CN111607106A - Dissolving of cellulose and preparation method of regenerated cellulose - Google Patents
Dissolving of cellulose and preparation method of regenerated cellulose Download PDFInfo
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- CN111607106A CN111607106A CN202010437250.7A CN202010437250A CN111607106A CN 111607106 A CN111607106 A CN 111607106A CN 202010437250 A CN202010437250 A CN 202010437250A CN 111607106 A CN111607106 A CN 111607106A
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 62
- 239000001913 cellulose Substances 0.000 title claims abstract description 62
- 239000004627 regenerated cellulose Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 23
- 239000000835 fiber Substances 0.000 claims abstract description 15
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- 229920000875 Dissolving pulp Polymers 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000001112 coagulating effect Effects 0.000 claims description 5
- 238000002166 wet spinning Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 6
- 239000008204 material by function Substances 0.000 abstract description 5
- 229920000298 Cellophane Polymers 0.000 abstract 2
- 235000010980 cellulose Nutrition 0.000 description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000004090 dissolution Methods 0.000 description 15
- 239000012528 membrane Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Images
Classifications
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- 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
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
-
- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Abstract
The invention provides a method for dissolving cellulose and preparing regenerated cellulose thereof, which is characterized in that inorganic salt solution with high concentration is prepared, 0.5-18 wt% of cellulose raw material is added under the stirring condition of 20-150 ℃, the cellulose is gradually dissolved to form solution cellulose solution with certain viscosity, and the solution cellulose solution is extruded and solidified in different modes to finally obtain cellophane films or fibers. The prepared cellophane film or fiber is easy to add functional materials in the preparation process, and the high-performance composite regenerated cellulose material is prepared. The inorganic salt has rich reserves, low price and no pollution to the environment, and the invention conforms to the concept of green development and greatly reduces the production cost, thereby having great market potential.
Description
Technical Field
The invention relates to a dissolving method of cellulose, in particular to a dissolving method of cellulose and a preparation method of regenerated cellulose thereof, belonging to the field of dissolving methods of cellulose.
Technical Field
Cellulose is an inexhaustible renewable resource in the nature, is one of the oldest and most abundant natural polymers on the earth, is mainly derived from plants such as wood, grass, bamboo, bast and seed hair, and has the advantages of short regeneration period, abundant and easily available reserves, environmental friendliness, good biocompatibility, low price, good biodegradability and the like. The efficient utilization of biomass resources is beneficial to relieving the problems of increasingly exhausted non-renewable resources such as petroleum and the like and increasingly severe environmental pollution in the world. However, cellulose is difficult to dissolve and infusible due to its high crystallinity and strong intramolecular and intermolecular hydrogen bonding, and is difficult to use as it is, and therefore, it is necessary to further treat it. Currently, the dissolution method of cellulose can be divided into two categories, wherein the derivatization method is to make some functional groups connected to the cellulose molecular chain through chemical reaction during the dissolution process, so that the cellulose molecular chain becomes soluble cellulose derivatives for dissolution, including sodium hydroxide/carbon disulfide (NaOH/CS)2) Systems, carbamates, paraformaldehyde/dimethylsulfoxide (PF/DMSO), protonic acids, and the like; the direct dissolution method is realized by directly destroying hydrogen bonds among and in cellulose molecules through small solvent molecules, and comprises a cuprammonium solution, N-methylmorpholine-N-oxide (NMMO), lithium chloride/N, N-dimethylacetamide (LiCl/DMAc), an ionic liquid, an alkali/urea and NaOH/thiourea system and the like.
The efficient dissolution of cellulose depends on the continuous development of a solvent system, and the research and the utilization of a green efficient solvent system are hot spots of the development of cellulose. In patent publication No. CN 102432892A, urea/thiourea, polyethylene glycol and sodium hydroxide/sodium hydroxide aqueous solution are selected as dissolving solvent of cellulose, and uniform and stable solution with cellulose concentration up to 15 wt% can be prepared for natural cellulose with polymerization degree of 250.
The method adopts a high-concentration inorganic salt solution to dissolve the cellulose raw material to obtain 0.5-18 wt% of cellulose solution. The high-concentration inorganic salt solution is a good solvent for cellulose, the dissolving process is simple, the conditions are mild, the inorganic salt is cheap and easy to obtain, the inorganic salt is easy to recover, and the use process cannot cause environmental pollution. The cellulose solution can be used for preparing a series of regenerated cellulose products including gel, fiber and membrane by the processes of coagulation regeneration in a coagulation bath, washing for desalting, drying and the like. The addition of the functional material enables the regenerated cellulose composite fiber or the composite membrane to obtain high added value, and can meet the market demands of various fields.
Disclosure of Invention
The invention aims to provide a method for dissolving cellulose and preparing regenerated cellulose thereof, and regenerated cellulose fibers or films are prepared from a cellulose solution by wet spinning or coating to form films, and functional materials are added to prepare multifunctional regenerated cellulose composite materials, so that the performance is optimized to meet variable market demands.
The cellulose dissolving process has mild condition, the inorganic salt is cheap and easy to obtain and is easy to recover, and the use process does not cause environmental pollution.
