CN113882188A - Protection method of paper cultural relics containing transition metal - Google Patents
Protection method of paper cultural relics containing transition metal Download PDFInfo
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- CN113882188A CN113882188A CN202111143483.7A CN202111143483A CN113882188A CN 113882188 A CN113882188 A CN 113882188A CN 202111143483 A CN202111143483 A CN 202111143483A CN 113882188 A CN113882188 A CN 113882188A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/0063—Preservation or restoration of currency, books or archival material, e.g. by deacidifying
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- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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Abstract
The invention provides a protection method of paper cultural relics containing transition metals, which comprises the following steps: contacting a region needing protection in the paper cultural relic with a polyacrylate compound, wherein the polyacrylate compound has a structure shown in a formula 1, and M is alkyl substituted by at least one hydroxyl. The invention provides a protection method of paper cultural relics containing transition metals, wherein on one hand, polyacrylate compounds have extremely low saturated vapor pressure and volatility and can be attached to the surface of paper for a long time, and on the other hand, the active free radical capture effect and the antioxidant degradation effect of the polyacrylate compounds can effectively avoid the damage of hydrogen peroxide and hydroxyl free radicals to the fiber framework of the paper, thereby prolonging the effective protection time of the paper cultural relics containing the transition metals.
Description
Technical Field
The invention relates to the technical field of paper cultural relic protection, in particular to a protection method of paper cultural relics containing transition metals.
Background
A large number of paper-based cultural relics stored in various parts of the world in recent years undergo severe deterioration and discoloration during long-term storage. The paper is formed by assembling cellulose macromolecules through polymer chains in a multi-scale mode, and on the molecular level, the degradation of cellulose leads to the reduction of the polymerization degree, the formation of terminal aldehyde groups and the generation of carbonyl or carboxyl-containing oxidation groups. Some of the transition metal species contained in the pigments also promote the degradation of cellulose in the paper. For example, the use of iron bladder ink can cause severe corrosion to the paper, causing perforation around the ink; in the Chinese painting using the malachite pigment, the paper base material around the pigment is yellowed and even embrittled, which directly affects the readability and appreciation value of the artwork and the stability of long-term storage.
Pigments containing transition metal species cause corrosive degradation of paper, essentially fenton-like oxidative degradation of cellulose. The hydroxyl radical generated by fenton-like reaction is a kind of active molecule, which can react with almost all biological macromolecules, organic matters or inorganic matters in various types, and has very high reaction rate and hydrophilicity, thus being capable of accelerating the degradation of cellulose and causing the damage of paper. In order to slow down the corrosion of the paper by the ink and the pigment,
and Cabrita et al use 1-ethyl-3-methylimidazolium bromide, magnesium calcium phytate, and like protective agents to slow down this process [ ChemSusChem 2008,1, 921-926; langmuir 2010,26,24,19084-](ii) a Potthast et al slow the corrosive degradation of pigments to paper by adding tetrabutylammonium bromide, gelatin, etc. [ carbohydr. Polymer.2015, 134,136-143]. But these protective agents are described inThe color, pH or surface pigment state of the paper is influenced to a certain extent, and free radicals cannot be effectively removed, so that the long-acting protection effect cannot be achieved.
Therefore, in order to solve the problems of the conventional protective agent, such as unsatisfactory protective effect on paper containing a transition metal pigment, short protective effect, repeated coating and the like, the attention is drawn to how to prolong the effective protective time of paper cultural relics without affecting the color, pH or surface pigment of the paper.
Disclosure of Invention
The invention provides a protection method of paper cultural relics containing transition metals, which is used for prolonging the effective protection time of the paper cultural relics containing the transition metals.
The invention provides a protection method of paper cultural relics containing transition metals, which comprises the following steps: contacting a region needing to be protected in a paper cultural relic with a polyacrylate compound, wherein the polyacrylate compound has a structure shown in a formula 1, and M is an alkyl group substituted by at least one hydroxyl group;
further, the transition metal is one or more of iron, copper, chromium, zinc, mercury and cadmium.
