WO2020228161A1 - 一种无水纳米脱酸液及其制备方法 - Google Patents

一种无水纳米脱酸液及其制备方法 Download PDF

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WO2020228161A1
WO2020228161A1 PCT/CN2019/101294 CN2019101294W WO2020228161A1 WO 2020228161 A1 WO2020228161 A1 WO 2020228161A1 CN 2019101294 W CN2019101294 W CN 2019101294W WO 2020228161 A1 WO2020228161 A1 WO 2020228161A1
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deacidification
nano
anhydrous
nanoparticles
anhydrous nano
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PCT/CN2019/101294
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French (fr)
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张世著
张尚峰
石欣超
张将
刘闯
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南京华鼎纳米技术研究院有限公司
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Publication of WO2020228161A1 publication Critical patent/WO2020228161A1/zh

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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
    • 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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  • the invention belongs to the field of paper deacidification, and relates to a paper deacidification liquid and a preparation method thereof, in particular to an anhydrous nano deacidification liquid and a preparation method thereof.
  • the acidification of paper its intuitive manifestation is that the paper becomes low-strength, fragile, fragile, yellowed and brittle, and it may be chipped all over with a light touch.
  • the main factor that causes the acidification of paper is that the cellulose (C 6 H 10 O 5 ) n of the paper accelerates the hydrolysis under the catalysis of the acid, resulting in a shorter cellulose length and a decrease in the mechanical strength of the paper.
  • the cellulose (C 6 H 10 O 5 ) n of the paper accelerates the hydrolysis under the catalysis of the acid, resulting in a shorter cellulose length and a decrease in the mechanical strength of the paper.
  • the situation of paper acidification in my country is even more severe. Almost all domestic libraries, archives, and museums have the problem of paper acidification. Among them, the literature of the Republic of China is particularly prominent.
  • paper deacidification methods can be divided into gas phase deacidification method and liquid phase deacidification method.
  • the gas phase deacidification method means that the deacidification substance is in a gas state.
  • Liquid phase deacidification means that the deacidification substance is in a liquid state, and the deacidification solution is usually composed of a deacidification agent dispersed in a deacidification solvent.
  • liquid deacidification can be divided into aqueous liquid deacidification, anhydrous liquid phase deacidification and organic dispersant deacidification.
  • the gas-phase deacidification method has been eliminated because of its toxic gas, complicated equipment and large investment.
  • Aqueous liquid phase deacidification method Because the cellulose with carbonyl and carboxyl groups in the deacidification solution will cause continuous oxidation and decomposition of paper; the deacidification process will cause the water-based pigment printing or writing handwriting patterns to dissolve, and cause the paper surface pigments The layer cracked and fell off.
  • Organic dispersant deacidification method due to the extremely strict requirements on the environment, personnel and operating procedures during use, and the deacidification liquid used is a dangerous product, not only flammable and explosive, but also harmful to the environment and human health. There are no archives and libraries to use this technology.
  • the anhydrous liquid phase deacidification method has become the mainstream of paper deacidification technology due to its ease of operation, relative safety of the reagents used, and reliability of no damage to paper.
  • the deacidification solution not only needs to have no major hidden dangers in the production and operation process, but also can realize the long-term stable dispersion of alkaline particles, which has become a technical bottleneck for the widespread promotion and application of anhydrous deacidification technology. .
  • the present invention provides an anhydrous nano deacidification solution that not only has no major safety hazards during production and operation, but also can achieve long-term stable dispersion of alkaline particles, with a stable dispersion time of up to 30 minutes Above, and after the paper is deacidified, the pH of the paper is> 8, and the alkali retention is> 2%.
  • Anhydrous nano deacidification liquid containing the following components by weight percentage:
  • the fluorocarbon surfactants with hydrophobic and oleophobic properties are fluorocarbon surfactants, preferably one or two of DuPont Zonyl FSH or Zonyl FSJ.
  • the main dispersant is perfluoroalkanes, preferably one or more of perfluorohexane, perfluorooctane or perfluoroheptane.
