on vinasse waste and a preparation method and application thereof.
Background
The vinasse is the largest waste source of all large wine brewing enterprises, such as three towns of Shen wine, maotai town, gujing town, yanghe town, carbofuran beer, qingdao beer and other wine enterprises, countless vinasse wastes exist every day, if the vinasse is utilized, the problem of environmental pollution caused by vinasse wastes can be effectively solved, and secondary profit can be realized. At present, the treatment method of the vinasse by most enterprises or individuals is simple and rough explosion, and the vinasse is basically used as feed or fertilizer for direct sale after simple drying treatment and even directly buried. However, the abundant protein in the distiller's grains is not fully utilized, which not only causes serious waste of resources, but also causes environmental pollution. Therefore, how to realize high-value comprehensive utilization of the vinasse has profound significance for economic benefits of the wine making industry and sustainable development of environmental protection.
The water soluble film is a film packaging material which can be quickly dissolved in water through special process treatment and processing, can be quickly and automatically denatured, decomposed and degraded into low molecular compounds under the action of natural factors, has the function of improving the land, and belongs to a novel environment-friendly packaging material. The environmental protection department has gained approval in Europe and America, japan, and the like. Because of its environmental protection characteristic, it has been widely regarded by developed countries in the world, and large companies in the fields of foreign daily chemicals, pesticides, chemical industry and the like have widely used water-soluble films to package the products.
The water-soluble film commonly used in the market at present is prepared by using polyvinyl alcohol as a base material, and the production process of the water-soluble polyvinyl alcohol film generally adopts a solution casting method. The film product prepared by the tape casting method has high thickness precision and good transparency and glossiness, but PVA needs to be dissolved at high temperature, so that the drying energy consumption is large, the production period is long, the efficiency is low, the cost is high, the application of the polyvinyl alcohol film is greatly limited, more importantly, PVA is a petroleum-based source, and from the aspects of carbon footprint and life cycle evaluation, the PVA-based water-soluble film is not environment-friendly in the true sense and does not accord with the strategy of sustainable green development, so the development of the full-degradable water-soluble film based on the biomass source is particularly urgent.
Based on the above, in order to utilize the vinasse agricultural waste more efficiently and change the cost into treasure, and simultaneously develop a fully-biodegradable water-soluble film based on a bio-based source, a fully-biodegradable thermoplastic water-soluble film based on the vinasse waste and a preparation method and application thereof are provided.
Disclosure of Invention
The invention provides a full-biodegradable thermoplastic water-soluble film based on vinasse waste, and a preparation method and application thereof, and solves the problems in the background technology.
The invention realizes the purpose through the following technical scheme:
the invention provides a full-biodegradable thermoplastic water-soluble film based on vinasse waste, which is obtained by taking modified vinasse protein as a raw material, adding an environment-friendly plasticizer, a dissolving promoter, a reducing agent, a dynamic cross-linking agent and a hydrophobic agent, and carrying out double-screw thermoplastic extrusion processing and film blowing.
The further improvement is that the fully biodegradable thermoplastic water-soluble film component comprises the following components in parts by weight: 50-80 parts of modified vinasse protein, 20-30 parts of environment-friendly plasticizer, 2-5 parts of dissolution promoter, 1-2 parts of reducing agent, 1-2 parts of dynamic cross-linking agent and 2-5 parts of hydrophobic agent.
The further improvement is that the modified vinasse protein is obtained by sequentially performing salinization, grafting modification and spray drying on the vinasse protein separated and purified from the vinasse waste, and the specific preparation steps are as follows:
(1) Salinization: placing the vinasse protein precipitate separated and purified from the vinasse waste into a container, adding water to dilute the vinasse protein precipitate into a suspension with the solid content of about 20-25wt%, adjusting the pH of the suspension system to 9-11 by adopting a sodium hydroxide solution, and controlling the heating temperature to be 90 ℃;
(2) Graft modification: adding an epoxy grafting agent in an amount of 25% by weight based on the oven-dried weight of the distillers' grains protein to the suspension, and stirring for reaction;
(3) Spray drying: adjusting pH of the whole distillers 'grain protein suspension to neutral, adjusting solid content to 8-10 wt%, and spray drying to obtain modified distillers' grain protein.