Further, the polyacrylate compound is one or more of poly-2-hydroxypropyl acrylate, poly-2, 5-dihydroxyhexyl acrylate, poly-2, 4-dihydroxypentyl acrylate and poly-2, 3, 4-trihydroxybutyl acrylate.
Further, the polyacrylate compound is prepared by the following preparation method:
step 1, under the protection of inert gas, activating an acrylate monomer containing a stabilizer to obtain the acrylate monomer, wherein the reaction process is shown as a formula 2:
R-R →. R +. R formula 3
further, the mass of the initiator is 0.01-0.2% of that of the acrylate monomer.
Further, the initiator is one or more of AIBN, DtBP, DCP, tBPB, DBPO or LP.
Further, the reaction temperature of the free radical addition reaction in the step 3 is 60-90 ℃, and the reaction time is 3-12 h.
Further, a polyacrylate compound is dissolved in a solvent to obtain a mixed solution, the mixed solution is contacted with an area needing to be protected in the paper cultural relic by adopting one or more methods of soaking, smearing and spraying, and the mass ratio of the polyacrylate compound to the solvent is 1:200-1: 10.
Further, the mixed solution also comprises a water-based protective agent, wherein the water-based protective agent is one or two of magnesium calcium phytate and magnesium hydroxide.
Further, the mass of the polyacrylate compound is 0.5-10% of the total mass of the mixed solution.
The invention provides a protection method of paper cultural relics containing transition metal, on one hand, polyacrylate compounds have extremely low saturated vapor pressure and volatility and can be attached to the surface of paper for a long time, and on the other hand, the active free radical capture effect and the antioxidant degradation effect of the polyacrylate compounds can effectively avoid the damage of hydrogen peroxide and hydroxyl free radicals to the cellulose skeleton of the paper, thereby prolonging the effective protection time of the paper cultural relics containing transition metal; in addition, the polyacrylate compound used in the invention has the advantages of low price, easy obtaining, rapid synthesis method, high utilization rate of raw materials, convenient operation, no toxicity, no harm, green and environmental protection.
Drawings
FIG. 1 shows the preparation of poly-2-hydroxypropyl 2-acrylate according to example 1 of the present invention1H-NMR spectrum;
FIG. 2 is a scanning electron micrograph of poly-2-hydroxypropyl acrylate treated paper and untreated paper reacted in Fenton-like reagent for 2 hours, 12 hours and 48 hours according to example 1 of the present invention;
FIG. 3a is a graph showing the color of poly-2-hydroxypropyl acrylate treated paper in Fenton-like reagent after 48 hours of reaction in a Fenton-like reagent, according to example 1 of the present invention;
FIG. 3b shows the color of paper without polyacrylate compound after 48 hours reaction in Fenton-like reagent;
FIG. 4 is a drawing showing the preparation of poly-2-propenoic acid-2, 4-dihydroxypentyl ester according to example 2 of the present invention1H-NMR spectrum;
FIG. 5 shows poly-2-propenoic acid-2, 3, 4-trihydroxybutyl ester provided in example 3 of the present invention1H-NMR spectrum.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1) Preparation of poly-2-hydroxypropyl acrylate
Since the commercially available acrylate monomers contain the stabilizer, the stabilizer needs to be removed firstly, specifically, the commercially available 2-hydroxypropyl acrylate is removed by neutral alumina column chromatography under the protection of additional pump pressure and inert gas, wherein the height of the neutral alumina chromatographic column is 10cm, and the collected monomer reagent needs to be evacuated for 3 times by inert gas to remove oxygen.
100mL of purified 2-hydroxypropyl 2-acrylate monomer was placed in a 150mL flask, and a magnetic stirrer and Azobisisobutyronitrile (AIBN) with a monomer mass fraction of 0.1% were added.
