A deacidification solution for soaking and deacidifying a whole volume of ancient books, and its preparation method and application
By using a homogeneous hydrofluoroether solution containing aminosilane as the deacid solution, the stability and drying problems in the deacidification treatment of the whole ancient book were solved, and effective deacidification and tensile strength of the paper were achieved.
Patent Information
- Application Number
- CN202311155911.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-09-07
- Publication Date
- 2025-05-06
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
The prior art is difficult to provide a stable deacid solution suitable for the entire ancient book, and the traditional method can easily lead to paper deformation, adhesion and secondary damage during the drying process.
A homogeneous solution of hydrofluoroether containing aminosilane is used as the deacid solution. By forming a stable homogeneous solution with hydrofluoroether, precipitation and uneven drying are avoided to ensure uniform dispersion and volatility of alkaline substances.
It realizes stable deacidification of ancient books, improves the tensile strength of the paper, avoids deformation and adhesion problems during drying, and ensures the integrity of ancient books and the protection of cultural relics.
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Figure CN117306309B_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of ancient book protection, and more specifically, relates to a deacidification solution for soaking and deacidifying a whole volume of ancient books, and a preparation method and application thereof. Background Art
[0002] Many valuable ancient books have been preserved in the long history of our country, but the existing ancient books are facing varying degrees of damage. The main raw material used for papermaking of ancient books is plant fiber. During long-term preservation, plant fiber will inevitably be disturbed by various external factors such as acidification, mildew or insect infestation, which will cause the stability of paper to decrease. Among them, the acidification of paper is one of the most important factors that cause damage to ancient books. This is because acidic conditions will accelerate the hydrolysis rate of cellulose in paper. The hydrolysis of cellulose will cause the chain structure in its molecular structure to break and the degree of polymerization to decrease, which will increase the brittleness of the paper and reduce the strength, thus destroying the paper. Therefore, the core issue of ancient book protection is to deacidify ancient books to solve the problem of paper acidification and avoid the damage of paper acidification to ancient books.
[0003] The simplest strategy for deacidification of ancient books is to use alkaline substances to treat ancient books based on the principle of acid-base neutralization. The currently reported strategies for neutralizing acidic substances in ancient books with alkaline substances are mainly divided into two categories. One is to use a silane coupling agent or silicic acid for simple modification. This is because silane or silicic acid is easily hydrolyzed, and the silanol Si-OH produced by hydrolysis interacts with C-OH in paper cellulose to achieve the purpose of deacidification and enhancing the performance of ancient books (Chinese Journal of Polymer Science, 2015, 33: 1672-1682., Carbohydr Polym, 2019, 209: 250-257., Materials, 2023, 16: 3351.). Another strategy is to use a nanoparticle dispersion containing alkaline oxides, hydroxides, and carbonates to apply to ancient books for deacidification (Paper and Papermaking, 2009, 28(05): 40-42.; Applied Clay Science, 2021, 213: 106231.; China Papermaking, 2022, 41, 45; Papermaking Science and Technology, 2019, 38, 6.; China Papermaking, 2022, 41, 52; CN16065421A). The core idea of this method is to use alkaline substances or alkaline substances formed by hydrolysis to neutralize the acidic substances in ancient books to achieve the purpose of deacidification. However, this deacidification method has problems such as the easy hydrolysis of alkaline substances, poor dispersion of nanoparticles, and easy aggregation and sedimentation of nanoparticles, which leads to poor stability of the prepared deacidification solution and difficulty in long-term storage. In addition, because the dispersion liquid used by dispersion liquid is mostly water system, and water volatilization speed is slow at room temperature, the dried paper is prone to wrinkles, deformation, and has an impact on the handwriting in ancient books, and is not easy to scale deacidification. To solve the problem that nanoparticles are easy to reunite and the water volatilization speed is slow, Ren Junli et al. invented a kind of multifunctional ancient book repair liquid (CN109518527B) composed of an alkaline mixed sol and an alcohol-water mixed solution containing a quaternary ammonium salt, which is dispersed in an inert solvent containing a surfactant by metal oxide nanoparticles. Although the method utilizes surfactant to increase the dispersibility and stability of nanoparticles in aqueous solution, the surfactant also can not avoid weakening the interaction between alkaline substances and ancient books. More importantly, in the volatilization process of the solution, due to the formation of nanoparticles and dispersion liquid, it is still a heterogeneous system, which will cause the occurrence of "coffee ring effect" in the drying process, that is, the dried nanoparticles will present a situation of uneven distribution, bringing secondary damage (such as CN108316054B etc.) to ancient books and cultural relics.
