CN114349881A - Preparation method of modified hemicellulose suitable for PBAT (poly (butylene adipate-co-terephthalate)) degradable membrane bag - Google Patents
Preparation method of modified hemicellulose suitable for PBAT (poly (butylene adipate-co-terephthalate)) degradable membrane bag Download PDFInfo
- Publication number
- CN114349881A CN114349881A CN202210039002.6A CN202210039002A CN114349881A CN 114349881 A CN114349881 A CN 114349881A CN 202210039002 A CN202210039002 A CN 202210039002A CN 114349881 A CN114349881 A CN 114349881A
- Authority
- CN
- China
- Prior art keywords
- hemicellulose
- pbat
- modified
- modified hemicellulose
- activating
- 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.)
- Pending
Links
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a preparation method of modified hemicellulose suitable for a PBAT (poly (butylene adipate-co-terephthalate)) degradable membrane bag, which comprises the steps of activating the hemicellulose to release hydroxyl, carrying out acylation reaction by using acetic anhydride and n-butyric acid, introducing acetyl and butyryl, and finally carrying out separation, cleaning and crushing on the modified hemicellulose to obtain modified hemicellulose powder.
Description
Technical Field
The invention relates to the field of hemicellulose modification, in particular to a preparation method of modified hemicellulose in a PBAT degradation membrane bag.
Background
The film bags on the market at present are basically made of petroleum-based polyolefin serving as a raw material and are very difficult to degrade. The film bag part is incinerated, and the rest is transported to a landfill, so that the ecological environment is easily damaged, and the cost is increased due to the continuous rise of the petroleum price due to the gradual depletion of petroleum resources. Therefore, a film bag product which can replace petroleum-based film bag products and relieve the pressure of resources is urgently sought.
The hemicellulose is the most abundant polysaccharide except the cellulose, accounts for one third of the renewable biological resources on the earth, is a renewable and easily degradable raw material with great potential for preparing the membrane, is filled into a membrane material product, and can improve the economic benefit of a paper making enterprise on the basis of protecting the environment. However, the potential value of hemicellulose has not been paid attention so far, for example, in chemical pulp, cellulose in agriculture and forestry biomass raw materials is mainly utilized, and hemicellulose accounting for about 20% -38% of the content of the cellulose is dissolved in waste liquid during cooking; even if these waste liquids are burned to obtain energy, a great waste of resources is caused due to the low calorific value of hemicellulose;
the hemicellulose is added into the degradable resin to prepare the membrane, so that the membrane is environment-friendly and degradable, and the shortage of resources is relieved, so that the high-value utilization of the hemicellulose in the aspect of degrading the membrane material is realized. However, hemicellulose molecular chains contain a large amount of hydroxyl groups, so that intramolecular and intermolecular strong hydrogen bond interaction is caused, the hemicellulose molecular chains have the characteristic of easy moisture absorption, and the hemicellulose base film material has poor compatibility with PBAT degradation resin, so that the mechanical property of the hemicellulose base film material is greatly reduced, and the application of the hemicellulose base film material is limited. Therefore, there is a need in the art to develop a modified hemicellulose to improve its hydrophobicity, thermoplasticity and good processability, thereby overcoming the disadvantages of hemicellulose in practical applications.
Disclosure of Invention
The invention provides a preparation method of modified hemicellulose in a PBAT (poly (butylene adipate-co-terephthalate)) degradable membrane bag, which aims to solve the technical problems.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of modified hemicellulose suitable for a PBAT degradation membrane bag is characterized by comprising the following specific preparation steps:
step one, activating hemicellulose: adding a solvent into hemicellulose according to the mass ratio of 1:10-100, adding an activating agent, uniformly stirring, and activating for 8-12 h.
Step two, acylation of hemicellulose: and (3) moving the activated hemicellulose to a reaction kettle, adding a catalyst and an acylating reagent, and heating to 60-90 ℃ for reaction for 1-5 h. After the reaction was completed, it was cooled to room temperature.
Step three, preparing modified hemicellulose powder: adding 4 times volume of 95% ethanol solution into the modified hemicellulose solution to precipitate the modified hemicellulose, washing with 95% ethanol for 2 times, washing with acetone for 1 time, air drying for 12h, drying in a 50 deg.C oven for 16-34h, and pulverizing with a pulverizer.