  • the fluorinated surfactants with hydrophobic and lipophilic properties are fluorinated alcohols, preferably tetrafluoropropanol, hexafluorobutanol, octafluoropentanol, dodecafluoroheptanol, One or more of 1H,1H-perfluoro-1-tetradecyl alcohol and hexadecafluorononanol.
  • the following step may be included between 1) and 2): slowly adding a fluorocarbon surfactant with hydrophobic and oleophobic properties to the alkaline nanoparticles.
  • the anhydrous nano deacidification liquid is sprayed, soaked or atomized to treat acidified paper.
  • the present invention uses alkaline compounds or oxide nanoparticles of metal elements, taking magnesium oxide alkaline nanoparticles as an example, especially magnesium oxide alkaline nanoparticles with a particle size of 20-100nm, which is beneficial to magnesium oxide alkaline nanoparticles Long-term uniform dispersion in the dispersion system is also conducive to the penetration of magnesium oxide alkaline nanoparticles into the paper and deposits on the surface of the cellulose during use, which improves the effectiveness of deacidification and increases the effective alkali Retention
  • the invention adopts a fluorine-containing surfactant with hydrophobic and lipophilic properties, reduces the amount of main dispersant and surfactant, further prolongs the agglomeration and sedimentation time of alkaline magnesium oxide particles, and improves the dispersion effect of alkaline magnesium oxide particles ;
  • the lipophilic end of the fluorine-containing surfactant with hydrophobic and lipophilic properties faces the main dispersant and has affinity with the main dispersant to increase the magnesium oxide base encapsulated in the dispersing aid
  • the dispersion uniformity and stability of the nanoparticle in the dispersion system, the stable dispersion time is more than 30 minutes, and during use, the main dispersant volatilizes quickly, and the hydrophobic end of the dispersing aid will interact with the hydrophobic and oleophobic cellulose.
  • Affinity occurs, guiding the alkaline nanoparticles of magnesium oxide to penetrate into the paper and deposit on the surface of the cellulose, which improves the effectiveness of deacidification and increases the effective alkali retention.
  • a layer of hydrophobic and oleophobic fluorosurfactant can be wrapped on the surface of the magnesium oxide alkaline nanoparticles, and the oleophobic end of the fluorosurfactant is close to and facing the magnesium oxide alkaline nanoparticles and fluorosurfactant.
  • the hydrophobic end is close to and towards the hydrophobic end of the dispersion aid, and has affinity with it to further improve the dispersion uniformity and stability of the magnesium oxide alkaline nanoparticles encapsulated in the surfactant in the dispersion system, and stabilize the dispersion
  • the time is more than 75 minutes, and during use, the main dispersant volatilizes quickly, and the hydrophobic end of the dispersing aid and the hydrophobic end of the fluorosurfactant will interact with the hydrophobic and oleophobic cellulose together to quickly guide the magnesium oxide Alkaline nanoparticles penetrate the paper and deposit on the surface of the cellulose, improving the effectiveness of deacidification and increasing the effective alkali retention.
  • alkaline nanoparticles of magnesium oxide When the anhydrous nano deacidification liquid of the present invention is subjected to deacidification treatment, alkaline nanoparticles of magnesium oxide will penetrate into the paper and deposit on the cellulose surface paper. After the paper absorbs moisture in the air, the acidic free H + It will react with alkaline nanoparticles of magnesium oxide to generate Mg 2+ and water. When the water evaporates, Mg 2+ is deposited on the surface of the paper in the form of metal salt nanoparticles, which plays a protective role in isolating acid gases. After the paper is deacidified, the pH value of the paper is> 8, and the alkali retention is> 2%, which can achieve effective paper deacidification and alkali retention.
  • the preparation method of the anhydrous nano deacidification liquid of the present invention realizes the uniformity and stability of the dispersion of magnesium oxide alkaline nanoparticles in a dispersion system, and is suitable for large-scale production and manufacture. After long-term use, if you find that there is agglomeration and sedimentation of magnesium oxide alkaline nanoparticles in the anhydrous nano deacidification solution, just shake it up and use it.
  • FIG. 1 Schematic diagram of the dispersion system of Example 2
  • FIG. 3 is a schematic diagram of the dispersion system of Example 3.
