CN116289318B - Paper deacidification and reinforcement method - Google Patents
Paper deacidification and reinforcement method Download PDFInfo
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- CN116289318B CN116289318B CN202310477923.5A CN202310477923A CN116289318B CN 116289318 B CN116289318 B CN 116289318B CN 202310477923 A CN202310477923 A CN 202310477923A CN 116289318 B CN116289318 B CN 116289318B
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- calcium carbonate
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000002787 reinforcement Effects 0.000 title abstract description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 28
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 23
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims description 27
- 239000000725 suspension Substances 0.000 claims description 22
- 238000005303 weighing Methods 0.000 claims description 21
- 238000009210 therapy by ultrasound Methods 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 18
- 238000005507 spraying Methods 0.000 claims description 18
- 238000005728 strengthening Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 229920002201 Oxidized cellulose Polymers 0.000 claims description 14
- 229940107304 oxidized cellulose Drugs 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 239000012279 sodium borohydride Substances 0.000 claims description 13
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- LGZDNJBUAAXEMN-UHFFFAOYSA-N 1,2,2,3-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1CCC[N+](C)([O-])C1(C)C LGZDNJBUAAXEMN-UHFFFAOYSA-N 0.000 claims description 8
- 229920001131 Pulp (paper) Polymers 0.000 claims description 8
- 239000003623 enhancer Substances 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 6
- 239000003517 fume Substances 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- -1 3-aminopropyl triethoxysilane modified calcium carbonate Chemical class 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000523 sample Substances 0.000 claims description 2
- 239000011122 softwood Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 23
- 239000003513 alkali Substances 0.000 abstract description 20
- 229920002678 cellulose Polymers 0.000 abstract description 7
- 239000001913 cellulose Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 abstract description 4
- 239000002270 dispersing agent Substances 0.000 abstract 2
- 239000000123 paper Substances 0.000 description 104
- 238000003860 storage Methods 0.000 description 19
- 238000001035 drying Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011087 paperboard Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 241000218631 Coniferophyta Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- BCZXFFBUYPCTSJ-UHFFFAOYSA-L Calcium propionate Chemical compound [Ca+2].CCC([O-])=O.CCC([O-])=O BCZXFFBUYPCTSJ-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004330 calcium propionate Substances 0.000 description 1
- 235000010331 calcium propionate Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004394 yellowing prevention Methods 0.000 description 1
Classifications
-
- 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
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/18—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00 of old paper as in books, documents, e.g. restoring
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
Abstract
The invention belongs to the technical field of paper deacidification, and particularly relates to a paper deacidification and reinforcement method. 3-aminopropyl triethoxy silane (APTES) modified calcium carbonate is used as a deacidification agent, the reduced nano cellulose is used as a reinforcing and reinforcing agent, and the deacidification and reinforcing of paper are realized by adopting a two-step method, so that the paper is protected and reinforced on the basis of not affecting the original performance of the paper, and the protection effect can be maintained after an aging test. Wherein the mass percentage of the modified calcium carbonate is 1.0-2.0%, and the dispersing agent is ethanol; the mass percentage of the reduced nano-cellulose is 0.03-0.1%, and the dispersing agent is 60% ethanol solution. The deacidification and reinforcement method for the paper has good deacidification and reinforcement effects on the paper, and a certain alkali reserve is reserved.
Description
Technical Field
The invention belongs to the technical field of paper deacidification, and particularly relates to a paper deacidification and reinforcement method.
Background
The paper cultural relics are used as carriers for cultural relic propagation, and have immeasurable historical values. However, since many rare paper relics are irreparably damaged due to acidification and the like in the prior paper relics for a long time, how to deacidify and protect paper is an important research subject of many researchers.
Cellulose is stable under general conditions and is not easy to chemically react; however, cellulose is easily degraded in acid conditions, resulting in a short fiber length and a decrease in the interweaving force between fibers, which is manifested in a decrease in paper strength and significant brittleness (er, afterglow, yang Guanghui, etc. chemical world, 2016). Therefore, the currently accepted effective means for solving the acidification problem of paper documents is deacidification treatment, namely, the deacidification treatment is to neutralize acidic substances in the paper and on the surface by using alkaline substances, and a certain reserve alkalinity is reserved in the paper, so that the aim of delaying the ageing of the paper is fulfilled.