The further improvement is that the vinasse protein separated and purified from the vinasse waste is one of beer vinasse protein, white spirit vinasse protein, red wine vinasse protein or yellow wine vinasse protein.
The further improvement is that the epoxy grafting modifier is one of propylene oxide, n-butyl glycidyl ether, C12-C14 alkyl glycidyl ether and benzyl glycidyl ether.
The further improvement is that the environment-friendly plasticizer is at least one of water, glycerol, sorbitol, polyethylene glycol and urea.
The further improvement is that the dissolution promoter is one of polyether polyol, oxidized starch and sodium carboxymethyl cellulose.
In a further improvement, the reducing agent is one of sodium sulfite or mercaptan.
In a further improvement, the dynamic cross-linking agent is one of calcium chloride, citric acid, phytic acid or boric acid.
The further improvement is that the hydrophobic agent is one of oleic acid, stearic acid or beeswax.
The invention also provides a preparation method of the fully-degradable thermoplastic water-soluble film, which comprises the following steps:
(1) Stirring and mixing the modified vinasse protein, a plasticizer, a dissolution promoter, a reducing agent, a dynamic cross-linking agent and a hydrophobic agent to obtain a premix;
(2) Placing the premix obtained in the step (1) in a double-screw extruder to perform thermoplastic processing treatment under the processing condition of 80-120 ℃, and cooling and dicing to obtain fully biodegradable thermoplastic water-soluble film master batches;
(3) And (3) placing the fully-degradable thermoplastic water-soluble master batch obtained in the step (2) under the conditions of constant temperature and constant humidity for balanced treatment for 24 hours, and extruding and blowing the film by a single screw to obtain the coiled fully-degradable thermoplastic water-soluble film.
The invention also provides an application of the fully-degradable thermoplastic water-soluble film in a water-soluble packaging material.
The further improvement lies in that the water-soluble packaging material belongs to the fields of washing condensed bead packaging, pesticide water-soluble packaging, crop seed packaging, water-soluble labels, medical care water-soluble washing bags, pet excrement garbage bags and the like.
The invention has the beneficial effects that:
(1) Agricultural waste vinasse is used as a source, biomass is used as a source, the biodegradable property is realized, the carbon footprint is lower, waste is changed into valuable, and the strategies of carbon peak reaching and carbon neutralization proposed by the state are perfectly matched.
(2) Under the alkaline condition, the salinization regulation and the epoxy grafting modification of the vinasse protein are synchronously realized. By utilizing the alkaline condition, the regulation and control of amino and carboxyl ion pairs in the molecular structure of the vinasse protein are realized, the water solubility of the vinasse protein is effectively improved, the epoxy grafting modification of the vinasse protein is realized at the same time, and the thermoplastic processability of the vinasse protein is effectively improved by introducing the epoxy group. The steric effect of the epoxy grafting group is utilized to prevent the aggregation and crystallization of protein molecular chains, and on the other hand, the epoxy grafting group weakens the internal hydrogen bond strength of the starch particle structure, thereby playing a good role in internal plasticization.
(3) By adding a proper amount of the cross-linking agent, the dynamic cross-linking between the vinasse protein is effectively realized in the thermoplastic processing process of the vinasse protein, the water-soluble performance of the modified vinasse protein film is not influenced, and the mechanical strength performance of the thermoplastic vinasse protein film is improved to a certain extent.
(4) The method is perfectly adapted to the existing high-molecular thermoplastic processing system, has excellent industrial operability, and greatly improves the production and processing efficiency and the production yield.
(5) The thermoplastic water-soluble film of the vinasse protein has good water-soluble performance, strength performance and packaging performance. Compared with the existing petroleum-based PVA water-soluble film in the market, the vinasse protein-based fully biodegradable thermoplastic water-soluble film has the advantages of lower preparation cost and higher industrial operability while meeting the basic performance requirement of the water-soluble film, can be adapted to the existing polymer plastic processing system, is more important to biomass source, has lower carbon dioxide emission and is more environment-friendly.
Drawings
FIG. 1 is a water-soluble performance test chart of the fully biodegradable thermoplastic water-soluble film of the present invention;
FIG. 2 is a sample of a concentrated laundry detergent package based on a fully biodegradable thermoplastic water-soluble film according to the present invention;
FIG. 3 is a sample of a soap package based on a fully biodegradable thermoplastic water-soluble film of the present invention;
fig. 4 is a picture of a printed label actual product based on a fully biodegradable thermoplastic water-soluble film according to the invention.