A method for dissolving cellulose, comprising the steps of:
1) preparing a high-concentration single or compound inorganic salt solution;
2) adding a certain amount of cellulose raw materials into the inorganic salt solution obtained in the step 1), and stirring and dissolving at a certain temperature to obtain a homogeneous cellulose solution.
In the step 1), the inorganic salt is metal salt, and the metal ions are respectively Li+、Mg2+、Al3+、Ca2+、Ti4+、Mn2+、Fe3+、Co2+、Cu2+、Zn2+The anion is one of Cl-and Br-.
The concentration of the inorganic salt solution in the step 1) is inorganic salt: the molar ratio of water is 1: 10-1: 2.
The adding amount of the cellulose raw material in the step 2) is 0.5-18 wt%.
The stirring temperature in the step 2) is 20-150 ℃.
A method for preparing regenerated cellulose, which is suitable for the method for dissolving cellulose, is characterized by comprising the following steps:
1) cooling a cellulose solution prepared by a cellulose dissolving method to obtain high-strength and high-toughness gel;
2) treating the gel obtained in the step 1) by a certain method, cooling and solidifying in a coagulating bath, washing to remove salt, and drying to obtain a regenerated cellulose product.
The gel treatment method in the step 2) is one of wet spinning and coating film forming, and regenerated cellulose products in two forms of fibers and films are obtained.
The coagulating bath in the step 2) is one of an organic solvent, a mixed solution of the organic solvent and water and a dilute acid solution.
Furthermore, functional materials are added into the cellulose solution obtained by the cellulose dissolving method disclosed by the invention, or functional materials are added into the coagulating bath, so that high-performance multifunctional fibers can be prepared; the functional material can be antibacterial materials such as zinc oxide and the like, conductive polymer materials such as polyaniline and the like, high-strength conductive materials such as carbon nano tubes and the like, has rich and various sources, gives the regenerated cellulose composite fiber or the composite film extremely high added value, and is applied to various fields.
The inorganic salt solution used in the invention belongs to a non-derivative solvent of cellulose, the metal ions and the complex thereof directly act with cellulose molecules, the cellulose can be quickly and efficiently dissolved, the cellulose solution is semitransparent and can form gel after cooling, the cellulose gel obtained by dissolving the cellulose by the inorganic salt solution, the regenerated cellulose fiber and the regenerated cellulose membrane, especially the regenerated cellulose composite material added with functional materials, have multifunctional characteristics, can meet the performance requirements of different application fields, and have great market potential.
Microscopic change patterns of cellulose gradual dissolution were characterized using a microscope; x-ray diffraction (XRD) was used to characterize the crystallinity and the change of crystalline form of the obtained cellulose before and after dissolution. The results are as follows:
(1) microscopic change pattern of cellulose complete dissolution, see fig. 3;
(2) XRD patterns of regenerated cellulose membranes and cellulose feedstock, see figure 4.
The innovation points of the invention are as follows:
(1) the inorganic salt solution has mild conditions for dissolving cellulose raw materials, and the inorganic salt is cheap and easy to obtain and easy to recover, and does not cause environmental pollution in the using process;
(2) the novel process for preparing the regenerated cellulose material by dissolving cellulose with the solvent is simple and can be produced and applied in a large scale. Especially, the regenerated cellulose composite fiber and the composite membrane product have multifunctional characteristics, high added value and are suitable for various market demands.
Drawings
FIG. 1 is a schematic diagram of the dissolution of cellulose and the preparation process of regenerated cellulose.
FIG. 2 is a schematic representation of the dissolution of cellulose to form a homogeneous solution in example 1.
FIG. 3 is a microscopic change in the complete dissolution of cellulose in example 2.
FIG. 4 is an XRD pattern of the regenerated cellulose film and cellulose raw material of example 2.
Detailed description of the preferred embodiments
The invention is further illustrated below with reference to specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. In addition, after reading the teaching of the present invention, those skilled in the art can make various changes or modifications to the invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example 1
With ZnCl2：H2Preparing solution with O being 1:3, stirring at 70 ℃ under normal pressure, and adding 3 wt% of wood pulp for dissolution; as shown in FIG. 2, it is seen that the cellulosic material is dissolved in the inorganic salt solution to form a homogeneous solution; after cooling, a clear gel was obtained.
Example 2
With ZnCl2：H2Preparing solution with O of 1:3, stirring at 80 ℃ under normal pressure, adding 3.5 wt% of wood pulp for dissolution(ii) a The dissolution of the cellulose was observed under a microscope, and as shown in FIG. 3, it was seen that the cellulose was completely dissolved.
Coating the dissolved cellulose solution at 50 ℃ to form a film, solidifying the film in absolute ethyl alcohol to form a film, washing the film for multiple times to remove inorganic salt, and drying the film to obtain a transparent regenerated cellulose film; as seen from fig. 4, the crystallinity of the regenerated cellulose film was reduced because the original crystalline regions of the cellulose were completely destroyed during the dissolution process, and thereafter, although the crystallinity was regenerated by the intermolecular rearrangement, the crystallinity was not high as fibrils. In addition, the cellulose has crystal form transformation before and after the zinc chloride solution is dissolved, and the position of the corresponding characteristic peak is changed.