From literature reports, researchers choose most of chemically stable alkaline substances for deacidification agents, and commonly used substances include calcium salts (calcium hydroxide and calcium propionate), magnesium salts (magnesium acetate and magnesium ethoxide), borohydrides (sodium borohydride and potassium borohydride), and borates (lithium tetraborate, sodium tetraborate and potassium tetraborate) (Cheng Lifen. University of Guangdong industries, 2014). As early as 2005, giorgi et al successfully synthesized nano magnesium oxide, which was dispersed in isopropanol for deacidification of paper (Giorgi R, bozzi C, dei L, et al langmuir, 2005). Whereas pH values of the nano calcium hydroxide solution and the nano magnesium hydroxide solution are about 12.5 and 10.6 respectively, too high alkalinity can promote alkaline hydrolysis of cellulose and can cause yellowing of lignin-containing paper. In the field of gas deacidification, researchers use ammonia gas for deacidification (an acidified paper batch deacidification research project group. Archives and construction, 2017), but the gas deacidification requires a large-scale deacidification device, has high cost, and has high toxicity of deacidification reagents and potential safety hazards of inflammability and explosiveness (ipet S, rouset E, cheradae h. Resurger, 2005). In the aspect of reinforcing paper, chitosan, starch and emulsion polymers are used as reinforcing agents (Fernandes S C M, free C S R, silvestre A J D, et al Industrial & engineering chemistry research,2010;Yoon S Y,Deng Y.Industrial&engineering chemistry research,2007), but the cost is high and the environment is polluted to a certain extent while reinforcing the paper.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a safe and effective paper deacidification and reinforcement method with good deacidification and reinforcement effects. Modified calcium carbonate is selected as a deacidification agent to improve the pH value and alkali storage of the paper. Calcium carbonate is used as a papermaking raw material, has the advantages of low destructiveness to paper, moderate alkalinity and low toxicity, but the problem of uneven dispersion in ethanol is solved, so that the calcium carbonate needs to be correspondingly modified, the modifier is 3-aminopropyl triethoxysilane (APTES) which contains amino groups and can strengthen the alkalinity of the calcium carbonate, and the modified calcium carbonate is more favorable for being attached to paper due to the existence of the amino groups; the reduced nanocellulose is selected as the reinforcing agent of the paper, the carboxyl content and the aldehyde content of the reduced nanocellulose are low, the paper is favorable for long-term storage and yellowing prevention, a large number of hydrogen bond sites are contained, the specific surface area is large, and the mechanical strength of the paper is increased.
The method for deacidifying and reinforcing paper comprises the following steps: preparing the paper deacidification agent into ethanol suspension, preparing the paper strengthening reinforcing agent into ethanol dispersion, and spraying the ethanol dispersion on the aged paper through a vacuum spray bottle.
The paper deacidification agent is APTES modified calcium carbonate particles.
The paper strengthening reinforcing agent is reduced nano cellulose.
The preparation method of the modified calcium carbonate comprises the following steps: weighing calcium carbonate particles, placing the calcium carbonate particles in a three-neck flask, adding toluene and 3-aminopropyl triethoxysilane (APTES), stirring at 80 ℃ for reaction for 24 hours, centrifuging the mixed solution at 4000r/min for 15min for three times after the reaction is finished, and finally obtaining the modified calcium carbonate through natural air drying.