Detailed Description
The present application will now be described in further detail with reference to the drawings, it should be noted that the following detailed description is given for illustrative purposes only and is not to be construed as limiting the scope of the present application, as those skilled in the art will be able to make numerous insubstantial modifications and adaptations to the present application based on the above disclosure.
Example 1
The preparation process of the fully-degradable thermoplastic water-soluble film in the embodiment is as follows:
(1) Vinasse protein modification treatment
Precipitating the vinasse protein after protein extraction, separation and purification, placing the vinasse protein into a stainless steel reaction kettle, adding water to dilute the vinasse protein into a suspension with the solid content of about 20-25wt%, then adjusting the pH of the whole suspension system to about 10 by using 0.5mol/L sodium hydroxide solution, controlling the heating temperature to be 90 ℃, finally adding an epoxy grafting agent which is 25wt% of the absolute dry mass of the vinasse protein, specifically propylene oxide, setting the stirring revolution number to be 200r/min, reacting for 2 hours, and synchronously realizing the salinization control and epoxy grafting modification of the vinasse protein.
Adjusting the pH of the vinasse protein suspension liquid after the reaction to be neutral, adjusting the solid content to be between 8 and 10 percent by weight, and performing spray drying treatment to obtain modified vinasse protein micro powder for subsequent thermoplastic processing.
(2) Thermoplastic extrusion processing and blown film
a. Fully dissolving sodium sulfite serving as a reducing agent and polyether glycol serving as a cosolvent in purified water, then adding glycerol to fully mix, pouring into the epoxypropane modified vinasse protein micro powder, placing in a high-speed stirrer to perform high-speed blending treatment, setting the revolution number to be 300r/min, and uniformly mixing for 15min to obtain a fully mixed premix. The premix comprises, by weight, 75 parts of modified vinasse protein micro powder, 10 parts of pure water, 15 parts of glycerol, 1 part of sodium sulfite, 1 part of polyether polyol, 2 parts of oleic acid and 1 part of calcium chloride.
b. And (3) moving the prepared uniformly mixed material into a double-screw extruder, wherein the diameter of a screw is 25dm, the length-diameter ratio is 40, the temperature of each heating section is set to 40 ℃, 60 ℃, 80 ℃, 100 ℃, 90 ℃ and 90 ℃ in sequence, the temperature of a machine head is 90 ℃, the rotating speed of a main machine screw is 100r/min, the feeding speed is 30r/min, and obtaining the vinasse protein film master batch after double-screw extrusion, bracing, cooling and grain cutting.
c. The vinasse film master batch obtained by extrusion and granulation is placed in a constant temperature and humidity environment (23 ℃,50 percent RH) for balanced treatment for 24h, and then the preparation of the thermoplastic water-soluble vinasse protein is realized by adopting a single-screw extrusion film blowing processing mode. The processing temperature range of screw extrusion film blowing is set to 80 ℃, 100 ℃, 110 ℃ and 100 ℃.
Example 2
The difference from example 1 is that the modified protein used is a C12-C14 alkyl glycidyl ether modified distillers' grains protein.
Example 3
The difference from example 1 is that the modified protein used is n-butyl glycidyl ether modified distillers' grains protein.
Comparative example 1
The difference from the example 1 is that the mixing material comprises, by mass, 75 parts of common vinasse protein micro powder, 10 parts of pure water, 15 parts of glycerol, 1 part of sodium sulfite, 1 part of polyether polyol, 2 parts of oleic acid and 1 part of calcium chloride. Wherein the common vinasse protein micro powder is obtained by spray drying the vinasse protein precipitate separated and purified from the vinasse waste.
Example 2
The difference from the example 1 is that the mixture comprises, by mass, 50 parts of modified vinasse protein micro powder, 15 parts of pure water, 35 parts of glycerol, 1 part of sodium sulfite, 1 part of polyether polyol, 2 parts of oleic acid and 1 part of calcium chloride.
Comparative example 3
The difference from the example 1 is that the mixture comprises, by mass, 75 parts of modified vinasse protein micro powder, 10 parts of pure water, 15 parts of glycerol, 1 part of sodium sulfite, 1 part of polyether polyol and 2 parts of oleic acid.
