CN117107548B - Preparation method and application of composite deacidification material with high alkali reserve and hydrophobicity after deacidification treatment of paper - Google Patents
Preparation method and application of composite deacidification material with high alkali reserve and hydrophobicity after deacidification treatment of paper Download PDFInfo
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- CN117107548B CN117107548B CN202310963515.0A CN202310963515A CN117107548B CN 117107548 B CN117107548 B CN 117107548B CN 202310963515 A CN202310963515 A CN 202310963515A CN 117107548 B CN117107548 B CN 117107548B
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- 239000000463 material Substances 0.000 title claims abstract description 109
- 239000002131 composite material Substances 0.000 title claims abstract description 105
- 239000003513 alkali Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- -1 compound magnesium hydroxide Chemical class 0.000 claims abstract description 33
- 239000011575 calcium Substances 0.000 claims abstract description 19
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 17
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 17
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 37
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 23
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 21
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 8
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LGUZHRODIJCVOC-UHFFFAOYSA-N perfluoroheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LGUZHRODIJCVOC-UHFFFAOYSA-N 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- UVWPNDVAQBNQBG-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-icosafluorononane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UVWPNDVAQBNQBG-UHFFFAOYSA-N 0.000 claims description 2
- OBAVAMUHCSFDSY-UHFFFAOYSA-N 1,1,1,2,3,3,4,4,5,5,6,6,7,8,8,8-hexadecafluoro-2,7-bis(trifluoromethyl)octane Chemical compound FC(F)(F)C(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(C(F)(F)F)C(F)(F)F OBAVAMUHCSFDSY-UHFFFAOYSA-N 0.000 claims description 2
- RKIMETXDACNTIE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorocyclohexane Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F RKIMETXDACNTIE-UHFFFAOYSA-N 0.000 claims description 2
- QIROQPWSJUXOJC-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6-undecafluoro-6-(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F QIROQPWSJUXOJC-UHFFFAOYSA-N 0.000 claims description 2
- USPWUOFNOTUBAD-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(trifluoromethyl)benzene Chemical compound FC1=C(F)C(F)=C(C(F)(F)F)C(F)=C1F USPWUOFNOTUBAD-UHFFFAOYSA-N 0.000 claims description 2
- CJFUEPJVIFJOOU-UHFFFAOYSA-N 2-perfluorobutyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1CCCO1 CJFUEPJVIFJOOU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 239000011777 magnesium Substances 0.000 abstract description 40
- 229920000642 polymer Polymers 0.000 abstract description 20
- 239000000835 fiber Substances 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 230000002787 reinforcement Effects 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 21
- 238000001556 precipitation Methods 0.000 description 19
- 230000009471 action Effects 0.000 description 18
- 238000001816 cooling Methods 0.000 description 18
- 239000012535 impurity Substances 0.000 description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 description 18
- HBZFBSFGXQBQTB-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HBZFBSFGXQBQTB-UHFFFAOYSA-N 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 239000002244 precipitate Substances 0.000 description 17
- 238000010521 absorption reaction Methods 0.000 description 14
- 230000032683 aging Effects 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 12
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 8
- 229920002678 cellulose Polymers 0.000 description 8
- 239000001913 cellulose Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 6
- 239000001639 calcium acetate Substances 0.000 description 6
- 229960005147 calcium acetate Drugs 0.000 description 6
- 235000011092 calcium acetate Nutrition 0.000 description 6
- 239000012466 permeate Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- WIMBFQPYJQMSCP-UHFFFAOYSA-N (1,2,2,3,3,4,4,5,5,6,6-undecafluorocyclohexyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F WIMBFQPYJQMSCP-UHFFFAOYSA-N 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- HPPDPHZGXWMRHN-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluoro-n-methylhexane-1-sulfonamide Chemical compound CNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HPPDPHZGXWMRHN-UHFFFAOYSA-N 0.000 description 2
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 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
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000037358 bacterial metabolism Effects 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000886 photobiology Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 238000004383 yellowing 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
-
- 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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- 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
- D21H25/02—Chemical or biochemical treatment
-
- 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 discloses a preparation method and application of a composite deacidification material with high alkali reserves and hydrophobicity after deacidification treatment of paper, and belongs to the technical field of deacidification treatment of precious paper cultural relics and the like. The composite deacidification material is prepared from nano alkaline compound magnesium hydroxide Mg (OH) 2 Or calcium hydroxide Ca (OH) 2 The surface coating fluoroalkyl methacrylate polymer (PPFOEMA). The PPFOEMA polymer is coated to enable the composite deacidification material to be suspended and dispersed in fluorocarbon medium in high stability for high-efficiency deacidification treatment of paper; the composite deacidification material is easy to uniformly infiltrate into the fiber gaps of the paper, and the PPFOEMA polymer coated on the surfaces of the nano particles can delay the release of alkaline compounds, so that the deacidified paper is still slightly alkaline under the condition of high alkali reserves, has excellent hydrophobicity and certain reinforcement effect, and is convenient for long-term storage.