Preferably, in the first step, the hemicellulose is added into the solvent according to the solid-to-liquid ratio of 1: 10-100.
Preferably, the solvent in the first step is one or more of N, N-Dimethylformamide (DMF), dimethylacetamide, dimethylsulfoxide, tetrahydrofuran or deionized water.
Preferably, the activating agent in the first step is one or more of liquid alkali, glacial acetic acid, acetic anhydride, concentrated sulfuric acid and butyric acid.
Preferably, the catalyst of the second step is one or more of bromosuccinimide (NBS), pyridine, 4-dimethylaminopyridine, N-methylpyrrolidone and sulfuric acid, and the amount of the catalyst is 0.2-0.5% of the equivalent of hemicellulose.
Preferably, the acylating agent in the second step is acetic anhydride and n-butyric acid, and the molar ratio of the two is 1-5: 1.
Preferably, the particle size of the modified hemicellulose obtained after the pulverization in the third step is less than 10 μm.
Compared with the prior art, the invention has the following beneficial effects:
1) the hemicellulose powder extracted and modified by the papermaking waste liquid and the PBAT resin are blended and modified, and the prepared PBAT film bag product still has good mechanical property and impact resistance and can meet the use requirement.
2) The hemicellulose dry powder extracted and modified by the papermaking waste liquid is filled into the PBAT resin, so that the use amount of plastic base materials can be reduced, and the cost of film bag products is reduced.
3) The modification process is simple and easy to operate, and can be operated and produced in large batch;
Detailed Description
The present invention is further illustrated by way of examples, but is not intended to be limited thereby within the scope of the examples described. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
Activating hemicellulose: adding N, N-Dimethylformamide (DMF) into 100g of hemicellulose according to a ratio of 1:20, adding 10g of glacial acetic acid and 10g of acetic anhydride, and activating for 8 hours.
② acylation of hemicellulose: the activated hemicellulose is transferred to a reaction kettle, 0.3g of bromosuccinimide (NBS) serving as a catalyst, 30.6g of acetic anhydride and 10g of n-butyric acid are added, and the mixture reacts for 2 hours at 80 ℃. After the reaction was completed, it was cooled to room temperature.
③ preparing modified hemicellulose powder: adding a 95% ethanol solution with the volume 4 times that of the modified hemicellulose solution to precipitate the modified hemicellulose, washing with 95% ethanol for 2 times, washing with acetone for 1 time, air-drying for 12 hours, drying in an oven at 50 ℃ for 16 hours, and finally crushing with a crusher, wherein the particle size of the crushed modified hemicellulose is below 10 mu m.
Example 2
Activating hemicellulose: adding N, N-Dimethylformamide (DMF) into 100g of hemicellulose according to a ratio of 1:30, adding 10g of glacial acetic acid and 10g of acetic anhydride, and activating for 8 hours.
② acylation of hemicellulose: the activated hemicellulose is transferred into a reaction kettle, 0.3g of 4-dimethylaminopyridine serving as a catalyst, 30.6g of acetic anhydride and 10g of n-butyric acid are added, and the mixture reacts for 2 hours at the temperature of 80 ℃. After the reaction was completed, it was cooled to room temperature.
③ preparing modified hemicellulose powder: adding a 95% ethanol solution with the volume 4 times that of the modified hemicellulose solution to precipitate the modified hemicellulose, washing with 95% ethanol for 2 times, washing with acetone for 1 time, air-drying for 12 hours, drying in an oven at 50 ℃ for 16 hours, and finally crushing with a crusher, wherein the particle size of the crushed modified hemicellulose is below 10 mu m.
Example 3
Activating hemicellulose: adding pure water into 100g of hemicellulose according to the ratio of 1:50, adding 30g of liquid alkali as an activating agent, and activating for 8 hours.
② acylation of hemicellulose: the activated hemicellulose is transferred to a reaction kettle, 0.3g of bromosuccinimide (NBS) serving as a catalyst, 30.6g of acetic anhydride and 10g of n-butyric acid are added, and the mixture reacts for 2 hours at 80 ℃. After the reaction was completed, it was cooled to room temperature.