The preparation method of the reduced nanocellulose comprises the following steps:
(1) Cutting bleached conifer sulfate pulp into 1cm multiplied by 1cm square pieces, placing the square pieces in a beaker, adding deionized water and 6.0M hydrochloric acid, soaking for 24 hours, and stirring by a household wall breaking machine to obtain paper pulp;
(2) Placing paper pulp in a three-neck flask, adding 100ml of water, adding sodium bromide and tetramethyl piperidine oxide (TEMPO) after ultrasonic treatment for 20min, respectively adding sodium hypochlorite at intervals of 1h for two times, stirring at room temperature for reaction for 2h, controlling the pH value of a system to be stable at 10.0 through 0.1M sodium hydroxide and 0.1M hydrochloric acid during the reaction, and carrying out suction filtration after the completion of the reaction to obtain oxidized cellulose fibers;
the mass ratio of the paper pulp to the sodium bromide to the tetramethylpiperidine oxide to the sodium hypochlorite is 1:0.15:0.024: (0.8-3.5).
(3) Weighing oxidized cellulose fibers, placing the oxidized cellulose fibers in a beaker, adding water and sodium borohydride, maintaining the pH value of the system to be 9 by adding 0.5M sodium bicarbonate solution at normal temperature, stirring and reacting for 48 hours at 500-600r/min, and performing suction filtration to obtain reduced oxidized cellulose fibers;
the mass ratio of the oxidized cellulose fiber to the sodium borohydride is 1: (2.0-2.5).
(4) And ultrasonically crushing the reduced oxidized cellulose fiber for 60 minutes to obtain the reduced nano cellulose.
The diameter of a probe of an ultrasonic breaker used for ultrasonic is 20mm, and the output power is 600W.
The specific method for deacidification and reinforcement enhancement comprises the following steps:
(1) Weighing modified calcium carbonate particles, placing the modified calcium carbonate particles in a beaker, adding ethanol, and preparing deacidification agent suspension by ultrasonic treatment for 5 min; the deacidification agent suspension is put into a vacuum spray bottle, and is sprayed on the aged paper of 18cm multiplied by 26cm for 4 times, and then the aged paper is placed in a fume hood for natural airing;
(2) Weighing reduced nanocellulose, placing the reduced nanocellulose in a beaker, adding 60% ethanol solution, and performing ultrasonic treatment for 5min to prepare reinforcing agent dispersion; the strengthening reinforcing agent dispersion liquid is filled into a vacuum spray bottle, and is sprayed on the deacidified aged paper completely for 4 times clockwise, and the paper is placed into a fume hood or a vacuum drying oven for airing.
Further, the mass percentage of APTES modified calcium carbonate particles in the deacidification agent suspension is 1.0-2.0%.
The mass percentage of the reduced nanocellulose in the strengthening agent dispersion liquid is 0.03-0.1%.
Preferably, each 20ml of the reinforcing agent contains 0.006-0.02g (absolute dry) of reduced nanocellulose, 12ml of ethanol and the balance of water.
Standing the treated aged paper at 23+/-1 ℃ and 50+/-2% RH for 24 hours, and measuring the pH value by using GB/T1545-2008 'determination of acidity or alkalinity of paper, paperboard and pulp water extract';
the alkali storage is measured by using GB/T24998-2010 'measurement of the alkali storage of paperboards and paperboards';
the tensile strength of the aged paper was measured using GB/T24998-2010 constant speed tensile method for determination of tensile Strength of paper and cardboard.
Preferably, the preparation method and application of the paper deacidification and strengthening reinforcing agent adopt ageing paper which is journal paper of popular movies published in 1980 and has the ration of 53.0+/-1.0 g/m 2 The pH was 4.6 and the alkali storage was 0.0131mol/kg.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
1. according to the invention, the modified calcium carbonate is used as a paper deacidification agent, the application range of metal carbonate is widened, the stability of the calcium carbonate in ethanol can be greatly enhanced by modifying the calcium carbonate by APTES, and meanwhile, amino groups on an APTES molecular chain have alkalinity and can react with acidic substances on the surface and inside of aged paper, so that the deacidification efficiency is improved, and the retention effect of the calcium carbonate on the surface of fibers is improved.