Description
Technical Field
The invention relates to a preparation method and application of a composite deacidification material with high alkali reserves and hydrophobicity after deacidification treatment of paper, and the composite deacidification material is applied to deacidification treatment of precious paper cultural relics, archives, books and the like.
Background
Paper is the most common base material for recording information, bears important tasks of human civilization and development inheritance, and is an essential component in human history development. However, there are hundreds of millions of paper materials worldwide that are currently undergoing severe aging and degradation (Trends in Microbiology,2010, 18:538-542), primarily due to the acidic species present in the paper. Acidic materials in paper are generally derived from acidic sizing agents in the papermaking process, acidic gases such as sulfur oxides and nitrogen oxides in the storage environment, and organic acids produced by bacterial metabolism, and these acidic materials can accelerate hydrolysis of cellulose in paper, resulting in reduced polymerization, yellowing and embrittlement of the cellulose, and severely compromising the life of paper cultural relics. Therefore, deacidification and strengthening of fragile paper literature has been an unprecedented task.
The paper deacidification process is divided into aqueous phase deacidification, organic phase deacidification and gas phase deacidification according to the difference of media in which the alkaline deacidification material is positioned. Among them, the aqueous phase deacidification process is applied on a large scale because of its advantages of safety, high efficiency, simple operation, etc., such as German Wei Duofa (Journal of Colloid and Interface Science,2022, 607:992-1004) and Austrian Vienna process (Chimia International Journal for Chemistry,2001, 55:981-989), etc. However, paper after aqueous deacidification can wrinkle; the organic mediums such as methanol, isopropanol and the like used for deacidifying the organic phase are inflammable and explosive, and are not friendly to human bodies and environment. In order to overcome the above drawbacks, the use of inert organic media to suspend and disperse alkaline deacidification materials has gradually become the mainstream process for large-scale paper deacidification in recent years. The most typical of this is the Bookkeper method using perfluoroheptane media (Microporous and Mesoporous Materials,2020, 293:109786). The perfluoro alkane such as perfluoro heptane has the advantages of nonflammability, non-explosive property, good chemical stability, easy volatilization, no residue, good permeability and the like (Journal of Photochemistry and Photobiology A: chemistry,2010, 214:86-91). However, the perfluoroalkane medium has low surface tension, is hydrophobic and oleophobic, so that the alkaline deacidification material is difficult to uniformly and stably suspend and disperse in the perfluoroalkane medium (CN 20161025757.2), which causes a series of problems of uneven deacidification of paper, poor deacidification effect, low utilization rate of the deacidification material and the like. The invention disclosed before well solves the problem of high-stability suspension dispersion of an alkaline deacidification material in a fluorocarbon medium (CN 114753186A, a paper deacidification composite material with high-stability suspension dispersion in the fluorocarbon medium, a preparation method and application thereof, and CN108589411A, an attapulgite composite material and application thereof).
The existing paper deacidification technology is developed based on the acid-base neutralization principle, namely, an alkaline substance is adopted to neutralize acidic substances in paper so as to inhibit acid-catalyzed hydrolysis of paper cellulose, thereby prolonging the service life of the paper cellulose. It is known that a certain amount of alkaline substances must be stored in order to avoid acid reversion for a long time in deacidified paper, and the definition and quantitative determination method of the alkali reserves can be according to the national standard GB/T24998-2010 method. The stored alkaline substances are used for neutralizing acidic substances generated by natural aging in the subsequent paper preservation process after deacidification, so that the paper aging speed can be reduced, and the paper preservation period can be prolonged. However, too high an alkali reserve of deacidified paper tends to give the paper too high a pH, which also adversely affects the life of the paper (Carbohydrate Polymers,2019,209: 250-257). Therefore, how to provide the deacidified paper with high alkali reserves and proper pH value, i.e. how to provide certain slow release property for the alkaline substances stored in the paper, is an important problem to be solved.
Cellulose, the most important component of paper, is a natural hygroscopic material, and generally shows hydrophilicity; meanwhile, the three-dimensional netlike abundant microporous structure formed by crosslinking between cellulose has capillary condensation, so that the cellulose has stronger water absorption and wettability. The strength of the paper after water absorption is greatly reduced, and the paper is more easily combined with acidic substances in the air, so that the ageing of the paper is accelerated. In contrast, hydrophobic paper is not easy to absorb water, and has good self-cleaning and corrosion resistance properties. In particular, hydrophobic papers are also effective in preventing adhesion of papers to each other during batch deacidification (International Journal of Biological Macromolecules,2022,207:232-241; cellulose,2022, 29:8863-8877), thereby facilitating large-scale and efficient deacidification of papers. Therefore, how to make deacidified paper possess certain hydrophobicity is another important problem that we need to solve.