  • FIG. 3 is a schematic diagram of the dispersion system of Example 3.
  • DuPont Zonyl FSJ 5 DuPont Zonyl FSJ; 52 DuPont Zonyl FSJ oleophobic end; 51 DuPont Zonyl FSJ hydrophobic end;
  • magnesium oxide basic nanoparticles 1 with a particle size of 20-100nm;
  • the structure of the dispersion system prepared in this embodiment is shown in Figure 2.
  • the magnesium oxide alkaline nanoparticles 1 are wrapped in DuPont Zonyl FSH4, and the DuPont Zonyl FSH oleophobic end 42 is close to and facing the magnesium oxide alkaline nanoparticles 1.
  • DuPont Zonyl The hydrophobic end 41 of FSH is away from and facing away from the basic magnesium oxide nanoparticles 1 and at the same time approaching and facing the hydrophobic end 21 of octafluoropentanol, and the lipophilic end 22 of octafluoropentanol is away from and facing away from the basic magnesium oxide nanoparticles 1.
  • the structure of the dispersion system prepared in this embodiment is shown in Figure 3.
  • the 1-magnesium oxide alkaline nanoparticles are wrapped in 5-DuPont Zonyl FSJ, and the 52-oleophobic end of 5-DuPont Zonyl FSJ is close to and facing 1-oxidation.
  • the 62-lipophilic end of fluoroheptanol is away from and facing away from the 1-magnesium oxide alkaline nanoparticles.
  • test results show that in the examples of the present invention, after the paper is deacidified, the pH value of the paper is> 8, and the alkali retention is> 2%; the magnesium oxide alkaline nanoparticles can be stably dispersed in the dispersion system for a long time More than 30min.

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  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