[0004] On the other hand, the current deacidification strategy for ancient books is only applicable to the processing of single pages or several pages of paper, which requires that the ancient books must be disassembled into single pages first, and then each paper document must be processed separately, and then rebound after completion. Although this treatment method can deacidify, due to the long storage time of ancient books and their low strength, the process of disassembling and binding is very easy to cause damage, resulting in secondary damage to the ancient books, and this method has a complicated treatment process and a long cycle. In addition, if an aqueous solution dispersion system is used to deacidify the entire volume of ancient books, it is necessary to accelerate the evaporation speed of the aqueous solution in the ancient books after immersion by drying at a higher temperature (40℃-80℃). The drying process will accelerate the aging of the fibers and the risk of fiber breakage, and even cause damage to the ancient books, causing secondary damage.
[0005] In summary, there is an urgent need to provide an ancient book deacidification liquid that can be used for the deacidification of a whole volume of ancient books. Such a deacidification liquid should be able to form a stable and easily volatile homogeneous solution with an alkaline substance. At the same time, when used for the deacidification of a whole volume of ancient books, the deacidification liquid should also prevent the paper from sticking to each other and prevent secondary damage to the ancient books. However, there are few reports on ancient book deacidification liquids that can fully meet the above requirements. Summary of the invention
[0006] In view of the shortcomings and deficiencies of the above prior art, the primary purpose of the present invention is to provide a method for preparing a deacidification solution for immersion deacidification of a whole volume of ancient books.
[0007] The above-mentioned purpose of the present invention is achieved through the following technical solutions:
[0008] A deacidification solution for soaking and deacidifying a whole volume of ancient books. The deacidification solution for soaking and deacidifying a whole volume of ancient books is a hydrofluoroether homogeneous solution containing aminosilane and has no precipitation.
[0009] Preferably, the aminosilane in the deacidification solution is any one or more of 3-aminopropylmethyldimethoxysilane, N-aminoethyl-3-aminopropyltriethoxysilane, di(3-trimethoxysilylpropyl)amine and diethylaminomethyltriethoxysilane.
[0010] More preferably, the aminosilane in the deacidification solution is 3-aminopropylmethyldimethoxysilane or N-aminoethyl-3-aminopropyltriethoxysilane.
[0011] Preferably, the hydrofluoroether in the deacidification solution is any one of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1-chloro-2,2,2-trifluoroethyldifluoromethyl ether, 1,1,2,2-tetrafluoroethyl ether, fluoromethyl-1,1,1,3,3,3-hexafluoroisopropyl ether, methyl nonafluorobutyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether and perfluorobutyl ether.
[0012] More preferably, the hydrofluoroether in the deacidification solution is 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1-chloro-2,2,2-trifluoroethyldifluoromethyl ether, or 1,1,2,2-tetrafluoroethyl ethyl ether.
[0013] More preferably, the aminosilane in the deacidification solution is 3-aminopropylmethyldimethoxysilane, and the hydrofluoroether in the homogeneous solution is 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether.
[0014] Preferably, in the deacidification solution, the volume ratio of aminosilane to hydrofluoroether is (0.75-15):100.
[0015] More preferably, the volume ratio of aminosilane to hydrofluoroether is (3.5-15):100.
[0016] More preferably, the volume ratio of aminosilane to hydrofluoroether is (10-15):100.
[0017] The application of the above-mentioned deacidification liquid for immersion deacidification of a whole volume of ancient books in deacidification of ancient books, i.e., a method for immersion deacidification of a whole volume of ancient books, comprises the following steps:
[0018] S1. Clean up impurities in ancient books;
[0019] S2. completely immerse the entire ancient book in the above-mentioned deacidification solution;
[0020] S3. Place the soaked ancient books in a ventilated place to dry (natural ventilation and drying will do).
[0021] Preferably, the soaking time in step S2 is 5-90 seconds.
[0022] Preferably, steps S2-S3 are repeated 1-4 times (ie, the total number of immersion times of the ancient books is 2-5 times).
[0023] After soaking in this method, the ancient books can be dried by natural ventilation, for example, at room temperature of 25°C (20-40°C) for 12-48 hours.
[0024] More preferably, in the above steps, the ancient books are immersed twice and the immersion time is 20 seconds.
[0025] The pH of ancient books treated with this deacidifying solution is between 8.0 and 9.5, and the residual alkali content reaches 0.5-2.5% calcium carbonate equivalent to the dry weight of the paper. After treatment, the surface of the paper is clean and smooth, there is no obvious change in the handwriting and ink, and the tensile strength is significantly improved.
