阅读说明：本技术 一种基于细菌纤维素的纸张脱酸增强修复液的制备方法与应用 (Preparation method and application of bacterial cellulose-based paper deacidification enhancement repair liquid ) 是由 牟洪燕 吴潇 樊慧明 于 2020-05-29 设计创作，主要内容包括：一种基于细菌纤维素的纸张脱酸增强修复液的制备方法与应用。本发明的脱酸增强修复液由0.1-1.0 wt%的细菌纤维素或其衍生物,8.0-22.0 wt%的碱及77.0-91.9 wt%的水溶液组成。该方法将细菌纤维素在碱溶液中溶解成细菌纤维素溶液,通过喷涂法、浸渍法、涂布法或超声雾化等多种方法将细菌纤维素负载到纸张上,对纸张进行脱酸增强处理,提高纸张的力学强度以及耐久性。所述细菌纤维素是由细菌微生物分泌合成的纤维素或改性细菌纤维素。细菌纤维素溶液是由无机碱或有机碱体系溶解细菌纤维素所得到的溶液。本发明的基于细菌纤维素的纸张脱酸增强修复液及对纸张的处理方法实现了对古籍纸张脱酸、增强一体化进程。(A preparation method and application of a paper deacidification strengthening repair liquid based on bacterial cellulose. The deacidification strengthening repair liquid consists of 0.1 to 1.0 weight percent of bacterial cellulose or derivatives thereof, 8.0 to 22.0 weight percent of alkali and 77.0 to 91.9 weight percent of aqueous solution. The method comprises the steps of dissolving bacterial cellulose in an alkali solution to form a bacterial cellulose solution, loading the bacterial cellulose on paper by a spraying method, a dipping method, a coating method or an ultrasonic atomization method and other methods, deacidifying and enhancing the paper, and improving the mechanical strength and durability of the paper. The bacterial cellulose is cellulose secreted and synthesized by bacterial microorganisms or modified bacterial cellulose. The bacterial cellulose solution is obtained by dissolving bacterial cellulose by an inorganic alkali or organic alkali system. The bacterial cellulose-based paper deacidification and reinforcement repair liquid and the paper treatment method realize the integrated process of deacidification and reinforcement of ancient book paper.)

1. A preparation method of a paper deacidification strengthening repair liquid based on bacterial cellulose is characterized by comprising the following steps:

(1) cleaning impurities on the surface of the ancient book paper, and carrying out constant temperature and humidity treatment;

(2) bacterial cellulose is disintegrated and then prepared into a uniformly dispersed solution;

(3) and loading the bacterial cellulose on ancient book paper, and performing deacidification and reinforcement treatment on the ancient book paper.

2. The preparation method according to claim 1, wherein in the step (1), the constant temperature and humidity treatment is to hang the paper in a constant temperature and humidity chamber with the temperature and humidity of 23 ℃ and the RH of 50% and balance the moisture for 24 h.

3. The method according to claim 1, wherein in the step (2), the bacterial cellulose is composed of bacterial cellulose or a derivative thereof, alkali and water; the base includes an inorganic base or an organic base.

4. The preparation method according to claim 3, wherein in the step (2), the bacterial cellulose solution comprises the following components in parts by mass: 0.1-1.0 wt% of bacterial cellulose or derivatives thereof, 8.0-22.0 wt% of alkali and 77.0-91.9 wt% of water.

5. The preparation method according to claim 1, wherein in the step (2), the bacterial cellulose is bacterial cellulose or modified bacterial cellulose synthesized by direct secretion of microorganisms; the modified bacterial cellulose is etherified and aminated modified bacterial cellulose which is modified by a chemical reagent or cultured by a bacterial culture solution.