一种无水纳米脱酸液及其制备方法。该无水纳米脱酸液含有如下重量百分比的组分：金属元素的碱性化合物或氧化物0.01～0.8wt％；具有疏水亲油特性的含氟表面活性剂0.1～18wt％，余量为主分散剂。制备方法包括如下步骤：1）将金属元素的碱性化合物或氧化物，通过研磨工艺制成粒径为20～200nm的碱性纳米颗粒；2）在碱性纳米颗粒中一边加入具有疏水亲油特性的含氟表面活性剂，同时一边进行搅拌，制成分散液体；3)在分散液体中一边加入主分散剂，同时一边进行搅拌，制成无水纳米脱酸液。

Description

一种无水纳米脱酸液及其制备方法 技术领域
本发明属于纸张脱酸领域，涉及一种纸张脱酸液及其制备方法，尤其涉及一种无水纳米脱酸液及其制备方法。
背景技术
纸张的酸化，其直观表现是纸张变得强度低、易碎、易裂、发黄变脆，轻轻触摸就可能碎屑遍地。引起纸张酸化的主要因素，就是纸张的纤维素(cellulose)(C 6H 10O 5)n在酸的催化作用下，加速水解，导致纤维素长度变短，纸张机械强度降低。当前，世界各国的馆藏图书、文献资料有1/3以上已经变脆，其余的图书、报纸也面临类似情况。我国纸张酸化的形势更为严峻，国内几乎所有的图书馆、档案馆、博物馆都存在纸张酸化的问题，其中以民国文献尤为突出。
根据使用的脱酸剂所处的状态，纸张脱酸方法可分为气相脱酸法和液相脱酸法。气相脱酸法即脱酸物质呈气体状态。液相脱酸即脱酸物质呈液体状态，脱酸溶液通常由脱酸剂分散在脱酸溶剂中构成。根据采用的溶剂类型和分散方式的不同，液相脱酸法又可分为含水液相脱酸、无水液相脱酸和有机分散剂脱酸。
气相脱酸法因其采用的气体具有毒性，并且设备复杂、投入资金多，已被淘汰。含水液相脱酸法，由于脱酸液中含有羰基和羧基基团的纤维素，会造成纸张持续氧化分解；脱酸过程中会造成水性颜料印刷或书写的字迹图案溶解，并且导致纸张表面颜料层开裂脱落。这些技术上目前难以克服的缺陷，限制了该方法的推广和应用。有机分散剂脱酸法，由于在使用过程中对环境、人员及操作程序要求极其严格，并且所用的脱酸液本身就属于危险品不仅是易燃易爆，并且对环境和人体健康有危害，目前已经没有档案馆和图书馆再使用该技术。无水液相脱酸法，以其操作的简便性、所用试剂的相对安全性，以及对纸张无损伤的可靠性，成为纸张脱酸技术的主流。
目前，无水液相脱酸法的已有技术中，主流的技术是美国专利“US006342098B1 Deacidification of Cellulose based materials using Hydrofluoroether Carriers”中所采用的技术，该技术使用氢氟醚类物质作为分散剂，但由于氢氟醚类物质具有易燃的特性，原料保存和产品生产制造过程中有重大的安全隐患；并且该技术使用全氟烷基聚醚类的易溶于水和有机溶剂的含氟阴离子型表面活性剂，造成表面活性剂与作为主体分散剂的全氟烷烃发生互溶，降低了分散体系的稳定性，导致脱酸液中的氧化镁碱性纳米颗粒容易发生团聚沉降，从而影响长期稳定地使用。中国专利“CN107012736A一种兼具纸张增强作用的脱酸液及其制备方法” 中，使用镁铝双金属氢氧化物或其焙烧产物作为碱性物质，生产工艺复杂，并且制备出的碱性颗粒的粒径均一性差，难以实现碱性颗粒的长期稳定分散，限制了其大规模的推广和应用。实际使用中，脱酸液既需要满足在生产和操作过程中无重大隐患，又能够实现碱性颗粒的长期稳定分散，这成为了无水脱酸技术得到大范围推广和应用的技术瓶颈。。
发明内容
1.要解决的问题
针对现有技术的不足，本发明提供一种既满足在生产和操作过程中无重大安全隐患，又能够实现碱性颗粒的长期稳定分散的无水纳米脱酸液，稳定分散的时间长达30min以上，并且在对纸张进行脱酸处理后，纸张的pH值＞8，碱存留量＞2％。
2.技术方案
为了解决上述问题，本发明所采用的技术方案如下：
一种无水纳米脱酸液，含有如下重量百分比的组分：
金属元素的碱性化合物或氧化物         0.01～0.8wt％