[0026] The present invention has the following beneficial effects:
[0027] 1. The aminosilane used in the ancient book deacidification liquid of the present invention can form a uniform and stable solution with hydrofluoroether. Compared with the traditional oxide particle / perfluoroalkane heterogeneous system, it has the characteristics of no phase separation and no sedimentation after long-term storage, and the alkaline substance is evenly dispersed after drying. After the liquid is dried, the aminosilane can be evenly attached to the paper without the coffee ring effect.
[0028] 2. After the ancient books are treated with this deacidification solution, the amino groups in the silane of the acidic group of the paper are neutralized, and the ancient book pages are finally restored to weak alkalinity. At the same time, the Si-O formed by the hydrolysis of the silane and the C-OH in the cellulose protect the paper. Therefore, it can deacidify the paper and enhance the tensile strength at the same time.
[0029] 3. The hydrofluoroether used in the present invention is a type of chemically inert liquid with a low boiling point and a fast volatilization rate, and will not have a significant impact on the pages of ancient books after volatilization.
[0030] 4. The deacidification liquid components of the ancient books of the present invention are all transparent and colorless liquids, which can ensure that the color difference and brightness of the ancient books and cultural relics after deacidification remain basically unchanged. At the same time, it also has the advantages of short processing time, low liquid consumption, and little impact on paper, and is suitable for one-time processing of the entire book. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Figure 1 This is a digital photo of the deacidification solution in Example 1.
[0032] Figure 2 The tensile strength and tensile strength improvement ratio of ancient books before treatment (control sample) and after treatment with deacidification solutions of different concentrations are compared (Examples 1-8).
[0033] Figure 3 The comparison is for the pH value and the alkali residue of the ancient books before treatment (control sample) and after treatment with deacidification solutions of different concentrations (Examples 1-8).
[0034] Figure 4 Digital photos of a 15% perfluoroheptane solution of commercially available magnesium oxide and the deacidified solution in Example 1 after being allowed to stand for three months. DETAILED DESCRIPTION
[0035] The present invention is further described below in conjunction with the accompanying drawings and specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.
[0036] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.
[0037] Example 1
[0038] 15 mL of 3-aminopropylmethyldimethoxysilane was added to 100 mL of 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, and the mixture was shaken thoroughly to prepare a deacidification solution. Figure 1 As shown, the deacidified solution is a clear and transparent uniform solution without stratification or sedimentation.
[0039] The whole book after impurity treatment was immersed in the deacidification solution for 5 seconds, then taken out and dried at 20°C for 12 hours. After drying, the above operation was repeated twice.
[0040] The paper samples treated in this embodiment were tested for tensile strength (GB / T 12914-2008), pH value (GB / T 13528-2015) and residual alkali content (GB / T 24998-2010) according to national standards. Figure 2 , Figure 3 As shown, the pH value of the treated paper sample increased from 5.10 to 9.01, the residual alkali content reached 2.24% calcium carbonate equivalent of the dry weight of the paper, and the tensile strength increased from 355N / m to 597N / m, indicating that the pH value of the paper was significantly increased after the deacidification solution treatment, slowing down the degradation of the paper, and the tensile strength of the paper increased by 68%, which can delay the embrittlement of the paper. After treatment, the surface of the paper is smooth and tidy, the handwriting is clear, there is no effect on the ink, no change in brightness and color difference, and no coffee ring effect.
[0041] Example 2
[0042] 13.5 mL of N-aminoethyl-3-aminopropyltriethoxysilane was added to 100 mL of 1-chloro-2,2,2-trifluoroethyldifluoromethyl ether, and the mixture was shaken thoroughly to prepare a deacidification solution.
[0043] The whole book after impurity treatment was immersed in the deacidification solution for 20 seconds, then taken out and dried at 25°C for 48 hours. After drying, the above operation was repeated twice.
[0044] The paper samples treated in this embodiment were tested for tensile strength (GB / T 12914-2008), pH value (GB / T 13528-2015) and residual alkali content (GB / T 24998-2010) according to national standards. Figure 2 , Figure 3 As shown in the figure, the pH value of the treated paper sample increased from 5.10 to 8.77, the residual alkali content reached 1.16% calcium carbonate equivalent of the dry weight of the paper, and the tensile strength increased from 355N / m to 579N / m, an increase of 63%. After treatment, the surface of the paper is smooth and tidy, the handwriting is clear, there is no effect on the ink, no change in brightness and color difference, and no coffee ring effect.
[0045] Example 3
[0046] To 100 mL of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 10 mL of di(3-trimethoxysilylpropyl)amine was added, and the mixture was shaken thoroughly to prepare a deacidification solution.