2. According to the invention, the reduced nanocellulose is used as the paper reinforcing enhancer, the carboxyl content and the aldehyde content of the reduced nanocellulose are reduced, so that additional acidic substances are not added while the paper is reinforced, yellowing of the paper due to the existence of aldehyde groups in the subsequent storage process can be avoided, and meanwhile, the increase of the hydroxyl content and the full swelling of fibers (as can be seen from fig. 4) are beneficial to the strength performance of the paper.
3. The invention utilizes the deacidification effect of the modified calcium carbonate to improve the acidity and alkali storage of the paper, slow down the corrosion of the acid to the paper and prolong the service life of the paper; the mechanical property of the paper is improved by utilizing the reinforcement and enhancement effects of the reduced nanocellulose, which is beneficial to prolonging the storage life of the paper.
Description of the drawings:
FIG. 1 is a Fourier infrared spectrum of the modified calcium carbonate prepared in example 1.
FIG. 2 is a graph comparing turbidity data of modified calcium carbonate prepared in example 1 with unmodified calcium carbonate.
FIG. 3 is a graph showing the carboxyl content data of reduced nanocellulose obtained from different ratios of sodium borohydride and nanocellulose prepared in example 1.
Fig. 4 is an optical microscopic image of the oxidized cellulose fibers (a) and the reduced oxidized cellulose fibers (b) prepared in example 1 and a TEM image of the nanocellulose (c) and the reduced nanocellulose (d).
Fig. 5 is an SEM image of the aged paper after deacidification strengthening and reinforcing in example 1.
FIG. 6 is a graph showing the relationship between the amount of modified calcium carbonate and the pH and alkali storage of the deacidified paper.
FIG. 7 is a graph showing the relationship between the amount of reduced nanocellulose and the tensile index of paper after deacidification reinforcement.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
The reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Putting 5g of calcium carbonate, 20mL of APTES (3-aminopropyl triethoxysilane) and 140mL of toluene into a three-necked flask, carrying out ultrasonic treatment for 20min, heating to 80 ℃ after uniform mixing, stirring for reaction for 24h at 500-600r/min, centrifuging and washing with ethanol after completion, and finally naturally air-drying to obtain modified calcium carbonate, wherein the Fourier infrared characteristics prove that a new functional group (shown in figure 1) appears in the calcium carbonate of 1640cm -1 The absorption peak at this point is generated by the NH bending vibration in the primary amine.
By comparison with the turbidity data of the unmodified calcium carbonate (as shown in fig. 2), it can be seen that the modified calcium carbonate particles are more stable to dispersion in ethanol.
0.3g of the modified calcium carbonate is placed in a beaker, 20mL of ethanol is added, and the mixture is subjected to ultrasonic treatment for 5min to prepare deacidification agent suspension 1.
Cutting bleached conifer sulfate pulp plate equivalent to 5g absolute dry pulp into small square pieces with the size of 1cm multiplied by 1cm, placing the small square pieces in a beaker, adding 800mL deionized water and 13.3mL 6.0M hydrochloric acid, wherein the final hydrochloric acid concentration is about 0.1M, stirring to obtain paper pulp after soaking for 24 hours, placing 1g (absolute dry) paper pulp in a three-neck flask, adding 100mL of water, adding 0.15g sodium bromide and 0.024g TEMPO (tetramethyl piperidine oxide) after ultrasonic treatment for 20 minutes, adding 3.75mL sodium hypochlorite firstly, adding 3.75mL sodium hypochlorite again at intervals of 1 hour, stirring at room temperature for 2 hours, controlling the pH of a system to be about 10 by 0.1M sodium hydroxide and 0.1M hydrochloric acid, and performing suction filtration after the end to obtain nanocellulose;
weighing 0.5g (absolute dry) of nano-cellulose, placing in a beaker, adding 95mL of water and 1.25g of sodium borohydride, adding 0.5M sodium bicarbonate solution at normal temperature to maintain the pH value of the system to be about 9, stirring and reacting for 48 hours at 500-600r/min, and performing suction filtration to obtain the reduced nano-cellulose.