Example 3
With FeCl3：H2O is 1: 6 preparing a solution, stirring at the normal pressure and the temperature of 95 ℃, and adding 3 wt% of absorbent cotton for dissolving; and (3) carrying out wet spinning on the dissolved cellulose solution at 50 ℃, solidifying the cellulose solution into fibers in anhydrous methanol, washing the fibers with water to remove inorganic salts, and drying the fibers to obtain the regenerated cellulose fibers.
Example 4
The reaction solution is prepared by mixing LiBr: h2O is 1:2 preparing a solution, stirring at 150 ℃, and adding 18wt% of microcrystalline cellulose for dissolution;
and (3) carrying out wet spinning on the dissolved cellulose solution at 50 ℃, solidifying the cellulose solution into fibers in dilute hydrochloric acid, washing the fibers with water to remove inorganic salts, and drying the fibers to obtain the transparent regenerated cellulose membrane.
Example 5
With CoCl2：H2O is 1:10 and CaCl2：H2O is 1: 4, preparing a solution, wherein the mixing mass ratio is 1: stirring at 1,120 deg.C, adding 0.5 wt% pulp, and dissolving; coating the dissolved cellulose solution at 50 ℃ to form a film, and soaking the film in absolute ethyl alcohol for many times; then dissolving 10 wt% of polyvinyl alcohol (PVA) solution for soaking, and drying to obtain the regenerated cellulose composite film with high strength and high modulus.
Example 6
With TiCl4：H2O is 1: 4 and ZnCl2：H2O is 1:3 preparing a solution, wherein the mixing mass ratio is 2: 8,adding 3 wt% of cellulose powder for dissolution under stirring at 20 ℃; coating the dissolved cellulose solution at 60 ℃ to form a film, and soaking the film in absolute ethyl alcohol for many times; then dissolving 1 wt% of sodium hydroxide (NaOH) solution, soaking, and drying to obtain the regenerated cellulose composite film with antibacterial function; the zinc ion remained in the regenerated cellulose membrane reacts with the sodium hydroxide to obtain zinc hydroxide precipitate; the zinc hydroxide is dried in the regenerated cellulose membrane to obtain the zinc oxide, and the regenerated cellulose composite membrane has the functions of mildew prevention and bacteria resistance and can be used for a long time.
Claims (8)
1. A method for dissolving cellulose, comprising the steps of:
1) preparing a high-concentration single or compound inorganic salt solution;
2) adding a certain amount of cellulose raw materials into the inorganic salt solution obtained in the step 1), and stirring and dissolving at a certain temperature to obtain a homogeneous cellulose solution.
2. The method according to claim 1, wherein the inorganic salt in step 1) is a metal salt, and the metal ions are each Li+、Mg2+、Al3+、Ca2+、Ti4+、Mn2+、Fe3+、Co2+、Cu2+、Zn2+The anion is one of Cl-and Br-.
3. The method for dissolving cellulose according to claim 1, wherein the concentration of the inorganic salt solution in the step 1) is inorganic salt: the molar ratio of water is 1: 10-1: 2.
4. The method for dissolving cellulose according to claim 1, wherein the cellulose raw material is added in an amount of 0.5 to 18wt% in the step 2).
5. The method for dissolving cellulose according to claim 1, wherein the stirring temperature in the step 2) is 20 to 150 ℃.
6. A method for producing regenerated cellulose suitable for the method for dissolving cellulose according to claim 1, comprising the steps of:
1) cooling the cellulose solution prepared in claim 1 to obtain a high strength and high toughness gel;
2) treating the gel obtained in the step 1) by a certain method, cooling and solidifying in a coagulating bath, washing to remove salt, and drying to obtain a regenerated cellulose product.
7. The method for preparing regenerated cellulose according to claim 6, wherein the gel in step 2) is processed by one of wet spinning and coating to form a film, so as to obtain regenerated cellulose products in both fiber and film forms.
8. The method of claim 6, wherein the coagulating bath in step 2) is one of an organic solvent, a mixture of an organic solvent and water, and a dilute acid solution.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010437250.7A CN111607106A (en) | 2020-05-21 | 2020-05-21 | Dissolving of cellulose and preparation method of regenerated cellulose |
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| CN202010437250.7A CN111607106A (en) | 2020-05-21 | 2020-05-21 | Dissolving of cellulose and preparation method of regenerated cellulose |
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| CN111607106A true CN111607106A (en) | 2020-09-01 |
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| CN114409813A (en) * | 2022-01-26 | 2022-04-29 | 中国科学院上海应用物理研究所 | Green recyclable cellulose solvent and preparation method thereof, and method for realizing cellulose regeneration |
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| CN113150336A (en) * | 2021-03-19 | 2021-07-23 | 浙江理工大学 | Method for preparing high-crystallization high-orientation regenerated cellulose material by high-voltage electrostatic field assisted self-assembly and product |
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