③ preparing modified hemicellulose powder: adding a 95% ethanol solution with the volume 4 times that of the modified hemicellulose solution to precipitate the modified hemicellulose, washing with 95% ethanol for 2 times, washing with acetone for 1 time, air-drying for 12 hours, drying in an oven at 50 ℃ for 16 hours, and finally crushing with a crusher, wherein the particle size of the crushed modified hemicellulose is below 10 mu m.
Example 4
Activating hemicellulose: adding pure water into 100g of hemicellulose according to the ratio of 1:50, adding 30g of liquid alkali as an activating agent, and activating for 8 hours.
② acylation of hemicellulose: the activated hemicellulose is transferred to a reaction kettle, 0.3g of bromosuccinimide (NBS) serving as a catalyst, 55g of acetic anhydride and 10g of n-butyric acid are added, and the mixture is reacted for 1 hour at 70 ℃. After the reaction was completed, it was cooled to room temperature.
③ preparing modified hemicellulose powder: adding a 95% ethanol solution with the volume 4 times that of the modified hemicellulose solution to precipitate the modified hemicellulose, washing with 95% ethanol for 2 times, washing with acetone for 1 time, air-drying for 12 hours, drying in an oven at 50 ℃ for 16 hours, and finally crushing with a crusher, wherein the particle size of the crushed modified hemicellulose is below 10 mu m.
Application effects example:
1. putting the modified hemicellulose, PBAT, corn starch, glycerol and TAS-2A into a high-speed blender together, and mixing for 50min at the rotating speed of 200rpm to obtain a primary mixture. The composition and the content are as follows according to the mass portion:
2. and (3) putting the primary mixture into a double-screw extruder for extrusion granulation, wherein the temperature from the first zone to the sixth zone is 105 ℃, 130 ℃, 145 ℃, 155 ℃, 165 ℃, 170 ℃, the head temperature is 170 ℃, and the screw rotation speed is 190rpm, and performing melt extrusion to obtain the master batch.
3. And (3) putting the master batches into a film blowing machine, and carrying out blow molding bag making and molding at 155 ℃ to prepare the PBAT film bag.
Comparative example 1
A PE shopping bag film and a preparation method thereof are disclosed, which comprises the following components in parts by weight:
the above formula is reacted according to the following steps:
1. and (3) putting the PBAT, the corn starch, the glycerol and the TAS-2A into a high-speed blender together, and mixing for 50min at the rotating speed of 200rpm to obtain a primary mixture.
2. And (3) putting the primary mixture into a double-screw extruder for extrusion granulation, wherein the temperature from the first zone to the sixth zone is 105 ℃, 130 ℃, 145 ℃, 155 ℃, 165 ℃, 170 ℃, the head temperature is 170 ℃, and the screw rotation speed is 190rpm, and performing melt extrusion to obtain the master batch.
3. And (3) putting the master batches into a film blowing machine, and carrying out blow molding bag making and molding at 155 ℃ to prepare the PBAT film bag.
Comparative example 2
A PE shopping bag film and a preparation method thereof are disclosed, which comprises the following components in parts by weight:
the above formula is reacted according to the following steps:
1. and (3) putting the PBAT, the corn starch, the calcium carbonate, the sorbitol and the stearic acid into a high-speed blender together, and mixing for 40min at the rotating speed of 400rpm to obtain a primary mixture.
2. And (3) putting the primary mixture into a double-screw extruder for extrusion granulation, wherein the temperature from the first zone to the sixth zone is 125 ℃, 130 ℃, 145 ℃, 155 ℃, 165 ℃, 170 ℃, the head temperature is 175 ℃, and the screw rotation speed is 200rpm, and performing melt extrusion to obtain the master batch.
3. And (3) putting the master batch into a film blowing machine, and carrying out blow molding bag making and molding at 165 ℃ to prepare the PE shopping bag film.
The performance of examples 1-4 and comparative examples was tested by a universal electronic tensile tester (model KY 8000C) according to the standard (GB/T1040.2-2006), and the specific data are shown in Table 1.