[0047] The whole book after impurity treatment was immersed in the deacidification solution for 20 seconds, then taken out and dried at 25°C for 48 hours. After drying, the above operation was repeated twice.
[0048] The paper samples treated in this embodiment were tested for tensile strength (GB / T 12914-2008), pH value (GB / T 13528-2015) and residual alkali content (GB / T 24998-2010) according to national standards. Figure 2 , Figure 3 As shown, the pH value of the treated paper sample increased from 5.10 to 8.76, the residual alkali content reached 0.91% calcium carbonate equivalent of the dry weight of the paper, and the tensile strength increased from 355N / m to 579N / m, an increase of 63%. After treatment, the surface of the paper is smooth and tidy, the handwriting is clear, there is no effect on the ink, no change in brightness and color difference, and no coffee ring effect.
[0049] Example 4
[0050] 8 mL of diethylaminomethyltriethoxysilane was added to 100 mL of 1,1,2,2-tetrafluoroethyl ether, and the mixture was shaken thoroughly to prepare a deacidification solution.
[0051] The whole book after impurity treatment was immersed in the deacidification solution for 20 seconds, then taken out and dried at 25°C for 48 hours. After drying, the above operation was repeated twice.
[0052] The paper samples treated in this embodiment were tested for tensile strength (GB / T 12914-2008), pH value (GB / T 13528-2015) and residual alkali content (GB / T 24998-2010) according to national standards. Figure 2 , Figure 3 As shown, the pH value of the treated paper sample increased from 5.10 to 8.61, the residual alkali content reached 0.87% calcium carbonate equivalent of the dry weight of the paper, and the tensile strength increased from 355N / m to 566N / m, an increase of 59%. After treatment, the surface of the paper is smooth and tidy, the handwriting is clear, there is no effect on the ink, no change in brightness and color difference, and no coffee ring effect.
[0053] Example 5
[0054] 5 mL of 3-aminopropylmethyldimethoxysilane was added to 100 mL of fluoromethyl-1,1,1,3,3,3-hexafluoroisopropyl ether, and the mixture was shaken thoroughly to prepare a deacidification solution.
[0055] The whole book after impurity treatment was immersed in the deacidification solution for 20 seconds, then taken out and dried at 25°C for 48 hours. After drying, the above operation was repeated twice.
[0056] The paper samples treated in this embodiment were tested for tensile strength (GB / T 12914-2008), pH value (GB / T 13528-2015) and residual alkali content (GB / T 24998-2010) according to national standards. Figure 2 , Figure 3 As shown, the pH value of the treated paper sample increased from 5.10 to 8.47, the residual alkali content reached 0.81% calcium carbonate equivalent of the dry weight of the paper, and the tensile strength increased from 355N / m to 542 / m, an increase of 53%. After treatment, the surface of the paper is smooth and tidy, the handwriting is clear, there is no effect on the ink, no change in brightness and color difference, and no coffee ring effect.
[0057] Example 6
[0058] 3.5 mL of N-aminoethyl-3-aminopropyltriethoxysilane was added to 100 mL of methyl nonafluorobutyl ether, and the mixture was shaken thoroughly to prepare a deacidification solution.
[0059] The whole book after impurity treatment was immersed in the deacidification solution for 20 seconds, then taken out and dried at 25°C for 24 hours. After drying, the above operation was repeated four times.
[0060] The paper samples treated in this embodiment were tested for tensile strength (GB / T 12914-2008), pH value (GB / T 13528-2015) and residual alkali content (GB / T 24998-2010) according to national standards. Figure 2 , Figure 3 As shown, the pH value of the treated paper sample increased from 5.10 to 8.33, the residual alkali content reached 0.61% calcium carbonate equivalent of the dry weight of the paper, and the tensile strength increased from 355N / m to 533N / m, which was a 50% increase in tensile strength. After treatment, the surface of the paper was smooth and tidy, the handwriting was clear, there was no effect on the ink, no change in brightness and color difference, and no coffee ring effect.
[0061] Example 7
[0062] 2.2 mL of diethylaminomethyltriethoxysilane was added to 100 mL of perfluorobutyl ether, and the mixture was shaken thoroughly to prepare a deacidification solution.
[0063] The whole book after impurity treatment was immersed in the deacidification solution for 60 seconds, then taken out and dried at 35°C for 48 hours. After drying, the above operation was repeated three times.
[0064] The paper samples treated in this embodiment were tested for tensile strength (GB / T 12914-2008), pH value (GB / T 13528-2015) and residual alkali content (GB / T 24998-2010) according to national standards. Figure 2 , Figure 3 As shown, the pH value of the treated paper sample increased from 5.10 to 8.36, the residual alkali content reached 0.56% calcium carbonate equivalent of the dry weight of the paper, and the tensile strength increased from 355N / m to 531N / m, an increase of 49.5%. After treatment, the surface of the paper is smooth and tidy, the handwriting is clear, there is no effect on the ink, no change in brightness and color difference, and no coffee ring effect.