Then weighing 5 parts of 0.5g (absolute dry) nanocellulose, placing the nanocellulose in a beaker, and adding 0.5g sodium borohydride, 1g sodium borohydride, 1.5g sodium borohydride, 2g sodium borohydride and 2.5g sodium borohydride into the nanocellulose respectively to obtain the reduced nanocellulose (the specific method is the same as above).
After reduction with sodium borohydride, the carboxyl content was significantly reduced (FIG. 3).
Weighing 0.02g (absolute dry) of the reduced nanocellulose, placing in a beaker, adding 12mL of ethanol and 8mL of water, and performing ultrasonic treatment for 5min to prepare a reinforcing enhancer dispersion liquid 1.
About 2.5g of a whole paper (26 cm. Times.18 cm) was cut out in 1980 journal (popular film), and a basis weight of about 53.68g/m was determined 2 The deacidification reinforcing agent is sprayed on the aged paper in sequence, and the specific process is as follows:
loading the deacidification agent suspension 1 into a vacuum spray bottle, spraying all the deacidification agent suspension on the aged paper for 4 times clockwise, and naturally airing in a fume hood; and then filling the reinforcing and reinforcing agent dispersion liquid 1 into the same vacuum spray bottle, spraying all the reinforcing and reinforcing agent dispersion liquid on the aged paper treated by the deacidification agent suspension liquid 1 for 4 times clockwise, and airing the aged paper in a fume hood or a vacuum drying oven.
After naturally drying, the paper is kept stand for 24 hours at 23+/-1 ℃ in 50+/-2% RH environment, the pH value, alkali storage, tensile index, color difference and whiteness (before aging after treatment) of the treated paper are measured, the modified calcium carbonate is uniformly distributed on the surface of the paper as can be seen by SEM (figure 4), and meanwhile, after a part of the paper kept stand for 24 hours is subjected to dry heat aging treatment for 72 hours at 105+/-2 ℃, the relevant properties (after aging) of the paper are tested.
The results are shown in Table 1 below:
TABLE 1
| pH value of | Alkali storage moL/kg | Tensile index N.times.m/g | Color difference delta E | Whiteness degree | |
| Blank space | 4.60 | 0.0131 | 37.8 | / | 54.5 |
| After treatment | 8.31 | 0.8056 | 56.7 | 1.07 | 58.0 |
| After dry heat aging | 8.25 | 0.7666 | 53.7 | 1.57 | 55.9 |
Example 2
Weighing 0.2g of modified calcium carbonate, putting into a beaker, adding 20mL of ethanol, and carrying out ultrasonic treatment for 5min to prepare deacidification agent suspension 2;
the reinforcing agent dispersion was the same as in example 1.
Cutting out about 2.5g of paper of 1980 journal (popular film), spraying deacidification agent suspension 2 on the paper, naturally drying, spraying reinforcing agent dispersion 1 on the paper (the method of example 1), standing the paper at 23+/-1 ℃ for 24 hours under 50+/-2% RH, measuring pH value, alkali storage, chromatic aberration and whiteness, and simultaneously, carrying out dry heat aging treatment on a part of the paper after standing for 24 hours at 105+/-2 ℃ for 72 hours, and testing the relevant performance (after aging) of the paper.
The results are shown in Table 2 below:
TABLE 2
| pH value of | Alkali storage mol/kg | Tensile index N.times.m/g | Color difference delta E | Whiteness degree | |
| Blank space | 4.60 | 0.0131 | 37.8 | / | 54.5 |
| After treatment | 8.31 | 0.5265 | 56.3 | 1.00 | 57.7 |
| After dry heat aging | 8.25 | 0.4831 | 52.9 | 1.37 | 55.2 |
Example 3
The deacidification agent dispersion was the same as in example 1;
weighing 0.006g (absolute dry) of reduced nanocellulose, placing in a beaker, adding 12mL of ethanol and 8mL of water, and performing ultrasonic treatment for 5min to prepare a reinforcing enhancer dispersion liquid 2;
the paper of journal 1980 (popular film) was cut to about 2.5g, the deacidification agent suspension 1 was sprayed on the paper, and after natural drying, the reinforcing agent dispersion 2 was sprayed on the paper (the same method as in example 1), after completion, the tensile index was measured after standing for 24 hours at 23.+ -. 1 ℃ under 50.+ -. 2% RH, and at the same time, after a part of the paper after standing for 24 hours was subjected to dry heat aging treatment at 105.+ -. 2 ℃ for 72 hours, the tensile index (after aging) of the paper was measured.
