CN114672174A - High-strength bio-based film material and preparation method thereof - Google Patents
High-strength bio-based film material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 239000012528 membrane Substances 0.000 claims abstract description 39
- 235000018553 tannin Nutrition 0.000 claims abstract description 26
- 239000001648 tannin Substances 0.000 claims abstract description 26
- 229920001864 tannin Polymers 0.000 claims abstract description 26
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005018 casein Substances 0.000 claims abstract description 19
- 235000021240 caseins Nutrition 0.000 claims abstract description 19
- 239000002028 Biomass Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 21
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000005022 packaging material Substances 0.000 abstract description 4
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- 102000004169 proteins and genes Human genes 0.000 abstract description 2
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- 239000004952 Polyamide Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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
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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
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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Abstract
The invention belongs to the technical field of packaging material preparation, and particularly relates to a high-strength bio-based film material and a preparation method thereof; the method specifically comprises the steps of taking casein as a substrate raw material of a membrane material, carrying out cross-linking modification treatment on the casein by adopting a hyperbranched compound and tannin, and comparing with a biomass film added with glycerol to obtain a protein membrane with excellent mechanical strength, wherein the prepared membrane material is degradable, has good comprehensive performance and wide application range.
Description
Technical Field
The invention belongs to the technical field of packaging material preparation, and particularly relates to a high-strength biomass membrane material and a preparation method thereof.
Background
The natural degradation process of plastics produced from fossil-based materials is extremely slow, for decades or even centuries, so that plastic contamination is considered difficult to reverse. The global environment is threatened by white pollution which is continuously accumulated, and a large amount of plastic fragments enter rivers, lakes, oceans and soil. Plastics have posed a serious threat to the natural system and human health.
With the rapid development of express logistics and takeaway industries, the consumption of packaging film materials used in a short period of time is increased sharply, and the influence on the environment is further aggravated. Although the generation and the use of the fossil-based packaging film material are convenient for the daily life of people, the development of a sustainable substitute, namely a green packaging material, is vital to promote the environmental and economic greenness and sustainable growth. The green packaging material is developed rapidly, has wide application prospect and mainly comprises cellulose derivatives, polyamides, polyesters, polyolefins, ethylene polymers, silicon-containing polymers, fluorine-containing polymers and the like, wherein the biomass membrane material which is researched most at the earliest is a cellulose membrane material. The biomass membrane material has the advantages of being renewable, good in biocompatibility, capable of being completely degraded after being discarded and the like.
Earlier researches show that a single biomass membrane material has good membrane forming property, but has poor mechanical strength and barrier property to water vapor. Therefore, a single biomass membrane material needs to be modified, and the prior art mainly comprises modification before membrane formation, including means such as chemical modification, graft copolymerization and crosslinking; the modification after film formation mainly comprises surface modification, such as plasma treatment, surface etching, surface chemical reaction, surface molecular assembly, surface physical coating, surface grafting modification and the like.
The patent document with publication number CN113321936A discloses a high-strength biomass membrane material and a preparation method thereof, and particularly relates to a protein membrane with excellent mechanical strength and elongation limit, which is obtained by using casein as a substrate raw material of the membrane material and performing cross-linking modification treatment on the casein by adopting microcrystalline cellulose and tannin. The main purpose is to improve the tensile strength and the tensile rate of the biological membrane material, particularly the improvement effect on the tensile rate is obvious, but the tensile strength and the barrier property to water vapor cannot reach a more ideal state.
Disclosure of Invention
In order to solve the problems, the invention adopts a hyperbranched compound and tannin as a modified crosslinking agent, aims to prepare a high-strength biomass membrane material with excellent mechanical strength and excellent water vapor barrier property, and provides a preparation method thereof.
The method is realized by the following technical scheme:
1. a high-strength biomass membrane material comprises the following components in parts by weight: 5-10 parts of casein, 3-5 parts of modifier and 100 parts of water.
Further, the modifier consists of 3-4 parts of hyperbranched compound and 0-1 part of tannin in parts by weight.
Furthermore, the hyperbranched compound is prepared by catalyzing tetraethyl titanate triethanolamine 1:1-3mol at the temperature of 100-140 ℃ and under the acidic condition by using one thousandth of mol of p-toluenesulfonic acid as a catalyst.
