CN112853814B - Transparent ion conductive cellulose paper and preparation method thereof - Google Patents
Transparent ion conductive cellulose paper and preparation method thereof Download PDFInfo
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- CN112853814B CN112853814B CN202110201106.8A CN202110201106A CN112853814B CN 112853814 B CN112853814 B CN 112853814B CN 202110201106 A CN202110201106 A CN 202110201106A CN 112853814 B CN112853814 B CN 112853814B
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 126
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- INUNLMUAPJVRME-UHFFFAOYSA-N 3-chloropropanoyl chloride Chemical compound ClCCC(Cl)=O INUNLMUAPJVRME-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 235000010980 cellulose Nutrition 0.000 claims description 111
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 150000002500 ions Chemical class 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- JEQDSBVHLKBEIZ-REOHCLBHSA-N (2s)-2-chloropropanoyl chloride Chemical compound C[C@H](Cl)C(Cl)=O JEQDSBVHLKBEIZ-REOHCLBHSA-N 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 3
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 3
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 claims description 3
- -1 1-allyl-3-methylimidazole chloride salt Chemical class 0.000 claims description 2
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical group [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 claims description 2
- IXPWKHNDQICVPZ-UHFFFAOYSA-N 2-methylhex-1-en-3-yne Chemical compound CCC#CC(C)=C IXPWKHNDQICVPZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 7
- 229920000875 Dissolving pulp Polymers 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000002608 ionic liquid Substances 0.000 description 5
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 4
- QVRCRKLLQYOIKY-UHFFFAOYSA-M 1-methyl-3-prop-2-enylimidazol-1-ium;chloride Chemical compound [Cl-].C[N+]=1C=CN(CC=C)C=1 QVRCRKLLQYOIKY-UHFFFAOYSA-M 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 238000010923 batch production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 150000000778 D-glucopyranose derivatives Chemical class 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
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- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 238000011109 contamination Methods 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 239000004753 textile Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Images
Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paper (AREA)
Abstract
A preparation method of transparent ion-conductive cellulose paper comprises the following steps: (1) dissolving cellulose into clear transparent liquid by using a solvent to obtain a cellulose solution; (2) chloropropionyl chloride is added into the cellulose solution to prepare chloropropionyl chloride modified cellulose; (3) introducing acrylic amino ethyl ester into a cellulose solution modified by chloropropionyl chloride to prepare modified ionized cellulose containing double bonds; (4) and carrying out free radical polymerization on the modified ionized cellulose containing the double bonds to obtain the transparent ion-conductive cellulose paper. The invention also provides the transparent ion-conductive cellulose paper prepared by the preparation method. The cellulose is used for preparing the transparent ion conductive cellulose paper, and a conductive nano material is not required to be added, so that the prepared transparent ion conductive cellulose paper has high light transmittance, conductivity and excellent bendability, and has good environmental stability; the preparation method of the transparent ion conductive cellulose paper has the advantages of simple process, small pollution and low cost.
Description
Technical Field
The invention relates to the technical field of cellulose papermaking, in particular to transparent ion conductive cellulose paper and a preparation method thereof.
Background
In recent years, the development of electronic products has been rapidly advanced, and the development track of the society has been completely changed. Especially in the field of flexible electronics, from wearable electronic devices to flexible foldable electronic screens, people's consumption concepts are constantly being refreshed and people's productive lifestyles are being changed. However, with the mass production and rapid renewal of electronic devices in recent years, the contamination of electronic wastes has attracted much attention. Especially in the field of flexible electronics, equipment is more prone to failure due to long-term large-scale deformation or external force damage. For this reason, it is desirable that electronic products be able to spontaneously and easily "metabolize" themselves in the face of performance degradation or damage without burdening the surrounding environmental systems. Therefore, in order to solve the problems of the current electronic products, it is necessary to develop a functional substrate with biodegradable properties.