Comparative example 4
The difference from the example 1 is that the mixture comprises, by mass, 75 parts of modified vinasse protein micro powder, 10 parts of pure water, 15 parts of glycerol, 1 part of sodium sulfite and 1 part of polyether polyol.
The specific formulations of the films prepared in examples 1-3 and comparative examples 1-4 are shown in the following table:
in order to verify the effects of the present invention, the films prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to film sample strength property and water solubility property tests.
1. After the film sample was placed in a constant temperature and humidity chamber (23 ℃ C., 50 RH%) and subjected to a balancing treatment for 24 hours, the film strength was measured in accordance with ISO 1184-1983, "measurement of tensile Properties of Plastic films". The results are shown in the following table.
2. Cutting the thermoplastic water-soluble film into squares (the thickness is about 50 mu m) with the size of 6 multiplied by 6cm, immersing the squares in a watch glass filled with normal-temperature water, and observing the starting dissolving time and the complete dissolving time of the film without static stirring for judging the water-soluble performance of the film. The results are shown in the following table.
The table above shows that, in combination with the table above and fig. 1, the thermoplastic processing performance, strength and water solubility of the distillers 'grain protein are effectively improved after salinization and single epoxy grafting modification, and the distillers' grain protein can be seamlessly adapted to the existing thermoplastic film processing system. The modified vinasse protein has good mechanical property and water solubility, can be dissolved within 5 seconds, can be completely dissolved statically within 5 minutes, has no residue, can be used for replacing the conventional PVA petroleum-based water-soluble film, and has lower carbon dioxide emission.
The production and processing of the films prepared in comparative example 1 and comparative example 3 are not effectively completed, and the related performance test cannot be carried out; compared with the comparative example 2 and the examples 1 to 3, the thermoplastic processing of the modified vinasse protein in the examples 1 to 3 can be realized by more glycerol plasticizers than that of the unmodified vinasse protein, the thermoplastic processing performance of the modified vinasse protein is improved, less plasticizers are required to be added, and the performance is more excellent; as can be seen from comparative example 4, the tensile strength of the film without the dynamic crosslinking agent is significantly reduced, the elongation at break is increased in a large extent, and the performance of the water-soluble film is influenced to a certain extent.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention.
Claims (9)
1. The fully-biodegradable thermoplastic water-soluble film based on the vinasse waste is characterized in that the fully-biodegradable thermoplastic water-soluble film is obtained by taking modified vinasse protein as a raw material, adding an environment-friendly plasticizer, a dissolution promoter, a reducing agent, a dynamic cross-linking agent and a hydrophobic agent, and carrying out double-screw thermoplastic extrusion processing and film blowing;
the fully biodegradable thermoplastic water-soluble film component comprises the following components in parts by weight: 50-80 parts of modified vinasse protein, 20-30 parts of environment-friendly plasticizer, 2-5 parts of dissolution promoter, 1-2 parts of reducing agent, 1-2 parts of dynamic cross-linking agent and 2-5 parts of hydrophobic agent;
the modified vinasse protein is obtained by sequentially performing salinization, grafting modification and spray drying on vinasse protein separated and purified from vinasse waste, and the preparation method specifically comprises the following steps:
(1) Salinization: placing the vinasse protein precipitate separated and purified from the vinasse waste into a container, adding water to dilute the vinasse protein precipitate into a suspension with the solid content of 20-25wt%, adjusting the pH of the suspension system to 9-11 by adopting a sodium hydroxide solution, and controlling the heating temperature to be 90 ℃;
(2) Graft modification: adding an epoxy grafting agent in an amount of 25% by weight based on the oven-dried weight of the distillers' grains protein to the suspension, and stirring for reaction;
(3) Spray drying: adjusting the pH of the vinasse protein suspension liquid after the grafting modification reaction to be neutral, adjusting the solid content to be 8-10 wt%, and performing spray drying treatment to obtain modified vinasse protein;
the dissolution promoter is one of polyether polyol, oxidized starch and sodium carboxymethyl cellulose;
the dynamic cross-linking agent is one of calcium chloride, citric acid, phytic acid or boric acid.