具有疏水亲油特性的含氟表面活性剂     0.1～18wt％
余量为主分散剂。
作为本发明的进一步改进，所述的无水纳米脱酸液，还含有如下重量百分比的组分：
具有疏水疏油特性的氟碳表面活性剂     0.1～0.3wt％。
作为本发明的进一步改进，所述的具有疏水疏油特性的氟碳表面活性剂为氟碳表面活性剂类，优选为杜邦Zonyl FSH或Zonyl FSJ中的一种或两种。
作为本发明的进一步改进，所述的金属元素的碱性化合物或氧化物粒径为20～200nm，优选粒径为20～100nm的氧化镁纳米颗粒。所述的氧化镁纳米颗粒即氧化镁碱性纳米颗粒。
作为本发明的进一步改进，所述的主分散剂为全氟烷烃类，优选为全氟己烷、全氟辛烷或全氟庚烷中的一种或几种。
作为本发明的进一步改进，所述的具有疏水亲油特性的含氟表面活性剂为含氟醇类，优选为四氟丙醇、六氟丁醇、八氟戊醇、十二氟庚醇、1H,1H-全氟-1-十四(烷)醇、十六氟壬醇中的一种或几种。
本发明还提供一种无水纳米脱酸液的制备方法，包括如下步骤：
1)将金属元素的碱性化合物或氧化物，通过研磨工艺制成粒径为20～100nm的碱性纳米颗粒；
2)在碱性纳米颗粒中一边加入分散助剂，同时一边进行搅拌，制成分散液体；
3)在分散液体中一边加入主分散剂，同时一边进行搅拌，制成无水纳米脱酸液。
作为本发明的进一步改进，还可以在第1)和第2)之间包括如下步骤：在碱性纳米颗粒中缓慢加入具有疏水疏油特性的氟碳表面活性剂。
作为本发明的进一步改进，所述的一种无水纳米脱酸液，采用喷洒、浸泡或雾化的方式对酸化纸张进行处理。
3.有益效果
相比于现有技术，本发明的有益效果为：
本发明采用金属元素的碱性化合物或氧化物纳米颗粒，以氧化镁碱性纳米颗粒为例，尤其是粒径为20～100nm的氧化镁碱性纳米颗粒，既有利于氧化镁碱性纳米颗粒在分散体系中实现长期均匀地分散，也有利于氧化镁碱性纳米颗粒在使用过程中渗透进入纸张内部并沉积在纤维素的表面，提高了脱酸的有效性，并增大了有效的碱存留量；
本发明采用全氟烷烃作为主分散剂，避免了脱酸过程中引起纸张的变形和褶皱，并且表面张力低、在纸张中渗透能力强，有利于氧化镁碱性纳米颗粒在使用过程中渗透进入纸张内部并沉积在纤维素的表面。全氟烷烃易于挥发，可以在实际生产过程中实现回收利用；
本发明采用具有疏水亲油特性的含氟表面活性剂，降低了主分散剂和表面活性剂的用量，进一步延长了氧化镁碱性颗粒的团聚沉降时间，提高了氧化镁碱性颗粒的分散效果；
本发明采用不属于危化品目录的含氟醇类作为具有疏水亲油特性的含氟表面活性剂，使用不属于危化品目录的杜邦Zonyl含氟表面活性剂作为表面活性剂，大幅度地提高了生产和操作的安全性，适于大规模地生产和使用；
本发明的分散体系，具有疏水亲油特性的含氟表面活性剂即分散助剂的亲油端朝向主分散剂，并与主分散剂发生亲和，以提高分散助剂内包裹的氧化镁碱性纳米颗粒在分散体系中的分散均匀性和稳定性，稳定分散的时间长达30min以上，并且在使用过程中，主分散剂快速挥发，分散助剂的疏水端会与疏水疏油的纤维素发生亲和，引导氧化镁碱性纳米颗粒渗入纸张并沉积到纤维素表面，提高了脱酸的有效性，并增大了有效的碱存留量。进一步地，还可以在氧化镁碱性纳米颗粒表面包裹一层疏水疏油的含氟表面活性剂，含氟表面活性剂的疏油端靠近并朝向氧化镁碱性纳米颗粒、含氟表面活性剂的疏水端靠近并朝向分散助剂的疏水端，并与之发生亲和，以进一步提高表面活性剂内包裹的氧化镁碱性纳米颗粒在分散体系中的分散均匀性和稳定性，稳定分散的时间长达75min以上，并且在使用过程中，主分散剂快速挥发，分散助剂的疏水端和含氟表面活性剂的疏水端会共同与疏水疏油的纤维素发生亲和，快速引导氧化镁碱性纳米颗粒渗入纸张并沉积到纤维素表面，提高了脱酸的有效性，并增大了有效的碱存留量。