2. The preparation method of the high-strength bio-based film material specifically comprises the following steps:
(1) adding tetraethyl titanate and triethanolamine into a three-neck flask according to the proportion of 1:1-3mol, adding a catalyst of p-toluenesulfonic acid, and mixing and stirring at the temperature of 100-;
(2) dissolving casein in an alkali solution to enable the pH value of the system to be 11, and uniformly stirring to obtain a base solution;
(3) mixing and stirring the hyperbranched compound and the substrate liquid uniformly for 10min, adding tannin, heating to 80 ℃, stirring in a constant-temperature water bath for 20min until the mixture becomes a resin film liquid uniformly, cooling and defoaming, and pouring into a mold for casting to form a film.
When the using amount of the tannin is 0, mixing the hyperbranched compound and the substrate liquid, uniformly stirring for 10min, heating to 80 ℃, stirring in a constant-temperature water bath for 20min until the mixture is uniformly formed into a resin film liquid, cooling, defoaming, and pouring into a mold to pour and form a film.
Further, the alkali solution is specifically a 30 wt% sodium hydroxide solution.
In conclusion, the beneficial effects of the invention are as follows: the invention takes casein as a substrate raw material of a film material, adopts hyperbranched compound and tannin to carry out cross-linking modification treatment on the casein, the hyperbranched compound has good solubility and excellent structural performance, and the hyperbranched cross-linking structure with rich end groups can improve the reaction activity and the cross-linking strength of modified resin. The hyperbranched structure and the active sites of tannin react to form a firmer cross-linked network structure, and the performance of the membrane material can be effectively improved, so that the membrane material with excellent tensile strength and water vapor barrier property is obtained.
Drawings
FIG. 1 is a high strength bio-based film prepared using the method of examples 1-5; the color of the film deepens along with the increase of the adding amount of the tannin, and the whole color is brown.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
1. A preparation method of a high-strength bio-based film material specifically comprises the following steps:
(1) weighing 3g of hyperbranched compound obtained by reacting under high-temperature acidic condition, wherein the hyperbranched compound in the embodiment is prepared from tetraethyl titanate and triethanolamine in a proportion of 1:2.5 mol;
(2) dissolving 6g of casein in 100ml of distilled water, adjusting the pH value of the solution to 11 by using 2mol/L NaOH solution, and stirring for about 2 hours until the solution is uniform to obtain a base solution;
(3) and stirring the weighed hyperbranched compound and the substrate solution for 10 minutes, heating to 80 ℃, and stirring in a constant-temperature water bath for 20 minutes until the mixture is uniform to form a resin membrane solution. And cooling and defoaming the prepared film forming liquid, and pouring the film forming liquid into a mold for film forming.
Example 2
1. A preparation method of a high-strength bio-based film material specifically comprises the following steps:
(1) weighing 3g of hyperbranched compound obtained by reacting under high-temperature acidic condition, wherein the hyperbranched compound in the embodiment is prepared from tetraethyl titanate and triethanolamine in a proportion of 1:2.5 mol; 0.3g (5%) of tannin was weighed out and dissolved in 1ml of distilled water;
(2) dissolving 6g of casein in 100ml of distilled water, adjusting the pH value of the solution to 11 by using 2mol/L NaOH solution, and stirring for about 2 hours until the solution is uniform to obtain a base solution;
(3) and stirring the weighed hyperbranched compound and the substrate solution for 10 minutes, adding tannin, heating to 80 ℃, and stirring in a constant-temperature water bath for 20 minutes until the mixture is uniform to form a resin membrane solution. And cooling and defoaming the prepared film forming solution, and pouring the solution into a mold to form a film.
Example 3
1. A preparation method of a high-strength bio-based film material specifically comprises the following steps:
1) weighing 3g of hyperbranched compound obtained by reacting under high-temperature acidic condition, wherein the hyperbranched compound in the embodiment is prepared from tetraethyl titanate and triethanolamine in a proportion of 1:2.5 mol; 0.6g (10%) of tannin was weighed out and dissolved in 1ml of distilled water;
(2) dissolving 6g of casein in 100ml of distilled water, adjusting the pH value of the solution to 11 by using 2mol/L NaOH solution, and stirring for about 2 hours until the solution is uniform to obtain a base solution;
(3) and stirring the weighed hyperbranched compound and the substrate solution for 10 minutes, adding tannin, heating to 80 ℃, and stirring in a constant-temperature water bath for 20 minutes until the mixture is uniform to form a resin membrane solution. And cooling and defoaming the prepared film forming liquid, and pouring the film forming liquid into a mold for film forming.