2. The fully-biodegradable thermoplastic water-soluble film based on vinasse waste according to claim 1, wherein the vinasse protein separated and purified from the vinasse waste is one of beer vinasse protein, white spirit vinasse protein, red wine vinasse protein or yellow wine vinasse protein.
3. The fully biodegradable thermoplastic water-soluble film based on vinasse waste according to claim 1, wherein the epoxy grafting agent is one of propylene oxide, n-butyl glycidyl ether, C12-C14 alkyl glycidyl ether and benzyl glycidyl ether.
4. The fully biodegradable thermoplastic water-soluble film based on vinasse waste according to claim 1, wherein the environment-friendly plasticizer is at least one of water, glycerol, sorbitol, polyethylene glycol and urea.
5. The fully biodegradable thermoplastic water-soluble film based on vinasse waste according to claim 1, wherein the reducing agent is one of sodium sulfite or mercaptan.
6. The fully biodegradable thermoplastic water-soluble film based on vinasse waste according to claim 1, wherein the hydrophobic agent is one of oleic acid, stearic acid or beeswax.
7. A process for the preparation of a fully biodegradable thermoplastic water-soluble film according to any one of claims 1 to 6, comprising the steps of:
(1) Stirring and mixing the modified vinasse protein, an environment-friendly plasticizer, a dissolution promoter, a reducing agent, a dynamic cross-linking agent and a hydrophobic agent to obtain a premix;
(2) Placing the premix obtained in the step (1) in a double-screw extruder to perform thermoplastic processing treatment under the processing condition of 80-120 ℃, and cooling and dicing to obtain fully biodegradable thermoplastic water-soluble film master batches;
(3) And (3) placing the master batch of the fully biodegradable thermoplastic water-soluble film obtained in the step (2) under the conditions of constant temperature and constant humidity for balanced treatment for 24 hours, and extruding and blowing the film by a single screw to obtain the coiled fully biodegradable thermoplastic water-soluble film.
8. Use of a fully biodegradable thermoplastic water-soluble film according to any one of claims 1 to 6 in a water-soluble packaging material.
9. The use of a fully biodegradable, thermoplastic, water-soluble film according to claim 8 in a water-soluble packaging material, wherein said water-soluble packaging material is a laundry bead package, a pesticide water-soluble package, a crop seed package, a water-soluble label, a medical care water-soluble laundry bag or a pet litter bag.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111609843.8A CN114196216B (en) | 2021-12-27 | 2021-12-27 | Full-biodegradable thermoplastic water-soluble film based on vinasse waste and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111609843.8A CN114196216B (en) | 2021-12-27 | 2021-12-27 | Full-biodegradable thermoplastic water-soluble film based on vinasse waste and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114196216A CN114196216A (en) | 2022-03-18 |
| CN114196216B true CN114196216B (en) | 2023-01-06 |
Family
ID=80656689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111609843.8A Active CN114196216B (en) | 2021-12-27 | 2021-12-27 | Full-biodegradable thermoplastic water-soluble film based on vinasse waste and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114196216B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103640290A (en) * | 2013-12-13 | 2014-03-19 | 山东汇盈新材料科技有限公司 | Completely biodegradable composite membrane with high barrier property |
| CN109400962A (en) * | 2018-11-09 | 2019-03-01 | 陕西科技大学 | A kind of preparation method of cellulose microgel film |
| CN109486211A (en) * | 2018-09-26 | 2019-03-19 | 长沙乐远化工科技有限公司 | A kind of casein base packing film and preparation method thereof and the application in bacon is fresh-keeping |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9267027B2 (en) * | 2009-05-28 | 2016-02-23 | Fibria Innovations Inc. | Resin compositions comprising lignin derivatives |
| BR112012030535B1 (en) * | 2010-05-14 | 2021-06-01 | Alltech Inc. | METHOD TO DETECT A YEAST CELL WALL COMPONENT |
| BR102012029731A2 (en) * | 2012-11-22 | 2018-07-31 | Cnpem Centro Nac De Pesquisa Em Energia E Materiais | process and equipment for multi-stage continuous fermentation with recovery, reactivation and recycling of yeast to obtain high alcohol wines |