Disclosure of Invention
The invention aims to provide a preparation method of a composite deacidification material with high stability and suspension dispersion in fluorocarbon medium, and also provides a preparation method of a composite deacidification material with high alkali reserves and hydrophobicity characteristics of deacidified paper, so as to further innovatively develop the prior art. The technical scheme provided by the invention is that the inorganic nano alkaline deacidification material is pre-adsorbed with fluoroalkyl methacrylate (PFOEMA) monomer capable of undergoing polymerization reaction, and then is polymerized in situ to form the composite deacidification material. The paper subjected to deacidification treatment by the composite deacidification material still presents weak alkalinity under the high alkali reserve, and has certain hydrophobicity. The composite deacidification material is magnesium hydroxide Mg (OH) which is an alkaline compound 2 Or calcium hydroxide Ca (OH) 2 The core-shell structure with the core and the fluoroalkyl methacrylate polymer (PPFOEMA) as shells has high stable suspension dispersibility in fluorocarbon media, and the composite material is easy to uniformly infiltrate into paper fiber gaps. Coating with basic compound Mg (OH) or Ca (OH) 2 The PPFOEMA polymer shell on the surface of the nano particle can delay the release of alkaline substances in the inner core, and the paper deacidified by the composite material is still weakly alkaline under the condition of high alkali reserve; in addition, the PPFOEMA polymer existing on the surface layer of the composite deacidification material which permeates into the gaps of the paper fibers has certain hydrophobicity; furthermore, the composite deacidification material which permeates into the fiber gaps of the paper can also improve the mechanical strength of the paper. The invention also aims to provide the application of the composite deacidification material prepared by the method in deacidification of paper.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a composite deacidification material with high alkali reserves and hydrophobicity after deacidification treatment of paper comprises the following steps:
1) Adding hydrazine hydrate (N) into aqueous solution of sodium hydroxide (NaOH) 2 H 4 ·H 2 O) an aqueous solution, obtaining a precipitant solution;
2) Configuration containsCalcium ion (Ca) 2+ ) Or magnesium ion (Mg) 2+ ) And fluoroalkyl methacrylate ethanol (CH) 3 CH 2 OH) solutions;
3) Mixing and stirring the solutions in the step 1) and the step 2), and placing the mixed solution in a reaction kettle for temperature control reaction;
4) And (3) centrifugally separating, washing and drying the reacted mixture to obtain the solid composite deacidification material.
According to the preparation method of the composite deacidification material, the paper is subjected to deacidification treatment and has high alkali reserves and hydrophobicity, and the alkaline compound in the solid composite deacidification material is any one of magnesium hydroxide and calcium hydroxide.
According to the preparation method of the composite deacidification material, the paper is subjected to deacidification treatment and has high alkali reserves and hydrophobicity, and the alkaline compound accounts for 50-95% of the mass fraction of the solid composite deacidification material.
According to the preparation method of the composite deacidification material, the paper is subjected to deacidification treatment and has high alkali reserves and hydrophobicity, the temperature of the temperature-controlled reaction in the reaction kettle is 150 ℃, and the reaction time is 12 hours.
The composite deacidification material which is obtained by the method and has high alkali reserves and hydrophobicity after deacidification treatment.
The composite deacidification material which enables the paper to have high alkali reserves and hydrophobicity after deacidification treatment is applied to deacidification of the paper.
The application comprises the steps of dispersing the composite deacidification material in a fluorocarbon medium, carrying out ultrasonic treatment, and then carrying out deacidification on paper.
The fluorocarbon medium is one or more of perfluorooctane, perfluoroheptane, perfluorononane, perfluorobutyl tetrahydrofuran, perfluorocyclic ether, perfluorocyclohexane, perfluoromethyl cyclohexane, perfluorotoluene and perfluoro-2, 7-dimethyloctane.
The application comprises the following specific steps:
(1) Dispersing the composite deacidification material in a fluorocarbon medium, and carrying out ultrasonic treatment for 30min to prepare a suspension, wherein the concentration of the composite deacidification material is 3.0-10.0 g/L;
(2) Soaking the paper to be deacidified in the suspension obtained in the step (1) for 30min, and then airing at room temperature to finish the deacidification treatment of the paper.
The chemical formulas of the fluoroalkyl methacrylate (PFOEMA) are as follows (1) and (2):
(1) In (a): n has a value of 4 to 11; in (2): n is 0 to 3, and x is 0 to 2.