The results are shown in Table 3 below:
TABLE 3 Table 3
| Tensile index (N.times.m/g) | |
| Blank space | 37.8 |
| Before aging | 50.5 |
| After dry heat aging | 46.5 |
Example 4
Weighing 0.4g of modified calcium carbonate, putting into a beaker, adding 20mL of ethanol, and carrying out ultrasonic treatment for 5min to prepare deacidification agent suspension 3;
weighing 0.01g (absolute dry) of reduced nanocellulose, placing in a beaker, adding 12mL of ethanol and 8mL of water, and performing ultrasonic treatment for 5min to prepare reinforcing enhancer dispersion 3;
cutting out about 2.5g of the whole paper of 1980 journal (popular film), spraying the deacidification agent on the paper, naturally drying, spraying the strengthening reinforcing agent on the paper (the method of example 1), standing for 24 hours at 23+/-1 ℃ and 50+/-2% RH, measuring the tensile index (before aging), and simultaneously, carrying out dry heat aging treatment on a part of the paper after standing for 24 hours at 105+/-2 ℃ for 72 hours, and testing the tensile index of the paper.
The results are shown in Table 4 below:
TABLE 4 Table 4
| Tensile index (N.times.m/g) | |
| Blank space | 37.8 |
| Before aging | 53.5 |
| After dry heat aging | 50.8 |
Example 5
Weighing 0.1g of modified calcium carbonate, putting into a beaker, adding 20mL of ethanol, and carrying out ultrasonic treatment for 5min to prepare deacidification agent suspension 4;
weighing 0.002g (absolute dry) of reduced nanocellulose, placing in a beaker, adding 12mL of ethanol and 8mL of water, and performing ultrasonic treatment for 5min to prepare a reinforcing enhancer dispersion 4;
cutting out about 2.5g of paper of 1980 journal (popular film), spraying deacidification agent suspension 4 on the paper, naturally drying, spraying reinforcing agent dispersion 4 on the paper (the method of example 1), standing for 24h at 23+/-1 ℃ and 50+/-2% RH, measuring the tensile index (before aging), and simultaneously, carrying out dry heat aging treatment on a part of paper after standing for 24h at 105+/-2 ℃ for 72h, and testing the tensile index of the paper.
The results are shown in Table 5 below:
TABLE 5
| pH | Alkali store (kg/mol) | Tensile index (N.times.m/g) | |
| Blank space | 4.60 | 0.0131 | 37.8 |
| Before aging | 8.27 | 0.2317 | 47.0 |
| After dry heat aging | 7.66 | 0.1820 | 44.8 |
Example 6
Weighing 0.1g of modified calcium carbonate, putting into a beaker, adding 20mL of ethanol, and carrying out ultrasonic treatment for 5min to prepare deacidification agent suspension 4;
the solid reinforcing agent dispersion was the same as in example 1;
cutting about 2.5g of paper of 1980 journal (popular film), spraying the deacidification agent on the paper, naturally drying, spraying the strengthening and reinforcing agent on the paper (the method of example 1), standing at 23+ -1deg.C under 50+ -2% RH for 24h, and measuring pH, alkali storage and tensile index.