Example 4
1. A preparation method of a high-strength bio-based film material specifically comprises the following steps:
1) weighing 3g of hyperbranched compound obtained by reacting under high-temperature acidic condition, wherein the hyperbranched compound in the embodiment is prepared from tetraethyl titanate and triethanolamine in a proportion of 1:2.5 mol; 0.9g (15%) of tannin was weighed out and dissolved in 1ml of distilled water;
(2) dissolving 6g of casein in 100ml of distilled water, adjusting the pH value of the solution to 11 by using 2mol/L NaOH solution, and stirring for about 2 hours until the solution is uniform to obtain a base solution;
(3) and stirring the weighed hyperbranched compound and the substrate solution for 10 minutes, adding tannin, heating to 80 ℃, and stirring in a constant-temperature water bath for 20 minutes until the mixture is uniform to form a resin membrane solution. And cooling and defoaming the prepared film forming liquid, and pouring the film forming liquid into a mold for film forming.
Example 5
1. A preparation method of a high-strength bio-based film material specifically comprises the following steps:
(1) weighing 3g of hyperbranched compound obtained by reacting under high-temperature acidic condition, wherein the hyperbranched compound in the embodiment is prepared from tetraethyl titanate and triethanolamine in a proportion of 1:2.5 mol; weighing 1.2g (20%) of tannin and dissolving in 1ml of distilled water;
(2) dissolving 6g of casein in 100ml of distilled water, adjusting the pH value of the solution to 11 by using 2mol/L NaOH solution, and stirring for about 2 hours until the solution is uniform to obtain a base solution;
(3) and stirring the weighed hyperbranched compound and the substrate solution for 10 minutes, adding tannin, heating to 80 ℃, and stirring in a constant-temperature water bath for 20 minutes until the mixture is uniform to form a resin membrane solution. And cooling and defoaming the prepared film forming liquid, and pouring the film forming liquid into a mold for film forming.
Example 6
1. A preparation method of a high-strength bio-based film material specifically comprises the following steps:
(1) weighing 3g of hyperbranched compound obtained by reacting under high-temperature acidic condition, wherein the hyperbranched compound in the embodiment is prepared from tetraethyl titanate and triethanolamine in a proportion of 1:1 mol; weighing 1.2g (20%) of tannin and dissolving in 1ml of distilled water;
(2) dissolving 6g of casein in 100ml of distilled water, adjusting the pH value of the solution to 11 by using 2mol/L NaOH solution, and stirring for about 2 hours until the solution is uniform to obtain a base solution;
(3) and stirring the weighed hyperbranched compound and the substrate solution for 10 minutes, adding tannin, heating to 80 ℃, and stirring in a constant-temperature water bath for 20 minutes until the mixture is uniform to form a resin membrane solution. And cooling and defoaming the prepared film forming liquid, and pouring the film forming liquid into a mold for film forming.
Comparative example 1
The membrane material is prepared by adopting the raw material ratio and the preparation method of the embodiment 1, and the difference is that the hyperbranched compound and the tannin are not added, and the glycerol with the same mass ratio is added.
Comparative example 2
The membrane material is prepared by adopting the raw material proportion and the preparation method of the embodiment 2, and the difference is that the hyperbranched compound is not added, and the glycerol with the same mass ratio is added.
Comparative example 3
The membrane material was prepared by the raw material ratio and the preparation method of example 3, except that the hyperbranched compound was not added, and glycerol with the same mass ratio was added.
Comparative example 4
The membrane material was prepared by the raw material ratio and preparation method of example 4, except that glycerol with the same mass ratio was added without adding a hyperbranched compound.
Comparative example 5
The membrane material was prepared by the raw material ratio and preparation method of example 5, except that the hyperbranched compound was not added, and glycerol with the same mass ratio was added.
Comparative example 6
A comparison was made of the best case of the previous membrane material patent (application No. 202110740000.5) as follows:
(1) weighing 1g of microcrystalline cellulose, dissolving the microcrystalline cellulose in 50ml of distilled water, adding 0.6g of 6mol/L sodium periodate solution, and mixing and stirring for 2 hours until the mixture is uniform to obtain oxidized microcrystalline cellulose; 0.6g (10%) of tannin was weighed out and dissolved in 2ml of distilled water; uniformly mixing oxidized microcrystalline cellulose and tannin water solution, placing the mixture in a constant-temperature water bath at the temperature of 60 ℃, and stirring and reacting for 10 to 30 minutes to enable the mixture to be crosslinked into a modified reinforcement;
(2) dissolving 6g of casein in 100ml of distilled water, adjusting the pH value of the solution to 8 by using a potassium hydroxide solution, and intensively stirring for about 0.5h until the solution is uniform to obtain a base solution;
(3) and stirring the modified reinforcement and the substrate solution for 10 minutes, adding 2g of glycerol, heating to 80 ℃, stirring in a constant-temperature water bath for 40 minutes until the mixture is uniform to obtain a resin membrane solution. And cooling and defoaming the prepared film forming liquid, and pouring the film forming liquid into a mold for film forming.