Further, the fluoroalkyl methacrylate is 2- (perfluorooctyl) ethyl methacrylate, and has a structure shown in (3);
the composite deacidification material with high alkali storage capacity and hydrophobicity after deacidification treatment is prepared by precipitating calcium ions (Ca) by using precipitant sodium hydroxide and hydrazine hydrate aqueous solution 2+ ) Or magnesium ion (Mg) 2+ ) First, an alkaline compound Ca (OH) is produced 2 Or Mg (OH) 2 Then pre-adsorbing fluoroalkyl methacrylate (PFOEMA) monomer, and then carrying out in-situ polymerization to generate fluoroalkyl methacrylate (PPFOEMA) polymer. Experimental results show that the composite deacidification material adopts an alkaline compound Ca (OH) 2 Or Mg (OH) 2 "core-shell" structure Ca (OH) with nano particles as core and PPFOEMA polymer as shell 2 @PPFOEMA or Mg (OH) 2 PPFOEMA (see fig. 1 and 2) not only shows high stable suspension dispersibility in fluorocarbon media (see fig. 3), but also the composite deacidification material is easily and uniformly infiltrated into the paper fiber gaps (see fig. 4) during deacidification treatment. As shown in Table 1, the deacidified paper had a high alkali content of 466.29mmol/kg and was coated with an alkaline compound Mg (OH) 2 Or Ca (OH) 2 The PPFOEMA polymer shell on the surface of the nano particles can delay the release of alkaline substances in the inner core, so that the deacidified paper is still weakly alkaline (pH value is between 7 and 8) under the condition of high alkali reserveThe method comprises the steps of carrying out a first treatment on the surface of the The PPFOEMA polymer on the surface layer of the composite deacidification material which permeates into the gaps of the paper fibers has certain hydrophobicity, so that the paper after deacidification treatment has certain hydrophobicity, and the stable contact angle with water is greatly increased from 25 degrees before deacidification treatment to 130 degrees after deacidification treatment; in particular, the composite deacidification material which permeates into the fiber gaps of the paper can also improve the mechanical strength of the paper.
Compared with the prior art, the invention has the beneficial effects that:
1) The fluoro alkyl methacrylate polymer (PPFOEMA) coated on the surface of the composite deacidification material can be suspended and dispersed in fluorocarbon medium with high stability, and the composite material is easy to uniformly infiltrate into the gaps of paper fiber and is coated on the alkaline compound Mg (OH) 2 Or Ca (OH) 2 The PPFOEMA polymer shell on the surface of the nano particle can delay the release of alkaline substances in the inner core, and the paper deacidified by the composite material is still weakly alkaline under the condition of high alkali reserve; the invention not only solves the problem of poor suspension dispersion stability of deacidification materials in fluorocarbon media, but also solves the problems of low alkali reserves, easy acid return or high alkali reserves, overhigh pH of the paper surface and the like of the paper after deacidification treatment of the existing deacidification materials;
2) The PPFOEMA polymer coated on the surface of the composite deacidification material prepared by the invention has hydrophobicity, and the composite deacidification material uniformly permeates into the gaps of the paper fiber in the deacidification treatment process, so that the surface of the paper also shows strong hydrophobicity, thereby being beneficial to the preservation of the paper;
3) The invention adopts nano alkaline Ca (OH) of PPFOEMA polymer coated on the surface prepared by an in-situ polymerization reaction method 2 Or Mg (OH) 2 The composite material has the characteristics of simple method, simple steps, high synthesis efficiency, good paper deacidification effect, high alkali reserve, moderate surface pH, good hydrophobicity, obvious reinforcement effect and the like, and the prepared composite deacidification material is used for paper deacidification treatment.
Drawings
FIG. 1 is Mg (OH) of example 2 2 Scanning Electron Microscope (SEM) image of PPFOEMA sample, wherein PPFOEMA is a 2- (perfluorooctyl) ethyl methacrylate polymer;
FIG. 2 is Mg (OH) 2 (a) Mg (OH) prepared in example 2 2 Infrared spectra of PPFOEMA (b) and PFOEMA monomer (c), wherein PFOEMA is 2- (perfluorooctyl) ethyl methacrylate;
FIG. 3 is a composite deacidification material Mg (OH) prepared in example 2 2 Optical photographs of the @ PPFOEMA suspension (FIG. 3A) and comparative example 1Mg (OH) 2 Is shown in fig. 3B;
FIG. 4 shows the Mg (OH) composite deacidified material prepared in example 18 and before deacidification of the paper (FIG. 4A) 2 SEM image after @ PPFOEMA deacidification treatment (fig. 4B);
FIG. 5 shows (a) a composite deacidification material Mg (OH) prepared in example 18 before deacidification of paper 2 (b) after deacidification treatment of PPFOEMA, (c) after aging treatment, and water.
Detailed Description
The present invention will be further described with reference to specific embodiments for the purpose of making the objects, technical solutions and advantages of the present invention more apparent. Unless otherwise indicated, all technical means used in the following examples are conventional means well known to those skilled in the art.