TABLE 1
| Tensile strength/MPa | Elongation at break/% | |
| Example 1 | 18.2 | 350.5 |
| Example 2 | 17.5 | 335.2 |
| Example 3 | 18.5 | 343.5 |
| Example 4 | 18.4 | 325.9 |
| Comparative example 1 | 18.2 | 343.1 |
| Comparative example 2 | 17.9 | 339.5 |
The data result in table 1 shows that the hemicellulose modified by extracting the papermaking waste liquid is suitable for the tensile property and impact property data display of the PBAT film bag, and the hemicellulose modified PBAT film bag extracted and modified by the papermaking waste liquid can meet the use requirement.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A preparation method of modified hemicellulose suitable for a PBAT degradation membrane bag is characterized by comprising the following specific preparation steps:
step one, activating hemicellulose: adding a solvent into hemicellulose according to the mass ratio of 1:10-100, adding an activating agent, uniformly stirring, and activating for 8-12 h.
Step two, acylation of hemicellulose: and (3) moving the activated hemicellulose to a reaction kettle, adding a catalyst and an acylating reagent, and heating to 60-90 ℃ for reaction for 1-5 h. After the reaction was completed, it was cooled to room temperature.
Step three, preparing modified hemicellulose powder: adding 4 times volume of 95% ethanol solution into the modified hemicellulose solution to precipitate the modified hemicellulose, washing with 95% ethanol for 2 times, washing with acetone for 1 time, air drying for 12h, drying in a 50 deg.C oven for 16-34h, and pulverizing with a pulverizer.
2. The method for preparing modified hemicellulose suitable for use in a PBAT degradation membrane bag according to claim 1, wherein in the first step, the hemicellulose is added to the solvent according to a solid-to-liquid ratio of 1: 10-100.
3. The method of claim 1, wherein the solvent in the first step is one or more of N, N-Dimethylformamide (DMF), dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, or deionized water.
4. The method for preparing modified hemicellulose suitable for use in a PBAT degradation membrane bag of claim 1, wherein the activating agent in the first step is one or more of liquid caustic soda, glacial acetic acid, acetic anhydride, concentrated sulfuric acid, and butyric acid.
5. The method of claim 1, wherein the catalyst used in step two is one or more selected from bromosuccinimide (NBS), pyridine, 4-dimethylaminopyridine, N-methylpyrrolidine, N-methylpyrrolidone, and sulfuric acid, and the amount of the catalyst is 0.2-0.5% of the equivalent weight of hemicellulose.
6. The method for preparing modified hemicellulose suitable for PBAT degradation membrane bags according to claim 1, wherein the acylating agent in the second step is acetic anhydride and n-butyric acid at a molar ratio of 1-5: 1.
7. The method for preparing modified hemicellulose suitable for use in PBAT degradable membrane bags according to claim 1, wherein the particle size of the modified hemicellulose obtained after the pulverization in step three is below 10 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210039002.6A CN114349881A (en) | 2022-01-13 | 2022-01-13 | Preparation method of modified hemicellulose suitable for PBAT (poly (butylene adipate-co-terephthalate)) degradable membrane bag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210039002.6A CN114349881A (en) | 2022-01-13 | 2022-01-13 | Preparation method of modified hemicellulose suitable for PBAT (poly (butylene adipate-co-terephthalate)) degradable membrane bag |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114349881A true CN114349881A (en) | 2022-04-15 |
Family
ID=81109981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210039002.6A Pending CN114349881A (en) | 2022-01-13 | 2022-01-13 | Preparation method of modified hemicellulose suitable for PBAT (poly (butylene adipate-co-terephthalate)) degradable membrane bag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114349881A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116606387A (en) * | 2023-04-21 | 2023-08-18 | 广东药科大学 | Chemically modified hemicellulose solid particles, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240034A (en) * | 2008-03-14 | 2008-08-13 | 中国科学院广州化学研究所 | Method for preparing cellulose acetate butyrate |