The film materials prepared in examples and comparative examples were subjected to tensile strength, water vapor transmission rate and water solubility tests, and the results are shown in table 1.
TABLE 1
As can be seen from Table 1, the film material prepared by the method has excellent tensile resistance and water vapor barrier property, compared with a comparative example, the biomass film obtained by the embodiment has higher tensile strength under the joint crosslinking action of the hyperbranched compound and the tannin, the film strength obtained by the embodiment is about several times of that of the comparative example, and the water vapor barrier property is obviously improved by about 2 times, especially, compared with the optimal scheme in the patent with the application number of 202110740000.5, the film material obtained by the technical scheme of the application has better water vapor barrier property, the water vapor transmission rate is about one third of that of the comparative example 6, and the advantages are obvious. The water solubility of the example as a whole is slightly reduced, but there is no significant effect. In addition, comparative examples 5 and 6 show that the molar ratio of tetraethyl titanate and triethanolamine in the hyperbranched compound has a large influence on the performance of the membrane material, and the molar ratio is changed from 1:2.5 to 1:1, so that the tensile strength and the water vapor transmission rate of the membrane material are greatly influenced.
Claims (7)
1. A high-strength bio-based film material is characterized by comprising the following components in parts by weight: 5-10 parts of casein, 3-5 parts of modifier and 100 parts of water; the modifier consists of 3-4 parts of hyperbranched compound and 0-1 part of tannin.
2. The high-strength biomass membrane material as claimed in claim 1, wherein the hyperbranched compound is prepared from tetraethyl titanate, triethanolamine and one-thousandth of mol of p-toluenesulfonic acid; wherein, in terms of mole ratio, tetraethyl titanate: triethanolamine is 1: 1-3.
3. The high-strength biomass membrane material as claimed in claim 2, wherein the hyperbranched compound is prepared by a method comprising: under the acidic condition, taking p-toluenesulfonic acid as a catalyst, and mixing and stirring tetraethyl titanate and triethanolamine at the temperature of 100-140 ℃ to prepare the hyperbranched compound.
4. The method for preparing the high-strength bio-based film material according to claim 1, wherein the high-strength bio-based film material is prepared by modifying casein with a modifier and then crosslinking the modified casein to form a film.
5. The method for preparing the high-strength biomass membrane material as claimed in claim 4, wherein the modification treatment is to prepare the hyperbranched compound, mix the hyperbranched compound with casein, and then perform a crosslinking reaction with tannin to modify the mixture.
6. The preparation method of the high-strength biomass membrane material as claimed in claim 5, which is characterized in that the specific preparation method comprises the following steps:
(1) preparing a hyperbranched compound by using p-toluenesulfonic acid as a catalyst at the temperature of 100 ℃ and 140 ℃ under an acidic condition;
(2) dissolving casein in an alkali solution, and uniformly stirring to obtain a base solution;
(3) mixing and stirring the hyperbranched compound and the substrate liquid, adding tannin, uniformly mixing, heating to 80 ℃, stirring in a constant-temperature water bath until the mixture is uniform to form a resin film liquid, cooling and defoaming, and pouring into a mold for casting to form a film.
7. The method for preparing a high-strength biomass membrane material as claimed in claim 6, wherein the alkali solution is a 30 wt% sodium hydroxide solution.
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|---|---|---|---|---|
| CN110483961A (en) * | 2019-09-30 | 2019-11-22 | 苏州中达航材料科技有限公司 | A kind of degradable mulch and preparation method thereof |
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| CN110483961A (en) * | 2019-09-30 | 2019-11-22 | 苏州中达航材料科技有限公司 | A kind of degradable mulch and preparation method thereof |
| CN113321936A (en) * | 2021-06-30 | 2021-08-31 | 西南林业大学 | High-strength biomass membrane material and preparation method thereof |
| CN114426779A (en) * | 2022-03-18 | 2022-05-03 | 西南林业大学 | Tannin biomimetic cross-linking-based all-biomass wood-bamboo composite material and preparation method thereof |
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