The reaction flask is placed in an oil bath at 90 ℃ to be stirred and heated, and transparent and clear poly 2-acrylic acid-2-hydroxypropyl ester is obtained after reaction for 3 hours, the reaction equation is as follows, and the yield of the poly 2-acrylic acid-2-hydroxypropyl ester is 99%.
Preparation of poly-2-hydroxypropyl 2-acrylate1The H-NMR spectrum is shown in FIG. 1.
2) Application of poly 2-acrylic acid-2-hydroxypropyl ester in Fenton-like system paper protection
80mL of ultrapure water and 20mmol of poly-2-hydroxypropyl acrylate were mixed to obtain a mixed solution, wherein the concentration of the poly-2-hydroxypropyl acrylate was 3.25 wt%. 1.6g of a paper sample containing the transition metal pigment is soaked in the mixed solution, and 1.6mmol of anhydrous copper sulfate and 16mmol of hydrogen peroxide are added simultaneously to simulate a Fenton-like reaction system for degrading the paper cultural relic containing the transition metal pigment. The reaction system was placed in an oven at 90 ℃ for 2, 6, 12, 24, and 48 hours, respectively, to fully simulate the oxidative degradation process that occurs over long periods of time for paper cultural relics containing transition metal pigments. And (3) taking out the paper sample after each reaction stage is finished, washing the paper sample with ultrapure water and naturally airing the paper sample, and finding that the treated paper has no obvious color change or damage after the reaction.
In order to better embody the protective effect of the invention, an unprotected group control experiment is carried out at the same time: in the unprotected group, 1.6g of paper is soaked in 80mL of ultrapure water, and 1.6mmol of anhydrous copper sulfate and 16mmol of hydrogen peroxide are added simultaneously to simulate a Fenton-like reaction system for initiating the degradation of the paper cultural relics containing the transition metal pigments. The reaction system was placed in an oven at 90 ℃ for 2, 6, 12, 24, and 48 hours to fully simulate the oxidative degradation process that occurs over an extended period of time for paper cultural relics containing transition metal pigments. After each reaction stage, the paper sample was taken out, washed with ultrapure water and air-dried naturally.
The observation result of observing the paper fiber by adopting a scanning electron microscope is shown in fig. 2, the fiber on the surface of the paper of the protective group can better maintain the original shape (fig. 2d-f) along with the prolonging of time, the fiber of the paper of the unprotected group is subjected to oxidative degradation by hydroxyl radical to form cavities and even breaks (fig. 2a-c), in fig. 2, a and d are electron microscope images of the paper after 2h of reaction, b and e are electron microscope images of the paper after 12h of reaction, and c and f are electron microscope images of the paper after 48h of reaction.
Taking out the paper sample after 48h of reaction, observing the colors of the protected group and the unprotected group as shown in figures 3a-3b, and testing the polymerization degree, the reduced carbonyl content and the carboxyl content of the paper respectively, wherein the process operations are as follows, and the test results are shown in table 1:
polymerization degree: the degree of polymerization of the paper was measured according to ISO 5351 using the copper ethylenediamine solution viscometry. Weighing a proper amount of paper samples to be detected in a certain amount of copper ethylenediamine solution, fully oscillating and dissolving, measuring the viscosity of the paper samples by using a viscometer under the condition of standard temperature, and calculating the polymerization degree of the paper samples according to the method specified by ISO 5351. Each set of samples was tested 3 times and the final polymerization results averaged.
Reducing the content of carbonyl: 0.5mL of a 0.5 % strength 2,3, 5-triphenyltetrazolium chloride solution and 0.5mL of a 0.5mol/L KOH solution were mixed, and 2 to 10mg of a paper sample was added to the solution. The reaction mixture was heated in an open 10mL tube in a water bath at 80 ℃ for 6 minutes. Then 8ml of methanol were added after the reaction suspension had cooled to room temperature. Finally, the absorbance of the liquid at 482nm was measured using an ultraviolet spectrophotometer, and a standard curve was constructed with glucose solutions of different concentrations. The results of the reduced carbonyl content are the average of 3 determinations.