6. The method according to claim 5, wherein the culture conditions of the microorganism are static or dynamic fermentation culture conditions; the microorganism is one of gluconacetobacter, acetobacter, agrobacterium, pseudomonas, achromobacter, alcaligenes, aerobacter, azotobacter, rhizobium and sarcina; the bacteria culture solution comprises a culture solution added with at least one of hydroxylamine hydrochloride, diethylenetriamine, polyethyleneimine and ammonia water;

the method for modifying the bacterial cellulose by etherification comprises the steps of soaking the bacterial cellulose by using sodium hydroxide to obtain alkali cellulose, and carrying out Williamson etherification or Michael addition reaction on the alkali cellulose and one of an alkyl compound, an alkoxy compound and a vinyl compound, wherein the alkyl compound, the alkoxy compound and the vinyl compound are one of methane chloride, chloroethane, sulfonyl ethane, ethylene oxide and acrylonitrile; the method for aminating and modifying the bacterial cellulose comprises the steps of bonding a nitrogen-containing compound with hydroxyl of the bacterial cellulose, and grafting a nitrogen-containing group, wherein the nitrogen-containing compound is one of hydroxylamine hydrochloride, polyacrylamide, ethylenediamine, diethylamine, tetraethylenepentamine, dimethylamine and N-methylimidazole.

7. The production method according to claim 3, wherein, in the step (2); the inorganic base is an alkali/urea/water system, an alkali/thiourea/water system or an alkali/thiourea/urea/water system; the organic base is one of a LiCl/dimethylacetamide (DMAc) system, a dimethyl sulfoxide (DMSO)/tetraethylammonium chloride (TEAC) system, N-methylmorpholine oxide (NMMO) or an ionic liquid solvent system.

8. The method according to claim 1, wherein the method for loading the bacterial cellulose on the ancient book paper in the step (3) is a spraying method, a dipping method, a coating method, or an ultrasonic atomization method.

9. A bacterial cellulose paper repair liquor made by the method of manufacture of any one of claims 1 to 8.

10. The bacterial cellulose paper repair liquid of claim 9 is applied to deacidification and reinforcement of ancient book documents.

Technical Field

The invention relates to the technical field of ancient book protection, in particular to a preparation method and application of a bacterial cellulose paper reinforcing agent.

Background

Ancient books are important record carriers of development and progress of history, culture and material civilization all over the world, are very important cultural relics, and have a large amount of storage in various large libraries and museums. However, ancient papers suffer from oxidation, acidification, aging, etc. Paper is a cellulose-based carrier structure containing small amounts of hemicellulose and lignin. Over time, hemicellulose and lignin are oxidized and hydrolyzed to form acidic species, which cause hydrolysis of cellulose in the paper, resulting in a decrease in the degree of polymerization of cellulose. In addition, the acid technological conditions of pulping and papermaking, and additives such as acid alum, acid rosin, alum water sizing material and the like are mostly acidic, so that the acidification of paper is further intensified. In addition, the paper is vulnerable to harmful gases and mold during storage, which is also one of the reasons for acidification and strength reduction of the paper. Therefore, protection and repair of ancient books are urgently needed. The traditional paper deacidification enhancing method has some problems such as complex process, long treatment period, poor treatment effect and the like, most researches focus on deacidification of ancient book paper, and the field of enhancing the mechanical property of the ancient book paper is less. Therefore, the preparation of the deacidification and reinforcement integrated paper repair liquid is of great importance for improving the protection effect on paper.

The bacterial cellulose is a special cellulose material synthesized by microorganisms in vitro, and is a porous reticular nano-scale high molecular polymer. The microstructure of the composite material is formed by interweaving superfine cellulose nanometer microfibrils with the width less than 100 nm, and the composite material has a large specific surface area, a high elastic modulus and a high tensile strength. The bacterial cellulose and the plant cellulose have the same chemical structure and rich hydroxyl structures, so that the bacterial cellulose and the plant fiber have strong binding capacity and are suitable for reinforcing paper. Santos et al have been used to directly culture bacterial cellulose on paper and use bacteria to secrete synthetic bacterial cellulose on the surface of paper to enhance paper performance. However, the method is difficult to operate, the conditions for culturing bacteria are too harsh, the growth period of the bacterial cellulose is long, and the added sugar source can cause pollution and damage to paper and is difficult to popularize and implement. (Paper re-forming by simple growth of bacterial cells. Journal of Materials Science, 2017, 52(10):5882-5893.Journal of Materials Science, 2017, 52(10): 5882-. Bacterial cellulose was pulped by Zhangzhihui from university of Yunnan and coated on ancient book paper under the condition of pH 7. The mechanical strength of the repaired paper is improved to a certain extent. Although the method is simple to operate, the bacterial cellulose is only coated on the surface of paper and is difficult to permeate into the fiber, so that the performance of the repaired paper is still obviously reduced (application research of the bacterial cellulose in paper archive repair [ D ]. Yunnan university 2015).