Example 1
Dissolving 0.429g of magnesium acetate tetrahydrate into 20mL of absolute ethyl alcohol under the action of ultrasonic waves (power 70w, frequency 40 Khz), adding 0.1g of 2- (perfluorooctyl) ethyl methacrylate (PFOEMA) monomer, and stirring at normal temperature for later use; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowly dripping the precipitate into the standby liquid, stirring for 30min at room temperature, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, separating, washing to remove impurities, and obtaining the composite deacidification material Mg (OH) 2 The weight percentage of the magnesium hydroxide in the solid composite deacidification material is 90-95%.
Example 2
Dissolving 0.429g of magnesium acetate tetrahydrate in 20mL of absolute ethyl alcohol under the action of ultrasonic wave (power 70w, frequency 40 Khz)Adding 0.2g of 2- (perfluorooctyl) ethyl methacrylate (PFOEMA) monomer, and stirring at normal temperature for later use; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowly dripping the precipitate into the standby liquid, stirring for 30min at room temperature, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, separating, washing to remove impurities, and obtaining the composite deacidification material Mg (OH) 2 The weight percentage of magnesium hydroxide in the solid composite deacidification material is 80-85%.
Example 3
Dissolving 0.429g of magnesium acetate tetrahydrate into 20mL of absolute ethyl alcohol under the action of ultrasonic waves (power 70w, frequency 40 Khz), adding 0.3g of 2- (perfluorooctyl) ethyl methacrylate (PFOEMA) monomer, and stirring at normal temperature for later use; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowly dripping the precipitate into the standby liquid, stirring for 30min at room temperature, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, separating, washing to remove impurities, and obtaining the composite deacidification material Mg (OH) 2 The weight percentage of magnesium hydroxide in the solid composite deacidification material is 70-75%.
Example 4
Dissolving 0.429g of magnesium acetate tetrahydrate into 20mL of absolute ethyl alcohol under the action of ultrasonic waves (power 70w, frequency 40 Khz), adding 0.4g of 2- (perfluorooctyl) ethyl methacrylate (PFOEMA) monomer, and stirring at normal temperature for later use; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowly dripping the precipitate into the standby liquid, stirring for 30min at room temperature, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, separating, washing to remove impurities, and obtaining the composite deacidification material Mg (OH) 2 PPFOEMA in which the magnesium hydroxide is in solid formThe mass fraction of the composite deacidification material is 60-65%.
Example 5
Dissolving 0.429g of magnesium acetate tetrahydrate into 20mL of absolute ethyl alcohol under the action of ultrasonic waves (power 70w, frequency 40 Khz), adding 0.5g of 2- (perfluorooctyl) ethyl methacrylate (PFOEMA) monomer, and stirring at normal temperature for later use; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowly dripping the precipitate into the standby liquid, stirring for 30min at room temperature, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, separating, washing to remove impurities, and obtaining the composite deacidification material Mg (OH) 2 The weight percentage of magnesium hydroxide in the solid composite deacidification material is 50-55%.
Example 6
Dissolving 0.429g of magnesium acetate tetrahydrate into 20mL of absolute ethyl alcohol under the action of ultrasonic waves (power 70w, frequency 40 Khz), adding 0.2g of perfluorocyclohexyl methacrylate (PFCHMA) monomer, and stirring at normal temperature for later use; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowly dripping the precipitate into the standby liquid, stirring for 30min at room temperature, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, separating, washing to remove impurities, and obtaining the composite deacidification material Mg (OH) 2 The weight percentage of magnesium hydroxide in the solid composite deacidification material is 80-85%.
Example 7
0.429g of magnesium acetate tetrahydrate was dissolved in 20mL of absolute ethanol under the action of ultrasonic waves (power 70w, frequency 40 Khz), and 0.2g of ethyl (N-methyl perfluorohexane sulfonamide) methacrylate (C) 6 SA) monomer, stirring at normal temperature for standby; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowing down the precipitation solutionSlowly dripping the standby liquid, stirring for 30min at room temperature, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, and washing to remove impurities to obtain the composite deacidification material Mg (OH) 2 @PC 6 SA(PC 6 SA represents methacrylic acid (N-methyl perfluoro hexane sulfonamide) ethyl ester polymer, wherein the mass fraction of magnesium hydroxide in the solid composite deacidification material is 80-85%.
Example 8
Dissolving 0.429g of magnesium acetate tetrahydrate into 20mL of absolute ethyl alcohol under the action of ultrasonic waves (power 70w, frequency 40 Khz), adding 0.2g of perfluoroalkyl ethyl acrylate (TEAc-8) monomer, and stirring at normal temperature for later use; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowly dripping the precipitate into the standby liquid, stirring for 30min at room temperature, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, separating, washing to remove impurities, and obtaining the composite deacidification material Mg (OH) 2 And @ PTAc-8 (PTAc-8 represents a perfluoroalkyl ethyl acrylate polymer), wherein the mass fraction of the magnesium hydroxide in the solid composite deacidification material is 80-85%.