Carboxyl group content: 150mg of paper was added to 50mL of H2And (4) in O. Then 5mL of NaCl solution with a concentration of 0.01mol/L was added to increase the conductivity. After stirring for 1 hour, 0.1 part of a solvent was addedThe pH was adjusted to 2.5 with mol/L HCl solution. Finally, 0.04mol/L NaOH solution was added at a rate of 0.1mL/min until the pH of the solution rose to 11, while the conductivity of the solution was measured on a conductivity meter. And calculating the carboxyl content of the paper sample according to the conductivity titration curve.
TABLE 1 color difference, degree of polymerization, reduced carbonyl and carboxyl content of the protected versus unprotected paper
| Protection group (48h) | Unprotected group (48h) | |
| Color difference | FIG. 3a | FIG. 3b |
| Degree of polymerization | 722 | 316 |
| Content of reduced carbonyl group (. mu. mol/g) | 372.9 | 1942.6 |
| Carboxyl group content (μmol/g) | 102.4 | 594.7 |
The results of the paper pattern after 48 hours of treatment in example 1 are shown in Table 1, the paper pattern after the treatment has no obvious color change and no breakage, the polymerization degree is reduced from 1022 to 722, the content of the reduced carbonyl group and the content of the carboxyl group are 372.9 mu mol/g and 102.4 mu mol/g respectively, the paper of the unprotected group has yellowing and embrittlement phenomena, the polymerization degree of the paper after 48 hours is sharply reduced from 1022 to 316, and the content of the reduced carbonyl group and the content of the carboxyl group of the paper after 48 hours are 1942.6 mu mol/g and 594.7 mu mol/g respectively, which shows that the poly-2-propenoic acid-2-hydroxypropyl ester provided by the example can effectively protect the paper containing the transition metal.
Example 2
1) Preparation of poly-2-propenoic acid-2, 4-dihydroxypentyl ester
The stabilizer was removed by chromatography on a neutral alumina column with a height of 10cm from a commercially available 100-200mL of monomeric 2-propenoic acid-2, 4-dihydroxyamyl ester under additional pump pressure and inert gas, and the collected monomeric reagent was evacuated 3 times with inert gas to remove oxygen.
100mL of purified 2-propenoic acid-2, 4-dihydroxypentyl ester monomer was placed in a 150mL flask, and a magnetic stirrer and Azobisisobutyronitrile (AIBN) with a monomer mass fraction of 0.1% were added.
And (3) placing the reaction flask in an oil bath at 90 ℃, stirring and heating, and reacting for 3 hours to obtain transparent and clear poly 2-acrylic acid-2, 4-dihydroxyamyl ester, wherein the yield of the product poly 2-acrylic acid-2, 4-dihydroxyamyl ester is 98%. Preparation of poly-2-propenoic acid-2, 4-dihydroxypentyl ester1The H-NMR spectrum is shown in FIG. 4.
2) Application of poly 2-acrylic acid-2, 4-dihydroxyamyl ester
80mL of ultrapure water and 20mmol of poly-2-propenoic acid-2, 4-dihydroxypentyl ester were mixed to obtain a mixed solution, wherein the concentration of poly-2-propenoic acid-2, 4-dihydroxypentyl ester was 4.70 wt%. A1.6 g paper sample containing the transition metal pigment is soaked in a protective agent solution, and simultaneously 1.6mmol of anhydrous copper sulfate and 16mmol of hydrogen peroxide are added to simulate a Fenton-like reaction system for degrading the paper cultural relic containing the transition metal pigment. The reaction system was placed in an oven at 90 ℃ for 2, 6, 12, 24, and 48 hours, respectively, to fully simulate the oxidative degradation process that occurs over long periods of time for paper cultural relics containing transition metal pigments. And (3) taking out the paper sample after each reaction stage is finished, washing the paper sample with ultrapure water and naturally airing the paper sample, and finding that the paper has no obvious color change or damage after the reaction.
The degree of polymerization, the content of reduced carbonyl groups and the content of carboxyl groups of the papers of the protected group and the unprotected group were measured in the same manner as in example 1, and the results are shown in Table 2.