For degradable materials, cellulose is a natural high molecular polymer with the most abundant content on earth, has the advantages of reproducibility, biocompatibility, biodegradability, chemical stability, safety, non-toxicity and the like, and is widely applied to the fields of paper, textiles, building materials, composite materials and the like. Cellulose is a linear polysaccharide formed by linking a series of D-glucopyranose rings by 1, 4 glycosidic linkages. However, cellulose molecules have a rigid structure and molecular segments move slowly in dynamics due to strong hydrogen bonds and considerable van der waals forces between and within the cellulose molecules. The functional modification of cellulose is an important means for improving the high-value utilization of cellulose. The modified cellulose which has been commercialized successfully at present includes cellulose esters (cellulose nitrate and cellulose acetate) and cellulose ethers (carboxymethyl cellulose and hydroxyethyl cellulose). In recent years, cellulose-based functional hydrogels have opened up new doors for the functional application of cellulose, such as conductive, stimuli-responsive, shape-memory, self-repairing cellulose hydrogels, and the like. However, hydrogels generally suffer from problems such as easy volatilization of water at high temperature or room temperature, easy crystallization at low temperature, and the like, resulting in poor device stability and durability. Therefore, it is still far and diligent to develop a cellulose-based functional material having versatility and excellent stability.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the transparent ion conductive cellulose paper and the preparation method thereof, the preparation method of the transparent ion conductive cellulose paper uses cellulose for preparing the transparent ion conductive cellulose paper, the process is simple, the pollution is little, the cost is low, and the prepared transparent ion conductive cellulose paper has high light transmittance, conductivity, excellent stretchability and bendability and good environmental stability. The technical scheme is as follows:
a preparation method of transparent ion-conductive cellulose paper is characterized by comprising the following steps:
(1) dissolving cellulose into clear transparent liquid by using a solvent to obtain a cellulose solution;
(2) adding chloropropionyl chloride into the cellulose solution to prepare chloropropionyl chloride modified cellulose;
(3) introducing acrylic amino ethyl ester into a cellulose solution modified by chloropropionyl chloride to prepare modified ionized cellulose containing double bonds;
(4) and carrying out free radical polymerization on the modified ionized cellulose containing the double bonds to obtain the transparent ion-conductive cellulose paper.
Preferably, in step (1), the cellulose is added to the solvent and stirred until the cellulose is completely dissolved to form a clear and transparent liquid, thereby obtaining a cellulose solution.
Preferably, the solvent in step (1) is an ionic liquid. More preferably, the solvent used in step (1) is 1-butyl-3-methylimidazolium chloride (BMIMCl) or 1-allyl-3-methylimidazolium chloride (AMIMCl). Before dissolving cellulose, 1-butyl-3-methylimidazole chloride salt and 1-allyl-3-methylimidazole chloride salt are heated and dissolved into liquid.
In the step (1), microcrystalline cellulose is preferably used as the cellulose.
Preferably, in the step (1), the weight of the solvent is 20 to 100 times that of the cellulose.
Preferably, in the step (2), N-dimethylformamide is added into the cellulose solution and is uniformly stirred, then chloropropionyl chloride is added into the cellulose solution in an ice-water bath environment, and then the reaction is carried out for a period of time (preferably 2 to 4 hours) at room temperature (20 to 30 ℃) to obtain the chloropropionyl chloride modified cellulose. The purpose of adding N, N-dimethylformamide in the step (2) is to reduce the viscosity of the cellulose solution system. And (2) carrying out substitution reaction of acyl chloride and hydroxyl on cellulose.
Preferably, the chloropropionyl chloride in the step (2) is one or a combination of 2-chloropropionyl chloride and 3-chloropropionyl chloride.
The amount of the N, N-dimethylformamide added is preferably 5 to 8 times the weight of the cellulose.
Preferably, the addition amount of the chloropropionyl chloride is 1-3 times of the weight of the cellulose.
Preferably, in the step (3), the acrylic amino ethyl ester is added into the cellulose molecular solution modified by chloropropionyl chloride, and the reaction is carried out for a period of time (preferably 24-48 hours) at room temperature to obtain the modified ionized cellulose molecular solution containing double bonds. And (3) carrying out quaternary ammonium salinization reaction.
Preferably, the amino ethyl acrylate in the step (3) is one or more of dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and N, N-diethylaminoethyl acrylate.
Preferably, in step (3), the weight ratio of the amino ethyl acrylate to the chloropropionyl chloride is between 1:1 and 1.2: 1.
Preferably, in the step (4), an initiator is added into the modified ionized cellulose molecular solution containing double bonds, and after free radical polymerization, the transparent ion conductive cellulose paper is obtained after washing and drying by deionized water.