Under appropriate conditions, the bacterial cellulose can be dissolved in an alkaline solvent to form a transparent, uniform and stable solution. Cellulose has strong hydrophilicity, and hydrogen bonds combined between fibers in the bacterial cellulose solution fully absorb the bacterial cellulose and the alkaline solution and enter the inside of the fibers. Can realize deacidification and reinforcing of ancient book paper, can effectual protection and repair ancient book paper.

Disclosure of Invention

The invention aims to provide a preparation method and application of a bacterial cellulose paper repair liquid in order to improve the acid environment of ancient book paper and improve the mechanical property, stability and durability of the ancient book paper. According to the invention, the bacterial cellulose is dissolved in the alkali solution, and the nano-mesh porous structure and the abundant hydroxyl groups on the surface of the bacterial cellulose are utilized and combined with the porous structure of the paper, so that the bacterial cellulose can effectively permeate into the ancient book paper, the strength of the paper is increased, the stability and durability of the paper in the using process are improved, and the paper has an application value in the field of deacidification and reinforcement of the ancient book paper.

The purpose of the invention is realized by the following technical scheme.

A preparation method of a paper deacidification strengthening repair liquid based on bacterial cellulose is characterized by comprising the following steps:

(1) cleaning impurities on the surface of the ancient book paper, and carrying out constant temperature and humidity treatment;

(2) bacterial cellulose is disintegrated and then prepared into a uniformly dispersed solution;

(3) and loading the bacterial cellulose on ancient book paper, and performing deacidification and reinforcement treatment on the ancient book paper.

Further, the constant temperature and humidity treatment in the step (1) is to hang the paper in a constant temperature and humidity chamber with the temperature of 23 ℃ and the RH of 50 percent, and balance the moisture for 24 hours.

Further, the bacterial cellulose in the step (2) is composed of bacterial cellulose or derivatives thereof, inorganic alkali or organic alkali and aqueous solution.

Further, the bacterial cellulose solution in the step (2) comprises the following components in parts by mass: 0.1-1.0 w t% of bacterial cellulose or derivatives thereof, 8.0-22.0% of inorganic alkali or organic alkali and 77.0-91.9% of water.

Further, the bacterial cellulose in the step (2) is bacterial cellulose or modified bacterial cellulose which is directly secreted and synthesized by microorganisms; the modified bacterial cellulose is etherified and aminated modified bacterial cellulose which is modified by a chemical reagent or cultured by adopting a special bacterial culture solution. The quantity and the variety of functional groups on the surface of the bacterial cellulose are improved through modification, more hydrogen bonds and chemical bonds are formed with plant fibers, the combination stability of the plant fibers and the bacterial cellulose is enhanced, and the durability of the repaired paper in the recycling process is ensured.

Further, the culture conditions of the microorganism are static or dynamic fermentation culture conditions; the microorganism is one of gluconacetobacter, acetobacter, agrobacterium, pseudomonas, achromobacter, alcaligenes, aerobacter, azotobacter, rhizobium and sarcina; the special bacteria culture solution comprises a culture solution added with at least one of hydroxylamine hydrochloride, diethylenetriamine, polyethyleneimine and ammonia water.

Furthermore, the method for modifying the bacterial cellulose by etherification comprises the steps of soaking the bacterial cellulose by using sodium hydroxide to obtain alkali cellulose, and carrying out Williamson etherification or Michael addition reaction on the alkali cellulose and an alkyl compound, an alkoxy compound and a vinyl compound, wherein the alkyl compound, the alkoxy compound and the vinyl compound are one of methane chloride, chloroethane, sulfonyl ethane, ethylene oxide and acrylonitrile.