| CN113248875A (en) * | 2021-03-29 | 2021-08-13 | 上海昶法新材料有限公司 | Fully-degradable shopping bag film and preparation method thereof |
| CN113603796A (en) * | 2021-08-31 | 2021-11-05 | 潍坊工程职业学院 | Preparation method of cellulose acetate butyrate |
-
2022
- 2022-01-13 CN CN202210039002.6A patent/CN114349881A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240034A (en) * | 2008-03-14 | 2008-08-13 | 中国科学院广州化学研究所 | Method for preparing cellulose acetate butyrate |
| CN113248875A (en) * | 2021-03-29 | 2021-08-13 | 上海昶法新材料有限公司 | Fully-degradable shopping bag film and preparation method thereof |
| CN113603796A (en) * | 2021-08-31 | 2021-11-05 | 潍坊工程职业学院 | Preparation method of cellulose acetate butyrate |
Non-Patent Citations (3)
| Title |
|---|
| 任俊莉等: ""半纤维素化学改性"", 《高分子通报》 * |
| 彭俏等: ""玉米芯半纤维素提取、乙酰化改性及结构表征"，https://doi.org/10.13386/j.issn1002-0306.2021080087", 《食品工业科技》 * |
| 彭锋等: ""木聚糖衍生物及膜材料研究进展"", 《林业工程学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116606387A (en) * | 2023-04-21 | 2023-08-18 | 广东药科大学 | Chemically modified hemicellulose solid particles, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Moubarik et al. | Structural and thermal characterization of Moroccan sugar cane bagasse cellulose fibers and their applications as a reinforcing agent in low density polyethylene | |
| Cao et al. | Water-soluble cellulose acetate from waste cotton fabrics and the aqueous processing of all-cellulose composites | |
| CN101463137B (en) | Method for preparing natural polymer blended membrane with ion liquid as solvent | |
| CN108587087B (en) | Degradable polylactic acid composite material for environment-friendly tableware and preparation method thereof | |
| CN112029123B (en) | Nano-cellulose/lignosulfonic acid composite film and preparation method and application thereof | |
| CN111690240A (en) | Polylactic acid/nano cellulose composite material and preparation method thereof | |
| CN106917309B (en) | A kind of preparation method of corn stalk stalks of rice, wheat, etc. cellulose short-term training film | |
| CN113248875A (en) | Fully-degradable shopping bag film and preparation method thereof | |
| CN113801339A (en) | Modified lignin and preparation method thereof | |
| CN105884907A (en) | Method for separating components of straws to prepare ultralow-viscosity carboxymethyl cellulose | |
| Shuaiyang et al. | Preparation of xylan citrate—A potential adsorbent for industrial wastewater treatment | |
| CN101709113B (en) | Preparation of macromolecular compatible additive, namely urea-formaldehyde modified lignin and application of macromolecular compatible additive | |
| CN102212212A (en) | Method for preparing organosolv lignin modified starch thermoplastic composite material | |
| CN111349253A (en) | Modified lignin/PBS (Poly Butylene succinate) bioplastic film and preparation method thereof | |
| CN107118393A (en) | The preparation method of modified cellulose/lactic acid composite material | |
| CN114349881A (en) | Preparation method of modified hemicellulose suitable for PBAT (poly (butylene adipate-co-terephthalate)) degradable membrane bag | |
| CN114292350B (en) | Hemicellulose cinnamate, preparation method thereof and application thereof in biodegradable composite material | |
| Roostazadeh et al. | Isolation and characterization of lignin-rich particles as byproducts of bioethanol production from wheat straw to reinforce starch composite films | |
| CN108359157B (en) | A kind of preparation method of polyethylene/calcium carbonate/sisal fiber crystallite composite material | |
| Zhang et al. | Co-modification of corn straw lignin and its enhancement on glue-free fiberboard based on freezing activated wood fibers | |
| Ju et al. | Thermal and mechanical properties of polyethylene glycol (PEG)-modified lignin/polylactic acid (PLA) biocomposites | |
| CN104497609B (en) | A kind of preparation method of Whole fiber degradable composite material | |
| Ju et al. | Efficient preparation of polyethylene glycol (PEG)-modified lignin from steam exploded hardwood biomass | |
| CN101831001B (en) | Method for preparing konjak glucomannan acetate thermoplastic material | |
| Tian et al. | Efficient separation of acetylated cellulose from eucalyptus and its enhancement on the mechanical strength of polylactic acid |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220415 |