本发明的无水纳米脱酸液在进行脱酸处理时，会将氧化镁碱性纳米颗粒渗入纸张并沉积 到纤维素表面纸，纸张在吸收了空气中的水分之后，酸性的游离态的H +会与氧化镁碱性纳米颗粒反应，生成Mg 2+与水，当水分挥发后，Mg 2+以金属盐纳米颗粒的形态沉积于纸张表面，起到将酸性气体隔离的保护作用。在对纸张进行脱酸处理后，纸张的pH值＞8，碱存留量＞2％，能够实现有效的纸张脱酸和碱存留。
本发明的无水纳米脱酸液的制备方法，实现了氧化镁碱性纳米颗粒在分散体系中的分散均匀性和稳定性，适于大规模地生产和制造。长期放置后再使用，若发现无水纳米脱酸液中有氧化镁碱性纳米颗粒的团聚沉降，只需摇匀即可使用。
附图说明
图1实施例1的分散体系的示意图；
图2实施例2的分散体系的示意图；
图3实施例3的分散体系的示意图。
1氧化镁碱性纳米颗粒；2八氟戊醇；21八氟戊醇疏水端；22八氟戊醇亲油端；
4杜邦Zonyl FSH；42杜邦Zonyl FSH疏油端；41杜邦Zonyl FSH的疏水端；
5杜邦Zonyl FSJ；52杜邦Zonyl FSJ疏油端；51杜邦Zonyl FSJ疏水端；
6十二氟庚醇；61十二氟庚醇疏水端，62十二氟庚醇十二氟庚醇亲油端。
具体实施方式
下面结合具体实施例对本发明进一步进行描述。
实施例1
无水纳米脱酸液的制备方法
1)将0.03wt％的块状氧化镁，通过湿法研磨工艺，在1200r/min的搅拌条件下，连续研磨3小时，制成粒径为20～100nm的-氧化镁碱性纳米颗粒1；
2)在氧化镁碱性纳米颗粒1中一边加入0.1wt％2-八氟戊醇，同时一边进行搅拌，搅拌的速度为1200r/min，搅拌的时长为0.5小时，制成分散液体；
3)在分散液体中一边加入99.87wt％全氟庚烷3，同时一边进行搅拌，搅拌的速度为1200r/min，搅拌的时长为0.5小时，制成无水纳米脱酸液。
本实施例制备出的分散体系的结构如图1所示，氧化镁碱性纳米颗粒1包裹在八氟戊醇2中，八氟戊醇疏水端21靠近并朝向氧化镁碱性纳米颗粒1，八氟戊醇亲油端22远离并背向氧化镁碱性纳米颗粒1。
实施例2
无水纳米脱酸液的制备方法
1)将0.5wt％的氧化镁，通过湿法研磨工艺，在1600r/min的搅拌条件下，连续研磨4 小时，制成粒径为20～100nm的氧化镁碱性纳米颗粒1；
2)在氧化镁碱性纳米颗粒中1，缓慢加入0.1wt％杜邦Zonyl FSH4，
3)在2)所得物中一边加入12wt％八氟戊醇2，同时一边进行搅拌，搅拌的速度为1500r/min，搅拌的时长为1小时，制成分散液体；
4)在分散液体中一边加入87.4wt％全氟庚烷3，同时一边进行搅拌，搅拌的速度为1500r/min，搅拌的时长为1小时，制成无水纳米脱酸液。
本实施例制备出的分散体系的结构如图2所示，氧化镁碱性纳米颗粒1包裹在杜邦Zonyl FSH4中，杜邦Zonyl FSH疏油端42靠近并朝向氧化镁碱性纳米颗粒1，杜邦Zonyl FSH疏水端41远离并背向氧化镁碱性纳米颗粒1、同时靠近并朝向八氟戊醇疏水端21，八氟戊醇亲油端22远离并背向氧化镁碱性纳米颗粒1。
实施例3
无水纳米脱酸液的制备方法
1)将0.8wt％的氧化镁，通过湿法研磨工艺，在1800r/min的搅拌条件下，连续研磨5小时，制成粒径为20～100nm的1-氧化镁碱性纳米颗粒；
2)在1-氧化镁碱性纳米颗粒中，缓慢加入0.3wt％杜邦Zonyl FSJ5；
3)在2)中所得物中一边加入18wt％十二氟庚醇6，同时一边进行搅拌，搅拌的速度为1800r/min，搅拌的时长为2小时，制成分散液体；
4)在分散液体中一边加入87.4wt％全氟辛烷7，同时一边进行搅拌，搅拌的速度为1800r/min，搅拌的时长为2小时，制成无水纳米脱酸液。
本实施例制备出的分散体系的结构如图3所示，1-氧化镁碱性纳米颗粒包裹在5-杜邦Zonyl FSJ中，5-杜邦Zonyl FSJ的52-疏油端靠近并朝向1-氧化镁碱性纳米颗粒，5-杜邦Zonyl FSJ的51-疏水端远离并背向1-氧化镁碱性纳米颗粒、同时靠近并朝向6-十二氟庚醇的61-疏水端，6-十二氟庚醇的62-亲油端远离并背向1-氧化镁碱性纳米颗粒。
测试方法：