TABLE 2 degree of polymerization, reduced carbonyl and carboxyl content of the protected versus unprotected paper
| Protection group (48h) | Unprotected group (48h) | |
| Degree of polymerization | 725 | 316 |
| Content of reduced carbonyl group (. mu. mol/g) | 389.1 | 1942.6 |
| Carboxyl group content (μmol/g) | 120.9 | 594.7 |
Experiments on the polymerization degree, the reduced carbonyl content and the carboxyl content prove that the polymerization degree of the paper added with the poly 2-acrylic acid-2, 4-dihydroxyamyl alcohol protective agent is only reduced to 725 from 1022 after reaction for 48 hours, and the reduced carbonyl content and the carboxyl content are 389.1 mu mol/g and 120.9 mu mol/g respectively, as shown in the table 2, the poly 2-acrylic acid-2, 4-dihydroxyamyl alcohol protective agent can effectively protect the paper containing the transition metal pigment.
Example 3
1) Preparation of poly-2-propenoic acid-2, 3, 4-trihydroxybutyl ester
Under the protection of an additional pump pressure and inert gas, the commercially available monomer 2-acrylic acid-2, 3, 4-trihydroxybutyl ester with the volume of 100-200mL is subjected to neutral alumina column chromatography to remove the stabilizer, wherein the height of a neutral alumina chromatographic column is 10cm, and the collected monomer reagent needs to be evacuated for 3 times by the inert gas to remove oxygen.
100mL of purified 2-propenoic acid-2, 3, 4-trihydroxybutyl ester monomer was placed in a 150mL flask, and magnetic stirrer and Azobisisobutyronitrile (AIBN) with a monomer mass fraction of 0.1% were added.
And (3) placing the reaction flask in an oil bath at 90 ℃, stirring and heating, and reacting for 3 hours to obtain transparent and clear poly 2-acrylic acid-2, 3, 4-trihydroxy butyl ester, wherein the yield of the poly 2-acrylic acid-2, 3, 4-trihydroxy butyl ester is 97%. Process for preparing poly-2-propenoic acid-2, 3, 4-trihydroxybutyl ester1The H-NMR spectrum is shown in FIG. 5.
2) Application of poly-2-propenoic acid-2, 3, 4-trihydroxy butyl ester
80mL of ultrapure water and 20mmol of poly 2-acrylic acid-2, 3, 4-trihydroxybutyl ester are mixed into a mixed solution, wherein the concentration of the poly 2-acrylic acid-2, 3, 4-trihydroxybutyl ester is 4.70 wt%. A1.6 g paper sample containing the transition metal pigment is soaked in a protective agent solution, and simultaneously 1.6mmol of anhydrous copper sulfate and 16mmol of hydrogen peroxide are added to simulate a Fenton-like reaction system for degrading the paper cultural relic containing the transition metal pigment. The reaction system was placed in an oven at 90 ℃ for 2, 6, 12, 24, and 48 hours, respectively, to fully simulate the oxidative degradation process that occurs over long periods of time for paper cultural relics containing transition metal pigments. And (3) taking out the paper sample after each reaction stage is finished, washing the paper sample with ultrapure water and naturally airing the paper sample, and finding that the paper has no obvious color change or damage after the reaction.
The degree of polymerization, the content of reduced carbonyl groups and the content of carboxyl groups of the papers of the protected group and the unprotected group were measured in the same manner as in example 1, and the results are shown in Table 3.