Furthermore, the method for aminating and modifying the bacterial cellulose is to bond a nitrogen-containing compound with a hydroxyl group of the bacterial cellulose and graft a nitrogen-containing group, wherein the nitrogen-containing compound is one of hydroxylamine hydrochloride, polyacrylamide, ethylenediamine, diethylamine, tetraethylenepentamine, dimethylamine and N-methylimidazole.

Further, the inorganic base in the step (2) is one of a base/urea/water system, a base/thiourea/water system, and a base/thiourea/urea/water system.

Further, the organic base in the step (2) is one of a LiCl/dimethylacetamide (DMAc) system, a Dimethylsulfoxide (DMSO)/tetraethylammonium chloride (TEAC) system, N-methylmorpholine oxide (NMMO), or an ionic liquid solvent system.

Further, the method for loading the bacterial cellulose on the ancient book paper in the step (3) is a soaking method, a coating method or an ultrasonic atomization method. The method has the beneficial effects of enhancing the uniform dispersibility of the bacterial cellulose on the surface of the paper, and improving the mechanical property and the recycling capability of the bacterial cellulose.

Further, the method for loading the bacterial cellulose on the ancient book paper is to uniformly coat, spin-coat or brush-coat the well-dispersed conductive filler solution on the ancient book paper by an automatic coating machine, a coating rod or a coating brush.

Furthermore, the method for loading the bacterial cellulose on the ancient book paper is to soak the ancient book paper into the uniformly dispersed bacterial cellulose solution.

Furthermore, the method for loading the bacterial cellulose on the ancient book paper comprises the steps of placing the ancient book paper in a closed deacidification device, and then introducing the bacterial cellulose solution into the deacidification device after atomization treatment.

The bacterial cellulose paper repair liquid prepared by the preparation method.

The bacterial cellulose repair liquid can be used for deacidifying and enhancing ancient book paper.

Further, the applications include (but are not limited to) ancient papers, silk cultural relics, wood cultural relics, and the like.

According to the invention, bacterial cellulose is subjected to disintegration, dispersion, activation modification and dissolution, an inorganic alkali and organic alkali system is adopted to prepare the bacterial cellulose into an alkaline transparent solution, and the bacterial cellulose is loaded on ancient book paper, so that the effective combination of the bacterial cellulose and the paper fiber and the acid-base neutralization are realized. After the ancient book paper is subjected to dry heat aging at 105 ℃ for 120 h, the mechanical property of the ancient book paper can be restored to the level before the ancient book paper is aged through the restoration of a bacterial cellulose solution, and meanwhile, the pH value of the ancient book paper is enabled to reach 8-10. After the repaired paper is subjected to dry heat aging at 105 ℃ for 240 hours, the mechanical property reduction ratio is only 14.6%, and the mechanical property reduction ratio of the unrepaired paper is 32.7%.

Compared with the prior art, the invention has the following advantages:

1. according to the invention, bacterial cellulose is subjected to disintegration, dispersion, activation and modification, the reactivity and the variety of functional groups on the surface of the bacterial cellulose are increased, the combination stability of the bacterial cellulose and ancient book paper fibers is improved, and the effective improvement of the mechanical properties of the ancient book paper is realized.

2. According to the invention, the bacterial cellulose is dissolved by using an alkaline solvent system, so that the dissolving performance and the fluidity of the bacterial cellulose are enhanced, and the ancient book paper deacidification and enhancement integration is realized.

Drawings

FIG. 1 is a flow chart of preparation of a bacterial cellulose-based paper deacidification enhancement repair solution of the present invention.

Detailed Description

The present invention will be described in further detail below with reference to examples, but the practice of the present invention is not limited thereto.

The preparation flow chart of the bacterial cellulose-based paper deacidification strengthening repair liquid is shown in figure 1.