Example 9
Dissolving 0.429g of magnesium acetate tetrahydrate into 20mL of absolute ethyl alcohol under the action of ultrasonic waves (power 70w, frequency 40 Khz), adding 0.2g of trifluoroethyl methacrylate (FMA) monomer, and stirring at normal temperature for later use; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowly dripping the precipitate into the standby liquid, stirring for 30min at room temperature, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, separating, washing to remove impurities, and obtaining the composite deacidification material Mg (OH) 2 PFMA (PFMA is trifluoroethyl methacrylate polymer), wherein the mass fraction of magnesium hydroxide in the solid composite deacidification material is 80-85%.
Example 10
Dissolving 0.316g of calcium acetate into 20mL of absolute ethyl alcohol under the action of ultrasonic waves (power 70w, frequency 40 Khz), adding 0.1g of 2- (perfluorooctyl) ethyl methacrylate (PFOEMA) monomer, and stirring at normal temperature for later use; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowly dripping the precipitate into the standby liquid, stirring for 30min at room temperature, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, and washing to remove impurities to obtain the composite deacidification material Ca (OH) 2 The weight percentage of calcium hydroxide in the solid composite deacidification material is 90-95%.
Example 11
Dissolving 0.316g of calcium acetate into 20mL of absolute ethyl alcohol under the action of ultrasonic waves (power 70w, frequency 40 Khz), adding 0.2g of 2- (perfluorooctyl) ethyl methacrylate (PFOEMA) monomer, and stirring at normal temperature for later use; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowly dripping the precipitate into the standby liquid, stirring for 30min at room temperature, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, and washing to remove impurities to obtain the composite deacidification material Ca (OH) 2 The weight percentage of calcium hydroxide in the solid composite deacidification material is 80-85%.
Example 12
Dissolving 0.316g of calcium acetate into 20mL of absolute ethyl alcohol under the action of ultrasonic waves (power 70w, frequency 40 Khz), adding 0.3g of 2- (perfluorooctyl) ethyl methacrylate (PFOEMA) monomer, and stirring at normal temperature for later use; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowly dripping the precipitate into the above standby solution, stirring at room temperature for 30min, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150deg.C for 12 hr, and coolingCentrifugally separating and washing to remove impurities after cooling to room temperature to obtain the composite deacidification material Ca (OH) 2 The weight percentage of calcium hydroxide in the solid composite deacidification material is 70-75%.
Example 13
Dissolving 0.316g of calcium acetate into 20mL of absolute ethyl alcohol under the action of ultrasonic waves (power 70w, frequency 40 Khz), adding 0.4g of 2- (perfluorooctyl) ethyl methacrylate (PFOEMA) monomer, and stirring at normal temperature for later use; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowly dripping the precipitate into the standby liquid, stirring for 30min at room temperature, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, and washing to remove impurities to obtain the composite deacidification material Ca (OH) 2 The weight percentage of calcium hydroxide in the solid composite deacidification material is 60-65%.
Example 14
0.316g of calcium acetate is dissolved in 20mL of absolute ethyl alcohol under the action of ultrasonic waves (power 70w, frequency 40 Khz), and 0.5g of 2- (perfluorooctyl) ethyl methacrylate (PFOEMA) monomer is added, and stirred at normal temperature for later use; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowly dripping the precipitate into the standby liquid, stirring for 30min at room temperature, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, and washing to remove impurities to obtain the composite deacidification material Ca (OH) 2 The weight percentage of calcium hydroxide in the solid composite deacidification material is 50-55%.
Example 15
1.0g of Mg (OH) in example 2 was taken 2 Uniformly dispersing the @ PPFOEMA in 200mL of perfluorooctane, and performing ultrasonic treatment (with the power of 70w and the frequency of 40 Khz) for 30min to obtain a high-stability suspension-dispersion composite deacidification material-perfluorooctane dispersion system.
FIG. 2 shows magnesium hydroxide (a), mg (OH) 2 Infrared spectrograms of the (b) PPFOEMA composite deacidification material and the (c) 2- (perfluorooctyl) ethyl methacrylate monomer. 3700cm in magnesium hydroxide (a) -1 The absorption peak at which corresponds to-OH vibration absorption; 1241cm in 2- (perfluorooctyl) ethyl methacrylate (c) -1 、1205cm -1 And 1149cm -1 The absorption peak at which corresponds to-CF 2 Vibration absorption 1725cm -1 The absorption peak at which corresponds to-c=o vibration absorption, 1639cm -1 The absorption peak at corresponds to the vibration absorption of c=c. Mg (OH) 2 The @ PPFOEMA composite deacidification material (b) has 3700cm -1 the-OH vibration absorption peak at the location also had a peak thickness of 1241cm -1 、1205cm -1 、1149cm -1 is-CF of (2) 2 Vibration absorption peak, but 1639cm did not appear -1 The vibration absorption peak at c=c, indicating CH in 2- (perfluorooctyl) ethyl methacrylate 2 Polymerization reaction of =c-, formation of- (CH) 2 -C-) n -a polymer; and the absorption peak of C=O in the infrared spectrogram of the composite deacidification material is from 1725cm -1 Displacement to 1735cm -1 The surface of magnesium hydroxide is coated with 2- (perfluorooctyl) ethyl methacrylate polymer, and certain interaction exists between the polymer and the magnesium hydroxide, so that a stable core-shell structure composite deacidification material Mg (OH) is formed 2 @PPFOEMA. The composite deacidification material can be stably suspended and dispersed in perfluorooctane for at least 10 days, and the optical photograph of the sample is shown in figure 3A.