The results are shown in Table 6 below:
TABLE 6
| pH value of | Alkali storage mol/kg | Tensile index N.times.m/g |
| 8.27 | 0.2317 | 56.0 |
Example 7
Weighing 0.4g of modified calcium carbonate, putting into a beaker, adding 20mL of ethanol, and carrying out ultrasonic treatment for 5min to prepare a deacidification agent 3;
the reinforcing enhancer dispersion was the same as in example 1;
cutting about 2.5g of paper of 1980 journal (popular film), spraying deacidification agent suspension 3 on the paper, naturally drying, spraying the above strengthening reinforcing agent on the paper (the method of example 1), standing at 23+ -1deg.C under 50+ -2% RH for 24h, and measuring pH, alkali storage and tensile index.
The results are shown in Table 7 below:
TABLE 7
| pH value of | Alkali storage mol/kg | Tensile index N.times.m/g |
| 8.37 | 0.8420 | 57.1 |
Example 8
The tensile index of the paper treated in the method of example 1 is shown in fig. 7, with 0.3g of modified calcium carbonate fixed in 20mL of ethanol solution, and the mass percentages of the reduced nanocellulose are respectively 0%,0.01%,0.02%,0.03%,0.05%, and 0.1%.
Comparative example 1
Weighing 0.3g of calcium carbonate, putting into a beaker, adding 20mL of ethanol, and carrying out ultrasonic treatment for 5min to prepare deacidification agent suspension 5;
the reinforcing enhancer dispersion was the same as in example 1;
cutting about 2.5g of paper of 1980 journal (popular film), spraying the deacidification agent on the paper, naturally drying, spraying the strengthening and reinforcing agent on the paper (the method of example 1), standing at 23+ -1deg.C under 50+ -2% RH for 24h, and measuring pH value and alkali storage.
The results are shown in Table 8 below:
TABLE 8
| pH value of | Alkali store (mol/kg) | |
| Blank space | 4.60 | 0.0131 |
| Calcium carbonate particles | 8.09 | 0.7091 |
| Modified calcium carbonate particles | 8.31 | 0.8056 |
Comparing the analysis of example 1 with comparative example 1, it can be seen that the addition of APTES (3-aminopropyl triethoxysilane) results in a significant increase in paper pH and alkali stock.
Comparative example 2
The deacidification agent suspension was the same as in example 1;
weighing 0.02g (absolute dry) of nano-cellulose which is not reduced, placing in a beaker, adding 12mL of ethanol and 8mL of water, and performing ultrasonic treatment for 5min to prepare a reinforcing and reinforcing agent dispersion liquid 5;
cutting out about 2.5g of the whole paper of 1980 journal (popular film), spraying the deacidification agent on the paper, naturally drying, spraying the strengthening and reinforcing agent on the paper (the method of example 1), standing for 24 hours at 23+/-1 ℃ and 50+/-2% RH, and measuring the tensile index.
The results are shown in Table 9 below:
TABLE 9
| Tensile index (N.times.m/g) | |
| Blank space | 37.8 |
| Nanocellulose | 49.5 |
| Reduced nanocellulose | 56.7 |
Comparing the analysis of example 1 with comparative example 2, it can be seen that the reduced nanocellulose has a more pronounced increase in the tensile index of the paper than the unreduced nanocellulose.
Therefore, the paper deacidification agent and the paper strengthening and reinforcing agent prepared by the invention take calcium carbonate and paper pulp as raw materials, so that the pH value, alkali storage and tensile index of paper are improved, and the paper can be still maintained after aging.
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations that can be made by one skilled in the art without departing from the spirit of the present invention are within the scope of the present invention.
Claims (9)
1. A method for deacidifying and reinforcing paper, characterized in that the method comprises the following steps: preparing an ethanol suspension from a paper deacidification agent, preparing an ethanol dispersion from a paper strengthening enhancer, and spraying the ethanol dispersion on aged paper through a vacuum spray bottle;
the paper deacidification agent is 3-aminopropyl triethoxysilane modified calcium carbonate; the paper strengthening reinforcing agent is reduced nano cellulose.
2. The method for deacidifying and reinforcing paper according to claim 1, wherein the preparation method of the modified calcium carbonate is as follows: weighing calcium carbonate particles, placing the calcium carbonate particles in a three-neck flask, adding toluene and 3-aminopropyl triethoxysilane (APTES), stirring at 80 ℃ for reaction for 24h, centrifuging the mixed solution at 4000r/min for 15min for three times after the reaction is finished, and finally naturally air-drying to obtain the modified calcium carbonate.
3. The method for deacidifying and reinforcing paper according to claim 1, wherein the preparation method of the reduced nanocellulose comprises the following steps:
(1) Cutting bleached softwood sulfate pulp into 1cm multiplied by 1cm square pieces, placing the square pieces in a beaker, adding deionized water and 6.0M hydrochloric acid, soaking 24h, and stirring by a household wall breaking machine to obtain paper pulp;
(2) Placing paper pulp in a three-neck flask, adding water, adding sodium bromide and tetramethyl piperidine oxide (TEMPO) after ultrasonic treatment for 20min, respectively adding sodium hypochlorite at intervals of 1h for two times, stirring at room temperature of 1000r/min for reaction of 2h, controlling the pH of the system to be stable at 10.0 through 0.1M sodium hydroxide and 0.1M hydrochloric acid during the reaction, and carrying out suction filtration after the completion to obtain oxidized cellulose fibers;
(3) Weighing oxidized cellulose fibers, placing the oxidized cellulose fibers in a beaker, adding water and sodium borohydride, adding 0.5-M sodium bicarbonate solution at normal temperature to maintain the pH value of the system to be 9, stirring and reacting at 500-600r/min for 48h, and performing suction filtration to obtain reduced oxidized cellulose fibers;
(4) And ultrasonically crushing the reduced oxidized cellulose fiber for 60 minutes to obtain the reduced nano cellulose.
4. A method of deacidifying and strengthening paper according to claim 3, wherein the mass ratio of pulp, sodium bromide, tetramethylpiperidine oxide and sodium hypochlorite in step (2) is 1:0.15:0.024: (0.8-3.5).
5. A method of deacidifying and strengthening paper according to claim 3, wherein the mass ratio of oxidized cellulose fibers to sodium borohydride in step (3) is 1: (2.0-2.5).
6. A method for deacidification and strengthening of paper according to claim 3, wherein the ultrasonic breaker probe diameter used in the ultrasonic breaking in the step (4) is 20mm and the output power is 600W.
7. The method for deacidifying and reinforcing paper according to claim 1, wherein the specific method steps of deacidifying and reinforcing are as follows:
(1) Weighing modified calcium carbonate particles, placing the modified calcium carbonate particles in a beaker, adding ethanol, and preparing deacidification agent suspension by ultrasonic treatment for 5 min; the deacidification agent suspension is put into a vacuum spray bottle, and is sprayed on aged paper of 18cm multiplied by 26cm for 4 times, and then is placed into a fume hood for natural airing;
(2) Weighing reduced nanocellulose, placing the reduced nanocellulose in a beaker, adding 60% ethanol solution, and carrying out ultrasonic treatment for 5min to prepare reinforcing agent dispersion; the strengthening reinforcing agent dispersion liquid is filled into a vacuum spray bottle, and is sprayed on the deacidified aged paper completely for 4 times, and the paper is placed into a fume hood or a vacuum drying oven for natural airing.
8. The method for deacidifying and reinforcing paper according to claim 1, wherein the mass percentage of the modified calcium carbonate in the deacidification agent suspension in the step (1) is 1.0-2.0%.
9. The method for deacidifying and reinforcing paper according to claim 7, wherein the mass percentage of the reduced nanocellulose in the reinforcing agent dispersion in step (2) is 0.03 to 0.1%.
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| AU2002350199A1 (en) * | 2001-11-16 | 2003-06-10 | Honeywell International Inc. | Method of deacidifying cellulose-based materials |
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| US4522843A (en) * | 1984-01-25 | 1985-06-11 | Kundrot Robert A | Deacidification of library materials |
| CA2142195A1 (en) * | 1995-02-08 | 1996-08-09 | D. James Worsfold | Deacidification of cellulosic material |
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