Preferably, the initiator in the step (4) is one or more of ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile and benzoyl peroxide.
The amount of the initiator added is preferably 1 to 5% by weight based on the weight of the cellulose.
Preferably, in step (4), the radical polymerization is carried out at 60 ℃ for 24 to 48 hours.
The invention also provides the transparent ion-conductive cellulose paper prepared by the preparation method.
Compared with the prior art, the method has the following beneficial effects that the cellulose is used for preparing the transparent ion conductive cellulose paper, and a conductive nano material is not required to be added, so that the prepared transparent ion conductive cellulose paper has high light transmittance, conductivity and excellent bendability, and has good environmental stability; the preparation method of the transparent ion conductive cellulose paper has the advantages of simple process, small pollution and low cost.
Drawings
FIG. 1 is a graph showing UV-visible light transmittance curves of transparent ion-conductive cellulose papers prepared in examples 1-2;
FIG. 2 is a thermogravimetric plot of the transparent ion-conductive cellulose paper prepared in examples 1-2;
FIG. 3 is a stress-strain curve of the transparent ion-conductive cellulose paper prepared in example 1-2;
FIG. 4 is a test for electrical property characterization of the transparent ion-conductive cellulose paper prepared in examples 1-2.
Detailed Description
Example 1
In this embodiment, the preparation method of the transparent ion-conductive cellulose paper includes the following steps:
(1) dissolving cellulose into clear transparent liquid by using a solvent to obtain a cellulose solution;
in the step (1), 0.972g of cellulose (all microcrystalline cellulose) is added into 30g of solvent (the solvent adopts 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride can be stirred for 1 hour at 100 ℃ to obtain clear and transparent ionic liquid, then the microcrystalline cellulose is added into the ionic liquid, and the stirring is carried out until the cellulose is completely dissolved to form clear and transparent liquid (the stirring time is 4 hours), so as to obtain cellulose solution;
(2) adding chloropropionyl chloride into the cellulose solution to prepare chloropropionyl chloride modified cellulose;
in the step (2), adding 5.5 mL of N, N-dimethylformamide into a cellulose solution, uniformly stirring, adding 1g of chloropropionyl chloride (all 2-chloropropionyl chloride) into the cellulose solution in an ice-water bath environment, and reacting at room temperature for 2 hours to obtain chloropropionyl chloride modified cellulose;
(3) introducing acrylic amino ethyl ester into a cellulose solution modified by chloropropionyl chloride to prepare modified ionized cellulose containing double bonds;
in the step (3), 1.2g of acrylic amino ethyl ester (all of which are dimethylaminoethyl methacrylate) is added into the cellulose molecular solution modified by chloropropionyl chloride, and the mixture reacts for 24 hours at room temperature to obtain a modified ionized cellulose molecular solution containing double bonds;
(4) adding 0.04g of initiator (ammonium persulfate) into the double-bond-containing modified ionized cellulose molecular solution, carrying out free radical polymerization (the free radical polymerization reaction is carried out at 60 ℃ and is carried out for 24 hours), washing by deionized water, and drying to obtain the transparent ion conductive cellulose paper.
Preparing various raw materials according to the proportion in batch production.
Example 2
In this embodiment, the preparation method of the transparent ion-conductive cellulose paper includes the following steps:
(1) dissolving cellulose into clear transparent liquid by using a solvent to obtain a cellulose solution;
in the step (1), 0.972g of cellulose (all microcrystalline cellulose) is added into 30g of solvent (the solvent adopts 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium chloride can be stirred for 1 hour at 100 ℃ to obtain clear and transparent ionic liquid, then the microcrystalline cellulose is added into the ionic liquid, and the stirring is carried out until the cellulose is completely dissolved to form clear and transparent liquid (the stirring time is 4 hours), so as to obtain cellulose solution;
(2) adding chloropropionyl chloride into the cellulose solution to prepare chloropropionyl chloride modified cellulose;
in the step (2), adding 8 mL of N, N-dimethylformamide into a cellulose solution, uniformly stirring, adding 1g of chloropropionyl chloride (all 3-chloropropionyl chloride) into the cellulose solution in an ice-water bath environment, and reacting at room temperature for 3 hours to obtain chloropropionyl chloride modified cellulose;
(3) introducing acrylic amino ethyl ester into a cellulose solution modified by chloropropionyl chloride to prepare modified ionized cellulose containing double bonds;
in the step (3), 1g of acrylic amino ethyl ester (all of which are dimethylaminoethyl acrylate) is added into the cellulose molecular solution modified by chloropropionyl chloride, and the mixture reacts for 36 hours at room temperature to obtain a modified ionized cellulose molecular solution containing double bonds;
(4) adding 0.02g of initiator (ammonium persulfate) into the modified ionized cellulose molecular solution containing double bonds, carrying out free radical polymerization (the free radical polymerization reaction is carried out at 60 ℃ and is carried out for 48 hours), washing by deionized water, and drying to obtain the transparent ion conductive cellulose paper.