Comparative example 1
Dissolving 0.429g of magnesium acetate tetrahydrate into 20mL of absolute ethyl alcohol under the action of ultrasonic waves (power 70w, frequency 40 Khz), and stirring at normal temperature for later use; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowly dripping the precipitate into the standby liquid, stirring at room temperature for 30min, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, and washing to remove impurities to obtain pure Mg (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the 1.0g of Mg (OH) 2 Dispersing in 200mL perfluorooctane, ultrasonic treating for 30min, standing for 30minWherein Mg (OH) 2 Significant sedimentation occurs and the optical photograph is shown in fig. 3B.
Comparative example 2
Dissolving 0.429g of magnesium acetate tetrahydrate into 20mL of absolute ethyl alcohol under the action of ultrasonic waves (power 70w, frequency 40 Khz), adding 0.2g of Sodium Dodecyl Sulfate (SDS) monomer, and stirring at normal temperature for later use; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowly dripping the precipitate into the standby liquid, stirring for 30min at room temperature, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, separating, washing to remove impurities, and obtaining the composite deacidification material Mg (OH) 2 SDS; 1.0g of Mg (OH) 2 The @ SDS is uniformly dispersed in 200mL of perfluorooctane, the dispersion is carried out for 30min by ultrasonic, and after the dispersion is kept stand for 30min, the solid particles in the dispersion are obviously settled.
Example 16
Dissolving 0.316g of calcium acetate into 20mL of absolute ethyl alcohol under the action of ultrasonic waves (power 70w, frequency 40 Khz), adding 0.2g of perfluorocyclohexyl methacrylate (PFCHMA) monomer, and stirring at normal temperature for later use; dissolving 0.16g of sodium hydroxide in 20mL of aqueous solution, and adding 4mL of hydrazine hydrate with mass fraction of 80% into the solution to prepare a precipitation solution; slowly dripping the precipitate into the standby liquid, stirring for 30min at room temperature, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, and washing to remove impurities to obtain the composite deacidification material Ca (OH) 2 PPFCHMA, 1.0g Ca (OH) 2 Uniformly dispersing the @ PPFCHMA in 200mL of perfluoro-cyclic ether, and carrying out ultrasonic treatment for 30min to obtain a high-stability suspension-dispersed composite deacidification material-perfluoro-cyclic ether dispersion system.
Example 17
Dissolving 0.429g of magnesium acetate tetrahydrate into 20mL of absolute ethyl alcohol under the action of ultrasonic waves (power 70w, frequency 40 Khz), adding 0.2g of perfluorocyclohexyl methacrylate (PFCHMA) monomer, and stirring at normal temperature for later use; 0.16g of sodium hydroxide was dissolved in 20mL of an aqueous solution, and added theretoAdding 4mL of hydrazine hydrate with mass fraction of 80% to prepare a precipitation solution; slowly dripping the precipitate into the standby liquid, stirring for 30min at room temperature, transferring the mixed solution into a 100mL reaction kettle with polytetrafluoroethylene lining, reacting at 150 ℃ for 12h, cooling to room temperature, centrifuging, washing, and removing impurities to obtain the composite deacidification material Mg (OH) 2 PPFCHMA, 1.0g Mg (OH) 2 Uniformly dispersing the @ PPFCHMA in 200mL of perfluoro-cyclic ether, and carrying out ultrasonic treatment for 30min to obtain a high-stability suspension-dispersed composite deacidification material-perfluoro-cyclic ether dispersion system.
Example 18
The composite deacidification material in example 15 was used for deacidification of paper, and the concentration of the composite deacidification material in the composite deacidification material-perfluorooctane dispersion system was 5g/L.
Soaking acid paper with surface average pH value of 4.02 in composite deacidification material Mg (OH) 2 In perfluorooctane medium @ PPFOEMA, the paper is gently shaken with tweezers, soaked for 30min, and then taken out, and dried for 24h at room temperature. The composite deacidified material Mg (OH) is detected by the national standard GB/T1545.2-2003 method 2 The pH value of the surface of the paper treated by PPFOEMA is 7.56, and the alkali storage amount is 466.29mmol/kg (see table 1), which shows that the paper treated by the composite deacidification material is still slightly alkaline under the condition of higher alkali storage amount.