TABLE 3 degree of polymerization, reduced carbonyl and carboxyl content of the protected versus unprotected paper
| Protection group (48h) | Unprotected group (48h) | |
| Degree of polymerization | 743 | 316 |
| Content of reduced carbonyl group (. mu. mol/g) | 364.3 | 1942.6 |
| Carboxyl group content (μmol/g) | 113.5 | 594.7 |
Experiments on the polymerization degree, the reduced carbonyl content and the carboxyl content are carried out to conclude that the polymerization degree of the paper added with the poly 2-acrylic acid-2, 3, 4-trihydroxy butyl ester alcohol protective agent is only reduced to 743 from 1022 after 48 hours of reaction, and the reduced carbonyl content and the carboxyl content are 364.3 mu mol/g and 113.5 mu mol/g respectively, which indicates that the poly 2-acrylic acid-2, 3, 4-trihydroxy butyl ester alcohol protective agent can effectively protect the paper containing the transition metal pigment.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for protecting paper cultural relics containing transition metals, which is characterized by comprising the following steps: contacting a region needing to be protected in a paper cultural relic with a polyacrylate compound, wherein the polyacrylate compound has a structure shown in a formula 1, and M is an alkyl group substituted by at least one hydroxyl group;
2. the method of claim 1, wherein the transition metal is one or more of iron, copper, chromium, zinc, mercury, and cadmium.
3. The method of claim 1, wherein the polyacrylate compound is one or more of poly-2-hydroxypropyl acrylate, poly-2, 5-dihydroxyhexyl acrylate, poly-2, 4-dihydroxypentyl acrylate, and poly-2, 3, 4-trihydroxybutyl acrylate.
4. The method according to claim 1, wherein the polyacrylate compound is prepared by the following preparation method:
step 1, under the protection of inert gas, activating an acrylate monomer containing a stabilizer to obtain the acrylate monomer, wherein the reaction process is shown as a formula 2:
step 2, generating active free radicals by an initiator under the heating condition, wherein the reaction process is shown as a formula 3;
R-R→.R+.r formula 3
Step 3, carrying out free radical addition reaction on the activated acrylate monomer and active free radicals to obtain a polyacrylate compound, wherein the reaction process is shown as a formula 4;
5. the method according to claim 4, wherein the mass of the initiator is 0.01 to 0.2% of the mass of the acrylate monomer.
6. The method of claim 4, wherein the initiator is one or more of AIBN, DtBP, DCP, tBPB, DBPO or LP.
7. The method according to claim 4, wherein the reaction temperature of the radical addition reaction in step 3 is 60 to 90 ℃ and the reaction time is 3 to 12 hours.
8. The method as claimed in claim 1, wherein the polyacrylate compound is dissolved in a solvent to obtain a mixed solution, and the mixed solution is contacted with the area to be protected in the paper cultural relic by one or more of soaking, smearing and spraying, wherein the mass ratio of the polyacrylate compound to the solvent is 1:200-1: 10.
9. The method according to claim 8, wherein the mixed solution further comprises a water-based protective agent, and the water-based protective agent is one or two of magnesium calcium phytate and magnesium hydroxide.
10. The method according to claim 8, wherein the mass of the polyacrylate compound is 0.5 to 10% of the total mass of the mixed solution.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105713155A (en) * | 2016-01-29 | 2016-06-29 | 江苏大学 | Preparation method of polymer material for paper cultural relic protection and application thereof |
| CN110924226A (en) * | 2019-12-03 | 2020-03-27 | 东南大学 | Deacidifying reinforcing protective agent and preparation method and application thereof |
| CN111303353A (en) * | 2020-03-19 | 2020-06-19 | 郑州大学 | Chitosan/nano TiO for paper protection2Acrylate reinforcing liquid and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105713155A (en) * | 2016-01-29 | 2016-06-29 | 江苏大学 | Preparation method of polymer material for paper cultural relic protection and application thereof |
| CN110924226A (en) * | 2019-12-03 | 2020-03-27 | 东南大学 | Deacidifying reinforcing protective agent and preparation method and application thereof |
| CN111303353A (en) * | 2020-03-19 | 2020-06-19 | 郑州大学 | Chitosan/nano TiO for paper protection2Acrylate reinforcing liquid and application thereof |
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| 刘博: "功能苯丙乳液的合成及纸质文物保护应用研究", 《中国优秀硕士学位论文全文数据库（硕士） 哲学与人文科学辑》 * |
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