| CN104725649A (en) * | 2013-12-24 | 2015-06-24 | 仲恺农业工程学院 | Preparation method of in-situ cross-linked feather keratin hybrid membrane |
| CN108178568A (en) * | 2016-12-08 | 2018-06-19 | 李光明 | A kind of preparation method of electric force pole tower |
| CN107675500A (en) * | 2017-10-10 | 2018-02-09 | 宿迁远扬生物科技有限公司 | A kind of purified cotton yarns environment-friendly size |
| CN109161030A (en) * | 2018-08-15 | 2019-01-08 | 中国林业科学研究院木材工业研究所 | A kind of vegetable protein and preparation method thereof of amino graft modification |
| CN109575540A (en) * | 2018-11-30 | 2019-04-05 | 深圳市裕同包装科技股份有限公司 | A kind of vinasse polylactic acid biodegradable composites, preparation method and application |
| CN110499141A (en) * | 2019-08-29 | 2019-11-26 | 贵州大学 | A kind of biomass crosslinking agent modified oil tea oil cake adhesive and preparation method and application |
| CN112709092B (en) * | 2019-10-24 | 2022-06-17 | 夏振明 | Paper made from waste residues of textile, industry and agriculture and paper making method |
| CN113502058A (en) * | 2021-07-28 | 2021-10-15 | 杭州靡特洛新材料科技有限公司 | Biodegradable vinasse protein film and preparation method and application thereof |
-
2021
- 2021-12-27 CN CN202111609843.8A patent/CN114196216B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103640290A (en) * | 2013-12-13 | 2014-03-19 | 山东汇盈新材料科技有限公司 | Completely biodegradable composite membrane with high barrier property |
| CN109486211A (en) * | 2018-09-26 | 2019-03-19 | 长沙乐远化工科技有限公司 | A kind of casein base packing film and preparation method thereof and the application in bacon is fresh-keeping |
| CN109400962A (en) * | 2018-11-09 | 2019-03-01 | 陕西科技大学 | A kind of preparation method of cellulose microgel film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114196216A (en) | 2022-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101712775B (en) | Preparation method of starch-base biodegradation material | |
| CN101486806A (en) | Natural polymer / degradable polymer composite material and preparation thereof | |
| CN103044716B (en) | Biodegradable material and preparation method thereof | |
| CN101948598B (en) | Method for preparing biodegradable membrane | |
| CN111423689B (en) | Modified polypropylene material and preparation method and application thereof | |
| CN106432814A (en) | Starch/polyvinyl alcohol composite material and preparation method thereof | |
| CN114196216B (en) | Full-biodegradable thermoplastic water-soluble film based on vinasse waste and preparation method and application thereof | |
| CN110938291A (en) | Polylactic acid composite material and preparation method thereof | |
| CN114933785A (en) | Modified lignin/PBAT biodegradable plastic and preparation method thereof | |
| CN113912989A (en) | Novel biodegradable tackifying master batch and preparation method thereof | |
| CN112442146B (en) | Polyvinyl alcohol-based degradable plastic, preparation method and application thereof, and recycling method thereof | |
| CN111944226A (en) | Photodegradable plastic packaging bag environment-friendly material and preparation method thereof | |
| CN101585932B (en) | Full biodegradable package film and preparation method thereof | |
| CN100509945C (en) | Biodegradeable plastics and preparing method thereof | |
| CN114685961B (en) | Modified polylactic acid film material | |
| CN109825049A (en) | A kind of high amylose starches/lactic acid composite material mother material production technology | |
| CN115260542A (en) | Preparation method of degradable polymer/starch masterbatch | |
| CN113563730A (en) | Ultrafine filler and fully-degradable composite material for vinasse protein purification residues, and preparation method and application thereof | |
| CN1478808A (en) | Starch base trielement system complete biodegradation film and blow moulding film forming method | |
| CN110591312A (en) | Biodegradable plastic bottle cap and preparation method thereof | |
| CN101486832A (en) | Carbon dioxide - epoxypropane copolymer and polycaprolactone blend and preparation | |
| CN107266760A (en) | A kind of degradable stalk polyethylene film and preparation method thereof | |
| CN116410606A (en) | Preparation method and application of high-performance water-soluble controllable biomass-based thermoplastic film | |
| CN116693920B (en) | Antibacterial packaging film and preparation method thereof | |
| CN114106358B (en) | Modified bio-based material, composite material, raw materials thereof, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |