CN115386011B - Preparation method of cyanoethyl cellulose - Google Patents
Preparation method of cyanoethyl cellulose Download PDFInfo
- Publication number
- CN115386011B CN115386011B CN202211030859.8A CN202211030859A CN115386011B CN 115386011 B CN115386011 B CN 115386011B CN 202211030859 A CN202211030859 A CN 202211030859A CN 115386011 B CN115386011 B CN 115386011B
- Authority
- CN
- China
- Prior art keywords
- cellulose
- reaction
- solution
- acrylonitrile
- cyanoethyl
- 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
- KXJGSNRAQWDDJT-UHFFFAOYSA-N 1-acetyl-5-bromo-2h-indol-3-one Chemical compound BrC1=CC=C2N(C(=O)C)CC(=O)C2=C1 KXJGSNRAQWDDJT-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229920002678 cellulose Polymers 0.000 claims abstract description 106
- 239000001913 cellulose Substances 0.000 claims abstract description 106
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 238000006266 etherification reaction Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000004090 dissolution Methods 0.000 claims abstract description 7
- 235000010980 cellulose Nutrition 0.000 claims description 103
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 74
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 claims description 53
- 238000001035 drying Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 25
- 150000007530 organic bases Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 3
- 229920001131 Pulp (paper) Polymers 0.000 claims description 3
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 3
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 3
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241001330002 Bambuseae Species 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 44
- 238000001556 precipitation Methods 0.000 description 24
- 239000003795 chemical substances by application Substances 0.000 description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 description 22
- 239000001569 carbon dioxide Substances 0.000 description 22
- 238000000921 elemental analysis Methods 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 239000000843 powder Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229920000875 Dissolving pulp Polymers 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 pulp Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/14—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with nitrogen-containing groups
- C08B11/155—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with nitrogen-containing groups with cyano groups, e.g. cyanoalkyl ethers
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The application discloses a preparation method of cyanoethyl cellulose. The preparation method comprises the following steps: uniformly mixing cellulose, organic alkali and organic solvent, and introducing CO 2 Carrying out dissolution reaction to obtain cellulose solution; and mixing the cellulose solution with acrylonitrile to carry out homogeneous etherification reaction, thus obtaining cyanoethyl cellulose. The preparation method provided by the application is that the cyanoethyl cellulose synthesized under homogeneous phase condition is free from water participation in the whole process, reduces the occurrence of side reaction, and has the advantages of mild condition, simple operation, less side reaction and no need of additional catalyst.
Description
Technical Field
The application relates to a preparation method of cyanoethyl cellulose, belonging to the technical field of chemical synthesis.
Background
As a natural polymer with the most abundant content in nature, cellulose is attracting attention, and the yield thereof is about 35% -50% of the total biomass raw material. Cellulose is a linear polymer of Anhydroglucose (AGU) linked by beta-1, 4 glycosidic bond, each AGU has three hydroxyl groups linked thereto, each at C 2 C 3 C 6 In the above, a series of reactions such as etherification and esterification may occur, thereby improving the functions thereof. The product has excellent properties such as high strength and high thermal stability, and can be widely applied to various industries such as packaging, cosmetics and the like.
Cyanoethyl cellulose (CEC) is a class of cellulose ether derivatives developed and developed earlier, and has been proposed by forensic first patent reports in 1938, and is prepared by michel addition reaction of cellulose and acrylonitrile in an alkaline environment, and is essentially a nucleophilic addition reaction of unsaturated carbon-nitrogen triple bonds on acrylonitrile with active proton hydrogen on cellulose. Low substituted (ds=0.3 to 0.5) cyanoethyl cellulose can prevent bacterial and mold attack for use in textiles; the highly substituted cyanoethyl cellulose has a high dielectric constant and low dielectric loss and is useful as a starting material component in electroluminescent devices.
Common methods for preparing cyanoethyl cellulose are both homogeneous and heterogeneous. The homogeneous reaction means that cellulose is dissolved to obtain a uniform cellulose solution, and then the uniform cellulose solution is subjected to etherification reaction with acrylonitrile, so that cyanoethyl cellulose is prepared. Zhang Lina et al successfully synthesized cyanoethyl cellulose in a sodium hydroxide/water/urea homogeneous system of cellulose (CN 201610124958.7). However, the system is an aqueous phase system, and side reactions such as hydrolysis of acrylonitrile and the like are inevitably generated, so that the purity and uniformity of the product are limited. The heterogeneous reaction is to firstly alkalize cellulose to obtain alkali cellulose, then directly carry out etherification reaction with acrylonitrile, thereby realizing the preparation of cyanoethyl cellulose, zhong Linglong and the like successfully synthesizes cyanoethyl cellulose in a cellulose sodium hydroxide/alcohol system through heterogeneous reaction (CN 2017/079429). However, cyanoethylcellulose produced by this method often requires a large amount of etherifying agent and the purity and uniformity of the product are limited.
Disclosure of Invention
The application mainly aims to provide a preparation method of cyanoethyl cellulose, which solves the defects of the traditional homogeneous or heterogeneous system for preparing cyanoethyl cellulose, and has the advantages of mild condition, simple operation, low price and less side reaction.
In order to achieve the purpose of the application, the technical scheme adopted by the application comprises the following steps:
the embodiment of the application provides a preparation method of cyanoethyl cellulose, which comprises the following steps:
uniformly mixing cellulose, organic alkali and organic solvent, and introducing CO 2 Carrying out dissolution reaction to obtain cellulose solution;
and mixing the cellulose solution with acrylonitrile to carry out homogeneous etherification reaction, thus obtaining cyanoethyl cellulose.
In some embodiments, the dissolution reaction is carried out at a temperature of 30 to 70 ℃ for a reaction time of 0.5 to 5 hours, CO 2 The pressure is 0.1-2.0 MPa.
In some embodiments, the homogeneous etherification reaction is at a temperature of 10 to 80 ℃ for a time of 0.5 to 20 hours.
Compared with the prior art, the application has the beneficial effects that at least:
the preparation method provided by the application is that the cyanoethyl cellulose synthesized under homogeneous phase condition is free from water participation in the whole process, reduces the occurrence of side reaction, and has the advantages of mild condition, simple operation, less side reaction and no need of additional catalyst.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a cyanoethylcellulose product prepared in example 1 of the present application 1 H NMR chart.
FIG. 2 is a FT-IR chart of cyanoethylcellulose as prepared in example 1 of the present application.
FIG. 3 is an XRD pattern of cyanoethylcellulose as prepared in example 1 of the present application.
FIG. 4 is a TGA graph of cyanoethylcellulose as a product prepared in example 1 of the present application.
Detailed Description
As described above, in view of the shortcomings of the prior art, the present inventors have long studied and have put forward a great deal of practice to propose the technical solution of the present application, specifically, to prepare cyanoethyl cellulose by reacting cellulose with acrylonitrile in a homogeneous system after dissolving cellulose. The technical scheme, the implementation process, the principle and the like are further explained as follows.
One aspect of the embodiment of the application provides a preparation method of cyanoethyl cellulose, which comprises the following steps:
uniformly mixing cellulose, organic alkali and organic solvent, and introducing CO 2 Carrying out dissolution reaction to obtain cellulose solution;
and mixing the cellulose solution with acrylonitrile to carry out homogeneous etherification reaction, thus obtaining cyanoethyl cellulose.
The reaction mechanism for homogeneously preparing cyanoethyl cellulose in the application may be as follows: mixing cellulose with organic alkali and organic solvent, and introducing CO 2 And dissolving cellulose, wherein a system can generate a cellulose carbonate ion intermediate in situ in the dissolving process, and the anion part of the intermediate has nucleophilicity and can perform Michael addition reaction with acrylonitrile containing double bonds, so that homogeneous etherification reaction is realized, and cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying after the reaction is finished.
In some embodiments, the method of making further comprises: and after the homogeneous etherification reaction is finished, sequentially precipitating, filtering, washing and drying the reaction system to obtain cyanoethyl cellulose.
In some more preferred embodiments, the preparation method of cyanoethyl cellulose specifically comprises the following steps:
step one: mixing cellulose with organic base and organic solvent, and introducing CO 2 And (3) reacting and dissolving cellulose to obtain a cellulose solution.
Step two: mixing the cellulose solution with acrylonitrile for homogeneous etherification reaction, and carrying out precipitation, filtration, washing and drying after the reaction is finished to obtain cyanoethyl cellulose.
In some embodiments, in step one, the cellulose has the formula:wherein n is the Degree of Polymerization (DP), and 100 < n < 2000.
Further, the cellulose is selected from microcrystalline cellulose, alpha-cellulose, and any one or a combination of two or more kinds of cellulose separated from corncob, cotton, pulp, wood pulp, bamboo pulp, agriculture and forestry straw, etc., but is not limited thereto.
In some embodiments, in step one, the organic base is an organic base having a pKa greater than 20, and the organic base includes any one or a combination of two or more of 1, 8-diazabicyclo-bis [5,4,0] -7-undecene (DBU), 1,5, 7-triazabicyclo [4, 0] dec-5-ene (TBD), 1, 5-diazabicyclo [4,3,0] non-5-ene (DBN), and the like, but is not limited thereto.
In some embodiments, in the first step, the organic solvent is a polar aprotic organic solvent having a boiling point higher than 150 ℃, and the organic solvent includes any one or a combination of two or more of dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), and the like, but is not limited thereto.
In some embodiments, in step one, the molar ratio of the organic base to anhydroglucose units (AGU) in the cellulose is (2-4) to 1.
In some embodiments, in the first step, the dissolution reaction is carried out at a temperature of 30-70 ℃ for a reaction time of 0.5-5 h, and CO 2 The pressure is 0.1-2.0 MPa.
In some embodiments, in step one, the concentration of the cellulose solution is from 1.0 to 10.0wt%.
In some embodiments, in step two, the molar ratio of acrylonitrile to anhydroglucose units (AGU) in the cellulose is (1-20) to 1.
In some embodiments, in step two, the homogeneous etherification reaction is carried out at a temperature of from 10 to 80 ℃ for a time of from 0.5 to 20 hours.
In conclusion, the preparation method provided by the application is that the cyanoethyl cellulose synthesized under the homogeneous phase condition has no water participation in the whole process, reduces the occurrence of side reaction, and has mild condition, simple operation and no need of additional catalyst.
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is further elucidated below with reference to the detailed description and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the present application, and the experimental conditions and setting parameters thereof should not be construed as limiting the basic technical scheme of the present application. And the scope of the present application is not limited to the following examples. In addition, the technical features of the embodiments of the present application described below may be combined with each other as long as they do not collide with each other.
Unless otherwise indicated, the starting materials and reagents in the examples of the application were all purchased commercially.
Example 1
Corncob cellulose (dp=1440) (4.72 g), DMSO (100.00 g), DBU (13.28 g) were mixed (molar ratio of DBU to AGU is 3:1), then carbon dioxide (0.1 MPa) was introduced, and the mixture was allowed to react at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 4 wt%; then 17.26g of the solution is taken, 3.33g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to the AGU is 13:1) is added, the reaction is carried out for 8 hours at 60 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder and is soluble in DMSO solution, and the nitrogen content in elemental analysis is 6.37%.
The product cyanoethyl cellulose prepared in this example 1 The H NMR chart is shown in FIG. 1, the FT-IR chart is shown in FIG. 2, the XRD chart is shown in FIG. 3, and the TGA chart is shown in FIG. 4.
Example 2
Microcrystalline cellulose (dp=180) (11.52 g), DMSO (100.00 g), DBU (34.56 g) were mixed (molar ratio of DBU to AGU is 3:1), then carbon dioxide (0.5 MPa) was introduced and reacted at 35 ℃ for 4 hours to obtain a cellulose solution having a cellulose concentration of 8 wt%; then 18.18g of the solution is taken, 3.27g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to AGU is 7:1) is added, the reaction is carried out for 2 hours at 60 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder and is soluble in dilute alkali solution, and the nitrogen content in elemental analysis is 2.83%.
Example 3
Pulp cellulose (dp=800) (2.17 g), DMSO (100.00 g), DBU (6.51 g) were mixed (molar ratio of DBU to AGU is 3:1), then carbon dioxide (0.1 MPa) was introduced and reacted at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 2 wt%; then 17.81g of the solution is taken, 1.72g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to AGU is 15:1) is added, the reaction is carried out for 11 hours at 60 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder and is soluble in DMSO solution, and the nitrogen content in elemental analysis is 2.83%.
Example 4
Corncob cellulose (dp=1440) (4.42 g), DMF (100.00 g), DBU (5.98 g) were mixed (molar ratio of DBU to AGU is 3:1), then carbon dioxide (0.1 MPa) was introduced, and the mixture was allowed to react at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 4 wt%; then 16.83g of the solution is taken, 1.51g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to the AGU is 7:1) is added, the reaction is carried out for 8 hours at 60 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder, and is soluble in DMSO solution and dilute alkali solution, and the nitrogen content in elemental analysis is 3.21%.
Example 5
Corncob cellulose (dp=1440) (4.47 g), DMAc (100.00 g) and DBU (7.12 g) were mixed (the molar ratio of DBU to AGU is 3:1), and then carbon dioxide (0.1 MPa) was introduced and reacted at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 4 wt%; then 18.71g of the solution is taken, 3.37g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to the AGU is 13:1) is added, the reaction is carried out for 8 hours at 60 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder and is soluble in dilute alkali solution, and the nitrogen content in elemental analysis is 2.93%.
Example 6
Corncob cellulose (dp=1440) (3.39 g), DMSO (100.00 g), TBD (9.54 g) were mixed (molar ratio of DBU to AGU 3:1), then carbon dioxide (1.0 MPa) was introduced and reacted at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 3 wt%; then 16.39g of the solution is taken, 2.37g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to AGU is 15:1) is added, the reaction is carried out for 20 hours at 60 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder, and is soluble in DMSO solution and dilute alkali solution, and the nitrogen content in elemental analysis is 3.61%.
Example 7
Corncob cellulose (dp=1440) (4.72 g), DMSO (100.00 g), DBN (13.28 g) were mixed (molar ratio of DBU to AGU is 3:1), then carbon dioxide (0.1 MPa) was introduced, and the mixture was allowed to react at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 4 wt%; then 20.53g of the solution is taken, 1.85g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to the AGU is 7:1) is added, the reaction is carried out for 5 hours at 60 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder and is soluble in DMSO solution, and the nitrogen content in elemental analysis is 5.08%.
Example 8
Corncob cellulose (dp=1440) (4.72 g), DMSO (100.00 g), DBU (13.28 g) were mixed (molar ratio of DBU to AGU is 3:1), then carbon dioxide (0.1 MPa) was introduced, and the mixture was allowed to react at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 4 wt%; then 17.24g of the solution is taken, 3.58g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to AGU is 15:1) is added, the reaction is carried out for 2 hours at 60 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder and is soluble in DMSO solution, and the nitrogen content in elemental analysis is 4.56%.
Example 9
Corncob cellulose (dp=1440) (4.72 g), DMSO (100.00 g), DBU (13.28 g) were mixed (molar ratio of DBU to AGU is 3:1), then carbon dioxide (0.1 MPa) was introduced, and the mixture was allowed to react at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 4 wt%; then 17.19g of the solution is taken, 2.43g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to the AGU is 11:1) is added, the reaction is carried out for 8 hours at 60 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder and is soluble in DMSO solution, and the nitrogen content in elemental analysis is 6.65%.
Example 10
Corncob cellulose (dp=1440) (7.78 g), DMSO (100.00 g), DBU (21.90 g) were mixed (molar ratio of DBU to AGU is 3:1), then carbon dioxide (1.5 MPa) was introduced, and the mixture was allowed to react at 65 ℃ for 1 hour to obtain a cellulose solution having a cellulose concentration of 6 wt%; then 16.91g of the solution is taken, 2.82g of acrylonitrile (the mol ratio of etherifying agent acrylonitrile to AGU is 7:1) is added, the reaction is carried out for 11 hours at 60 ℃, after the reaction is finished, cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder and is soluble in dilute alkali solution, and the nitrogen content in elemental analysis is 1.05%.
Example 11
Corncob cellulose (dp=1440) (4.72 g), DMSO (100.00 g), DBU (13.28 g) were mixed (molar ratio of DBU to AGU is 3:1), then carbon dioxide (0.1 MPa) was introduced, and the mixture was allowed to react at 55 ℃ for 3 hours to obtain a cellulose solution having a cellulose concentration of 4 wt%; then 20.46g of the solution is taken, 2.89g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to the AGU is 11:1) is added, the reaction is carried out for 8 hours at 50 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder and is soluble in DMSO solution, and the nitrogen content in elemental analysis is 5.83%.
Example 12
Corncob cellulose (dp=1440) (4.62 g), DMSO (100.00 g), DBU (10.83 g) were mixed (molar ratio of DBU to AGU is 2.5:1), then carbon dioxide (0.1 MPa) was introduced, and the mixture was allowed to react at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 4 wt%; then 16.80g of the solution is taken, 2.56g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to the AGU is 11:1) is added, the reaction is carried out for 8 hours at 60 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder and is soluble in dilute alkali solution, and the nitrogen content in elemental analysis is 1.41%.
Example 13
Corncob cellulose (dp=1440) (4.83 g), DMSO (100.00 g), DBU (15.86 g) were mixed (molar ratio of DBU to AGU is 3.5:1), then carbon dioxide (0.1 MPa) was introduced, and the mixture was allowed to react at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 4 wt%; then 17.54g of the solution is taken, 2.67g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to the AGU is 11:1) is added, the reaction is carried out for 8 hours at 60 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder and is soluble in dilute alkali solution, and the nitrogen content in elemental analysis is 3.11%.
Example 14
Corncob cellulose (dp=1440) (4.72 g), DMSO (100.00 g), DBU (13.28 g) were mixed (molar ratio of DBU to AGU is 3:1), then carbon dioxide (0.1 MPa) was introduced, and the mixture was allowed to react at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 4 wt%; then 22.34g of the solution is taken, 3.16g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to the AGU is 11:1) is added, the reaction is carried out for 8 hours at 20 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder and is soluble in dilute alkali solution, and the nitrogen content in elemental analysis is 1.44%.
Example 15
Corncob cellulose (dp=1440) (4.72 g), DMSO (100.00 g), DBU (13.28 g) were mixed (molar ratio of DBU to AGU is 3:1), then carbon dioxide (0.1 MPa) was introduced, and the mixture was allowed to react at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 4 wt%; then 21.79g of the solution is taken, 3.08g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to AGU is 11:1) is added, the reaction is carried out for 8 hours at 80 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder, and is soluble in DMSO solution and dilute alkali solution, and the nitrogen content in elemental analysis is 1.68%.
Example 16
Corncob cellulose (dp=1440) (4.72 g), DMSO (100.00 g), DBU (13.28 g) were mixed (molar ratio of DBU to AGU is 3:1), then carbon dioxide (0.1 MPa) was introduced, and the mixture was allowed to react at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 4 wt%; then 17.85g of the solution is taken, 2.52g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to the AGU is 11:1) is added, the reaction is carried out for 2 hours at 60 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder and is soluble in DMSO solution, and the nitrogen content in elemental analysis is 6.01%.
Example 17
Corncob cellulose (dp=1440) (4.72 g), DMSO (100.00 g), DBU (13.28 g) were mixed (molar ratio of DBU to AGU is 3:1), then carbon dioxide (0.1 MPa) was introduced, and the mixture was allowed to react at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 4 wt%; then 18.21g of the solution is taken, 2.57g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to AGU is 11:1) is added, the reaction is carried out at 60 ℃ for 11 hours, after the reaction is finished, cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder and is soluble in DMSO solution, and the nitrogen content in elemental analysis is 5.12%.
Example 18
Corncob cellulose (dp=1440) (4.72 g), DMSO (100.00 g), DBU (13.28 g) were mixed (molar ratio of DBU to AGU is 3:1), then carbon dioxide (0.1 MPa) was introduced, and the mixture was allowed to react at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 4 wt%; then 22.50g of the solution is taken, 3.18g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to the AGU is 11:1) is added, the reaction is carried out for 20 hours at 60 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder and is soluble in DMSO solution, and the nitrogen content in elemental analysis is 4.81%.
Example 19
Corncob cellulose (dp=1440) (4.72 g), DMSO (100.00 g), DBU (13.28 g) were mixed (molar ratio of DBU to AGU is 3:1), then carbon dioxide (0.1 MPa) was introduced, and the mixture was allowed to react at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 4 wt%; then 16.29g of the solution is taken, 1.88g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to the AGU is 9:1) is added, the reaction is carried out for 8 hours at 20 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder and is soluble in dilute alkali solution, and the nitrogen content in elemental analysis is 2.54%.
Example 20
Corncob cellulose (dp=1440) (4.72 g), DMSO (100.00 g), DBU (13.28 g) were mixed (molar ratio of DBU to AGU is 3:1), then carbon dioxide (0.1 MPa) was introduced, and the mixture was allowed to react at 55 ℃ for 2 hours to obtain a cellulose solution having a cellulose concentration of 4 wt%; then 16.15g of the solution is taken, 3.11g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to AGU is 15:1) is added, the reaction is carried out for 8 hours at 60 ℃, after the reaction is finished, the cyanoethyl cellulose is obtained through precipitation, filtration, washing and drying, the product is white powder, the product is soluble in DMSO and dilute alkali solution, and the elemental analysis nitrogen content is 3.46%.
Example 21
Corncob cellulose (dp=1440) (1.03 g), DMSO (100.00 g), DBU (1.93 g) (molar ratio of DBU to AGU is 2:1), and then carbon dioxide (1.2 MPa) is introduced, and the mixture is contacted and reacted for 5 hours at 30 ℃ to obtain a cellulose solution with a cellulose concentration of 1 wt%; then taking the solution, adding 0.34g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to the AGU is 1:1), carrying out contact reaction for 20h at 10 ℃, and carrying out precipitation, filtration, washing and drying after the reaction is finished to obtain cyanoethyl cellulose, wherein the product is white powder. Is soluble in dilute alkali solution and contains 0.57% of nitrogen in elemental analysis.
Example 22
Corncob cellulose (dp=1440) (19.06 g), DMSO (100 g), DBU (71.54 g) (molar ratio of DBU to AGU 4:1) were mixed, followed by introducing carbon dioxide (2 MPa), and contact-reacting at 70 ℃ for 0.5h to obtain a cellulose solution having a cellulose concentration of 10 wt%; then, 124.71g of acrylonitrile (the mol ratio of the etherifying agent acrylonitrile to AGU is 20:1) is added into the solution, the reaction is carried out for 0.5h at 80 ℃, and after the reaction is finished, cyanoethyl cellulose is obtained through precipitation, washing, drying and the like, and the product is white powder. Is soluble in DMSO and dilute alkali solution, and has a nitrogen content of 4.13% in elemental analysis.
The various aspects, embodiments, features and examples of the application are to be considered in all respects as illustrative and not intended to limit the application, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed application.
While the application has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the application. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the application without departing from the scope thereof. Therefore, it is intended that the application not be limited to the particular embodiment disclosed for carrying out this application, but that the application will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (7)
1. A method for preparing cyanoethyl cellulose, comprising:
uniformly mixing cellulose, organic alkali and organic solvent, and introducing CO 2 Carrying out dissolution reaction to obtain a cellulose solution with a homogeneous system;
mixing the cellulose solution with acrylonitrile for homogeneous etherification reaction to obtain cyanoethyl cellulose;
the conditions of the dissolution reaction include: the reaction temperature is 30-70 ℃, the reaction time is 0.5-5 h, and CO 2 The pressure is 0.1-0.5 MPa;
the molar ratio of the acrylonitrile to the anhydroglucose units in the cellulose is (7:1) - (15:1);
the organic base comprises any one or more than two of 1, 8-diazabicyclo [5,4,0] -7-undecene, 1,5, 7-triazabicyclo [4, 0] dec-5-ene and 1, 5-diazabicyclo [4,3,0] non-5-ene;
the molar ratio of the organic base to the anhydroglucose units in the cellulose is (2.5-3.5): 1, a step of;
the temperature of the homogeneous etherification reaction is 10-80 ℃ and the time is 0.5-20 h.
2. The method of claim 1, wherein the cellulose has the structural formula:
wherein n is the degree of polymerization and 100<n<2000。
3. The method of manufacturing according to claim 1, characterized in that: the cellulose is selected from microcrystalline cellulose, alpha-cellulose, and any one or more than two kinds of cellulose separated from corncob, cotton, paper pulp, wood pulp, bamboo pulp and agriculture and forestry straw.
4. The method of manufacturing according to claim 1, characterized in that: the organic solvent is a polar aprotic organic solvent with a boiling point higher than 150 ℃.
5. The method of manufacturing according to claim 1, characterized in that: the organic solvent comprises any one or more than two of dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
6. The method of manufacturing according to claim 1, characterized in that: the concentration of the cellulose solution is 1.0-10.0 wt%.
7. The method according to any one of claims 1 to 6, further comprising: and after the homogeneous etherification reaction is finished, sequentially precipitating, filtering, washing and drying the reaction system to obtain cyanoethyl cellulose.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211030859.8A CN115386011B (en) | 2022-08-23 | 2022-08-23 | Preparation method of cyanoethyl cellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211030859.8A CN115386011B (en) | 2022-08-23 | 2022-08-23 | Preparation method of cyanoethyl cellulose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115386011A CN115386011A (en) | 2022-11-25 |
| CN115386011B true CN115386011B (en) | 2023-11-07 |
Family
ID=84122278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211030859.8A Active CN115386011B (en) | 2022-08-23 | 2022-08-23 | Preparation method of cyanoethyl cellulose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115386011B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117600A (en) * | 2017-12-24 | 2018-06-05 | 贵州大学 | The synthetic method of cellulose carbonate material and the application of cellulose carbonate material |
| EP3398970A1 (en) * | 2017-05-05 | 2018-11-07 | Agency for Science, Technology and Research | A method of synthesizing cellulose carbonate |
| CN108840955A (en) * | 2018-06-13 | 2018-11-20 | 贵州大学 | A method of preparing cellulose carbonic acid mixed carboxylic ester |
| CN109134670A (en) * | 2018-08-30 | 2019-01-04 | 贵州大学 | A kind of preparation method of acetyl cellulose propionate and its mixed ester |
| CN110229354A (en) * | 2019-06-24 | 2019-09-13 | 中国科学院宁波材料技术与工程研究所 | A kind of method and system dissolving cellulose |
| CN113754899A (en) * | 2021-08-13 | 2021-12-07 | 中国科学院宁波材料技术与工程研究所 | Carbon dioxide composite solvent and method for dissolving cellulose |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2098539B1 (en) * | 2008-03-03 | 2017-05-10 | SE Tylose GmbH & Co.KG | Homogeneous synthesis of cellulose ethers in ionic liquids |
-
2022
- 2022-08-23 CN CN202211030859.8A patent/CN115386011B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3398970A1 (en) * | 2017-05-05 | 2018-11-07 | Agency for Science, Technology and Research | A method of synthesizing cellulose carbonate |
| CN108117600A (en) * | 2017-12-24 | 2018-06-05 | 贵州大学 | The synthetic method of cellulose carbonate material and the application of cellulose carbonate material |
| CN108840955A (en) * | 2018-06-13 | 2018-11-20 | 贵州大学 | A method of preparing cellulose carbonic acid mixed carboxylic ester |
| CN109134670A (en) * | 2018-08-30 | 2019-01-04 | 贵州大学 | A kind of preparation method of acetyl cellulose propionate and its mixed ester |
| CN110229354A (en) * | 2019-06-24 | 2019-09-13 | 中国科学院宁波材料技术与工程研究所 | A kind of method and system dissolving cellulose |
| CN113754899A (en) * | 2021-08-13 | 2021-12-07 | 中国科学院宁波材料技术与工程研究所 | Carbon dioxide composite solvent and method for dissolving cellulose |
Non-Patent Citations (1)
| Title |
|---|
| 申雨情."特殊官能团化纤维素碳酸酯设计、合成及性质研究".《万方数据库》.2021,第46-65页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115386011A (en) | 2022-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110551327B (en) | Method for preparing conductive composite material by using pyrrole grafted nano-cellulose | |
| JP2000513042A (en) | Reactive cellulose and method for producing the same | |
| CN108101996B (en) | Method for producing cellulosic proton type ionic liquid by using cellulose | |
| CN103539868B (en) | A kind of method of preparing CMC | |
| EP1969012B1 (en) | Method for preparation of hydroxyalkylalkylcellulose ethers with high yield | |
| EP0074631A1 (en) | Process for producing an alkali salt of a carboxymethylcellulose ether | |
| CN115386011B (en) | Preparation method of cyanoethyl cellulose | |
| Mi et al. | Homogeneous cyanoethylation of cellulose with acrylonitrile in a CO 2 switchable solvent | |
| KR100562091B1 (en) | Method for manufacturing high-cationic starch solutions | |
| JP3572213B2 (en) | Low substituted hydroxypropylcellulose | |
| CN116375892A (en) | Preparation method of polyanionic cellulose | |
| CN114773502A (en) | Alcoholysis method of polyvinyl acetate | |
| CN108530546B (en) | Synthesis and application of pseudochitosan and derivatives thereof | |
| JPH0157681B2 (en) | ||
| US2520963A (en) | Production of improved cellulosic materials | |
| CN110283254A (en) | A kind of preparation method of cellulose propene carbonate | |
| US20140048060A1 (en) | Method of dissolving natural polymers | |
| JPH0466881B2 (en) | ||
| CN115725003B (en) | Method for improving substitution degree of cyanoethyl cellulose | |
| JP2006077149A (en) | Polyglucuronic acid and method for producing the same | |
| JP2001114801A (en) | Production method for metal salt of carboxymethyl cellulose excellent in salt water resistance | |
| JPS6042241B2 (en) | Process for producing carboxymethyl cellulose ether alkali salt | |
| JPS62149701A (en) | Production of alkali metal salt of carboxymethylcellulose ether of low degree substitution | |
| CN117186250A (en) | Preparation process for producing high-viscosity CMC by slurry method | |
| CN117126217A (en) | Preparation method of methyl glucoside |
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 |