纸张脱酸效果测试
按照国家相关标准《GB/T 13528-1992纸和纸板表面pH值的测定法》和《GB/T 24998-2010纸和纸板碱储量的测定》，分别对实施例1、实施例2、实施例3制备的无水纳米脱酸液的纸张脱酸效果进行测试，纸张脱酸测试的结果如表-1所示。
表-1实施例的纸张脱酸测试的结果
Figure PCTCN2019101294-appb-000001
团聚沉降效果测试
采用测量原理为散射法(90°散射光)的德国WTW Turb550IR实验室台式浊度仪对无水纳米脱酸液中的碱性颗粒的分散性进行检测，浊度单位用NTU表示，与ISO标准所用的测量单位为FTU相一致。NTU值下降，意味着更多的氧化镁碱性纳米颗粒已在分散体系中团聚沉降。分别对实施例1、实施例2、实施例3制备的无水纳米脱酸液的团聚沉降效果进行测试，团聚沉降测试的结果如表-2所示。
表-2实施例的团聚沉降测试的结果
Figure PCTCN2019101294-appb-000002
测试结果表明，本发明的实施例，在对纸张进行脱酸处理后，纸张的pH值＞8，碱存留 量＞2％；氧化镁碱性纳米颗粒在分散体系中的稳定分散的时间长达30min以上。
应理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。对本领域普通技术人员而言，可以根据上述说明加以改进或变换，所做出的改进或变换均应属于本发明所附权利要求的保护范围。

Claims (11)

  1. 一种无水纳米脱酸液，其特征在于：所述无水纳米脱酸液含有如下重量百分比的组分：
    金属元素的碱性化合物或氧化物        0.01～0.8wt％
    具有疏水亲油特性的含氟表面活性剂    0.1～18wt％
    余量为主分散剂。
  2. 根据权利要求1所述的无水纳米脱酸液，进一步地，所述无水纳米脱酸液还含有重量百分比如下的组分：
    具有疏水疏油特性的氟碳表面活性剂    0.1～0.3wt％。
  3. 根据权利要求1或2所述的一种无水纳米脱酸液，所述的主分散剂为全氟烷烃。
  4. 根据权利要求3所述的一种无水纳米脱酸液，所述的氟碳表面活性剂为杜邦Zonyl FSH或Zonyl FSJ中的一种或两种；所述的全氟烷烃类为全氟己烷、全氟辛烷或全氟庚烷中的一种或几种。
  5. 根据权利要求3所述的无水纳米脱酸液，所述的金属元素的碱性化合物或氧化物为纳米氧化镁颗粒，所述的金属元素的碱性化合物或氧化物粒径为20～200nm。
  6. 根据权利要求5所述的无水纳米脱酸液，所述的金属元素的碱性化合物或氧化物为粒径20～100nm的氧化镁纳米颗粒。
  7. 根据权利要求3所述的无水纳米脱酸液，其特征在于，所述的具有疏水亲油特性的含氟表面活性剂为含氟醇类。
  8. 根据权利要求7所述的无水纳米脱酸液其特征在于，所述的含氟醇类为四氟丙醇、六氟丁醇、八氟戊醇、十二氟庚醇、1H,1H-全氟-1-十四(烷)醇、十六氟壬醇中的一种或几种。
  9. 根据权利要求1-8中任意一项权利要求所述一种无水纳米脱酸液，其特征在于，制备方法包括如下步骤：
    1)将金属元素的碱性化合物或氧化物，通过研磨工艺制成粒径为20～200nm的碱性纳米颗粒；
    2)在碱性纳米颗粒中一边加入具有疏水亲油特性的含氟表面活性剂，同时一边进行搅拌，制成分散液体；
    3)在分散液体中一边加入主分散剂，同时一边进行搅拌，制成无水纳米脱酸液。
  10. 根据权利要求9所述的一种无水纳米脱酸液，其特征在于：制备方法还可以在第1)和第2)之间包括如下步骤：
    在碱性纳米颗粒中缓慢加入具有疏水疏油特性的氟碳表面活性剂，制成浸润颗粒。
  11. 根据权利要求1所述的一种无水纳米脱酸液，其特征在于：采用喷洒、浸泡或雾化的方式对酸化纸张进行处理。
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