And (3) carrying out dry heat aging on the deacidified paper for 72 hours at 105 ℃. The pH value of the paper is 7.49 and the alkali storage is 456.87mmol/kg by using the national standard GB/T1545.2-2003 method, which shows that the paper after deacidification treatment and further dry heat aging treatment still has higher alkali storage and still is slightly alkaline. In contrast, the average pH value of the paper which is not deacidified after the dry heat aging treatment is 3.69, which shows that the composite deacidified material Mg (OH) 2 The paper treated by the PPFOEMA material has good deacidification effect and anti-acid return capability.
The hydrophobicity (water contact angle) of the paper before and after the deacidification treatment and the paper after the deacidification treatment and the dry heat aging treatment was measured, and the measured data are shown in fig. 5 and table 1.
As can be seen from fig. 5: the contact angle of the paper which is not deacidified with water is suddenly reduced from the initial 117 DEG to 25 DEG within 10min, but the contact angle of the paper which is deacidified and then subjected to dry heat aging treatment is 138 DEG, and the contact angle of the paper which is not deacidified with water is basically unchanged within 20min, which shows that the paper treated by the composite deacidified material shows excellent hydrophobicity.
The mechanical properties (folding strength, tensile strength and tear strength) of the paper before and after the deacidification treatment and the paper after the dry heat aging treatment were measured, and the data are shown in table 1. The result shows that the Mg (OH) is the deacidified material after being compounded 2 The mechanical properties of the paper treated by the PPFOEMA are improved to a certain extent compared with those of the paper which is not treated, and even if the paper is subjected to dry heat aging treatment, the mechanical properties of the paper are still superior to those of the paper which is not subjected to deacidification treatment.
Table 1 performance data for paper samples
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a composite deacidification material with high alkali reserves and hydrophobicity after deacidification treatment of paper is characterized by comprising the following steps:
1) Adding a hydrazine hydrate aqueous solution into a sodium hydroxide aqueous solution to obtain a precipitant solution;
2) Preparing an ethanol solution containing calcium and magnesium ions and fluoroalkyl methacrylate;
3) Mixing and stirring the solutions in the step 1) and the step 2), placing the mixed solution in a reaction kettle, controlling the temperature to be 150 ℃, and reacting for 12 hours;
4) And (3) centrifugally separating, washing and drying the reacted mixture to obtain the solid composite deacidification material.
2. The method for producing a composite deacidified material having a high alkali reserve and hydrophobicity as claimed in claim 1, wherein the alkali compound in the solid composite deacidified material is any one of magnesium hydroxide and calcium hydroxide.
3. The method for producing a composite deacidified material having a high alkali reserve and hydrophobicity as claimed in claim 1, wherein the alkali compound accounts for 50 to 95% by mass of the solid composite deacidified material.
4. A composite deacidified material having a high alkali reserve and hydrophobicity after deacidification of paper obtained by the process of any one of claims 1 to 3.
5. The composite deacidification material with high alkali reserves and hydrophobicity after deacidification treatment of paper according to claim 4 is applied to deacidification of paper.
6. The use according to claim 5, wherein the composite deacidification material is dispersed in a fluorocarbon medium and sonicated for 30min to obtain a stable suspension, which is then used for deacidification of paper.
7. The use according to claim 6, wherein the fluorocarbon medium is one or more of perfluorooctane, perfluoroheptane, perfluorononane, perfluorobutyl tetrahydrofuran, perfluorocyclic ether, perfluorocyclohexane, perfluoromethyl cyclohexane, perfluorotoluene, perfluoro-2, 7-dimethyloctane.
8. The use according to claim 6, characterized by the specific steps of:
(1) Dispersing the composite deacidification material in a fluorocarbon medium, and carrying out ultrasonic treatment for 30min to prepare a suspension, wherein the concentration of the composite deacidification material is 3.0-10.0 g/L;
(2) Soaking the paper to be deacidified in the suspension obtained in the step (1) for 30min, and then airing at room temperature to finish the deacidification treatment of the paper.
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| FR1551757A (en) * | 1967-01-23 | 1968-12-27 | ||
| KR20090067315A (en) * | 2007-12-21 | 2009-06-25 | 주식회사 코오롱 | Polymer beads having core-shell structure and preparation method of polymer beads by core-shell method |
| CN104652173A (en) * | 2015-02-04 | 2015-05-27 | 江志鑫 | Book treatment method |
| CN113863053A (en) * | 2021-09-30 | 2021-12-31 | 杭州众材科技股份有限公司 | Entire paper deacidification method |
| CN114753186A (en) * | 2022-04-15 | 2022-07-15 | 南京大学 | Paper deacidification composite material with high-stability suspension dispersion in fluorocarbon medium and preparation method and application thereof |
| CN115787350A (en) * | 2022-11-04 | 2023-03-14 | 国家图书馆 | Paper fluorine-containing deacidification liquid |
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