Preparing various raw materials according to the proportion in batch production.
The transparent ion-conductive cellulose paper prepared in example 1-2 was subjected to optical property test, and its ultraviolet-visible light transmittance curve is shown in FIG. 1. As can be seen from FIG. 1, the prepared transparent ion-conducting cellulose paper has excellent optical transmittance, and the average transmittance in the visible light range of 400-800 nm is about 90%.
The transparent ion-conductive cellulose paper prepared in example 1-2 was tested for thermal stability and its thermogravimetric curve is shown in FIG. 2. As can be seen from fig. 2, the prepared transparent ion-conductive cellulose paper has good thermal stability, in which the thermal decomposition temperature is around 250 ℃.
The transparent ion-conductive cellulose paper prepared in examples 1-2 was tested for mechanical properties and the stress-strain curve is shown in FIG. 3. As can be seen from figure 3, the prepared transparent ion conductive cellulose paper has good mechanical flexibility, the maximum tensile deformation is between 15% and 20%, and the maximum tensile stress is between 8 MPa and 9 MPa.
The electrical properties of the transparent ion-conducting cellulose paper prepared in examples 1-2 were characterized and tested and can be placed in series in a circuit to light a small bulb, see in particular fig. 4. As can be seen from fig. 4, the prepared transparent ion-conductive cellulose paper has excellent conductivity, and the small bulbs can be kept to emit light continuously and stably after the transparent ion-conductive cellulose paper is connected into a circuit.
Claims (2)
1. A preparation method of transparent ion-conductive cellulose paper is characterized by comprising the following steps:
(1) adding cellulose into a solvent, and stirring until the cellulose is completely dissolved to form a clear transparent liquid to obtain a cellulose solution;
the solvent is 1-butyl-3-methylimidazole chloride salt or 1-allyl-3-methylimidazole chloride salt; the weight of the solvent is 20-100 times of that of the cellulose; the cellulose is microcrystalline cellulose;
(2) adding N, N-dimethylformamide into a cellulose solution, uniformly stirring, adding chloropropionyl chloride into the cellulose solution in an ice-water bath environment, and reacting at room temperature for 2-4 hours to obtain chloropropionyl chloride modified cellulose;
the chloropropionyl chloride is one or the combination of 2-chloropropionyl chloride and 3-chloropropionyl chloride; the addition amount of chloropropionyl chloride is 1-3 times of the weight of cellulose; the adding amount of the N, N-dimethylformamide is 5-8 times of the weight of the cellulose;
(3) adding acrylic amino ethyl ester into the cellulose solution modified by chloropropionyl chloride, and reacting at room temperature for 24-48 hours to obtain a modified ionized cellulose solution containing double bonds;
the acrylic amino ethyl ester is one or the combination of more of dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and N, N-diethylaminoethyl acrylate;
the weight ratio of the added amino ethyl acrylate to the chloropropionyl chloride is 1:1 to 1.2: 1;
(4) adding an initiator into a modified ionized cellulose solution containing double bonds, carrying out free radical polymerization, washing by deionized water, and drying to obtain transparent ion conductive cellulose paper;
the initiator is one or the combination of more of ammonium persulfate, potassium persulfate, sodium persulfate, azodiisobutyronitrile and benzoyl peroxide; the addition amount of the initiator is 1-5% of the weight of the cellulose;
the free radical polymerization reaction is carried out at 60 ℃ for 24-48 hours.
2. The transparent ion-conductive cellulose paper produced by the production method according to claim 1.
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| CN112853814B true CN112853814B (en) | 2022-09-30 |
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