[0065] Example 8
[0066] 0.75 mL of 3-aminopropylmethyldimethoxysilane was added to 100 mL of 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, and the mixture was shaken thoroughly to prepare a deacidification solution.
[0067] The whole book after impurity treatment was immersed in the deacidification solution for 90 seconds, then taken out and dried at 40°C for 48 hours. After drying, the above operation was repeated five times.
[0068] The paper samples treated in this embodiment were tested for tensile strength (GB / T 12914-2008), pH value (GB / T 13528-2015) and residual alkali content (GB / T 24998-2010) according to national standards. Figure 2 , Figure 3 As shown, the pH value of the treated paper sample increased from 5.10 to 8.06, the residual alkali content reached 0.51% calcium carbonate equivalent of the dry weight of the paper, and the tensile strength increased from 355N / m to 478N / m, an increase of 34%. After treatment, the surface of the paper is smooth and tidy, the handwriting is clear, there is no effect on the ink, no change in brightness and color difference, and no coffee ring effect.
[0069] Comparative Example 1
[0070] 5 mL of 3-aminopropyltrimethoxysilane was added to 100 mL of perfluorobutyl ether, and the mixture was shaken thoroughly to prepare a deacidification solution. However, after shaking, white flocculent substances appeared in the deacidification solution, and a large amount of white precipitation appeared in the solution after standing for 5 minutes. After treatment, white particles appeared in some areas of the paper surface, and ink was blurred in some areas.
[0071] Comparative Example 2
[0072] A 15% mass fraction of commercially available magnesium oxide in perfluoroheptane solution was prepared, and the deacidified solution in Example 1 and the solution were allowed to stand for three months to observe the stability of the two solutions. Figure 4 As shown in (a), it can be seen that obvious white particles have settled at the bottom of the 15% magnesium oxide perfluoroheptane solution. Figure 4 As shown in (b), the deacidification solution of Example 1 is still clear and transparent, without any stratification and no particles are visible, which proves that the deacidification solution provided by the present invention has excellent stability.
[0073] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.
Claims
1. A method for deacidification of an entire volume of ancient books by immersion, characterized in that: The steps include: S1. Clean up impurities in ancient books; S2. Soak the entire ancient book in deacidification solution; S3. Ventilate and dry the soaked ancient books; The deacidification solution is composed of aminosilane and hydrofluoroether, the volume ratio of the aminosilane to the hydrofluoroether is (10-15):100, and the deacidification solution is a homogeneous solution without precipitation; The aminosilane is any one of N-aminoethyl-3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, di(3-trimethoxysilyl)propylamine and diethylaminomethyltriethoxysilane.
2. The method according to claim 1, characterized in that: The aminosilane in the deacidification solution is 3-aminopropylmethyldimethoxysilane or N-aminoethyl-3-aminopropyltriethoxysilane.
3. The method according to claim 1, characterized in that In the deacidification solution, the boiling point of the hydrofluoroether is required to be 40°C-100°C.
4. The method according to claim 1, characterized in that: The hydrofluoroether in the deacidification solution is any one of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1-chloro-2,2,2-trifluoroethyldifluoromethyl ether, 1,1,2,2-tetrafluoroethyl ether, fluoromethyl-1,1,1,3,3,3-hexafluoroisopropyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether and perfluorobutyl ether.
5. The method according to claim 1, characterized in that: The hydrofluoroether in the deacidification solution is 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1-chloro-2,2,2-trifluoroethyldifluoromethyl ether, and 1,1,2,2-tetrafluoroethyl ether.
6. The method according to claim 1, characterized in that: The aminosilane in the deacidification solution is 3-aminopropylmethyldimethoxysilane, and the hydrofluoroether in the homogeneous solution is 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether.
7. The method according to claim 1, characterized in that: Steps S2-S3 are repeated 1-4 times.
8. The method according to claim 1, characterized in that: Steps S2-S3 are repeated twice.
9. The method according to claim 1, characterized in that: The soaking time of step S2 is 5-90 seconds.
10. The method according to claim 1, characterized in that: The soaking time in step S2 is 20 seconds.
Citation Information
Patent Citations
An ancient book processing solution and a method for processing ancient books
CN108316054B
A multifunctional ancient book restoration solution and its treatment method
CN109518527B
Deacidification of cellulose based materials using hydrofluoroether carriers
US6080448A