CN107815921B - Yao channel protective agent and Yao channel protective method - Google Patents

Yao channel protective agent and Yao channel protective method Download PDF

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CN107815921B
CN107815921B CN201711068562.XA CN201711068562A CN107815921B CN 107815921 B CN107815921 B CN 107815921B CN 201711068562 A CN201711068562 A CN 201711068562A CN 107815921 B CN107815921 B CN 107815921B
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yao nationality
channel
yao
nationality
polymer
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CN107815921A (en
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徐菲
郑伟
王淏
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Zhengzhou University of Light Industry
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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
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • 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
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
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Abstract

Yao nationality channel protective agent. The Yao nationality channel has great value for understanding religious beliefs, social life and the like of the Yao nationality, and can provide a new material for researching propagation and development of the religion in Chinese minority nations and southeast Asia countries. The strengthened protection of the Yao nationality road can arouse the interest of foreign and domestic schools in Yao nationality literature, and promote more scholars to be added to Yao nationality teaching research teams to exert the due value of the Yao nationality road. The protective agent disclosed by the invention uses the polymer and the formula thereof to form a layer of protective film on the surface of the Yao nationality channel, so that the flexibility of the Yao nationality channel can be improved, the mechanical strength and the anti-tarnishing capability of the Yao nationality channel are improved, and the Yao nationality channel is prevented from being mildewed and damaged by worms.

Description

Yao channel protective agent and Yao channel protective method
Technical Field
The invention relates to a Yao nationality channel protective agent and a Yao nationality channel protective method, in particular to a protective agent and a protective method for protecting and repairing Yao nationality channel ancient books which are relatively long in survival time.
Background
The Yao nationality channel has great value for understanding religious beliefs, social life and the like of the Yao nationality, and can provide a new material for researching propagation and development of the religion in Chinese minority nations and southeast Asia countries. The strengthened protection of the Yao nationality road can arouse the interest of foreign and domestic schools in Yao nationality literature, and promote more scholars to be added to Yao nationality teaching research teams to exert the due value of the Yao nationality road.
The religious beliefs of the Yao nationalities have various forms, the beliefs of the Yao nationalities are different from place to place, and the Yao nationalities have original religious forms such as totem worship, natural worship and ancestor worship and have the religions of people handed from the Chinese nationality region. In the second thirty years of the century, the domestic scholars investigate the social life, religious beliefs and other conditions of the Yao nationality, and after relevant investigation reports are published, the scholars in various places comprehensively investigate the social history conditions of the Yao nationality, and after relevant investigation achievements are successively published in the eighties of the century, more domestic scholars publish their opinions about Yao nationality culture and religious beliefs, and the number of the scholars is considerable. The research on Yao nations in foreign countries starts with early Japanese scholars, such as white bird Fanglang, researching Yao nations in North Tai China in the year, books such as Yao ren literature and Yao nan mountain national folk are published in the seventy years, books such as Yao nationality history and culture and Yao nationality Hanhua observation are successively published in Zhu cun Zong II, Shen-chuan university also specially establishes Yao nationality research institute, periodically compiles and prints research communication, and publishes achievements such as Yao nationality artistic energy research in Hunan lake and Yao nationality instrument literature in Yao county in Hunan province in China. The research results of western scholars are represented by books such as Yao nationality Shen Picture and Huanan Yao nationality played by Remeng En of French scholars in southeast Asia for a long time, and deep analysis on the teaching beliefs of Yao nationality is emphasized in articles such as Daozhi of America scholars 'deficiency, Daozhi of Taoism and Yao dish New Duo of Netherlands' Tianhai. The Yao nationality channel is usually a line-mounted hand-made notebook, the font style, the size and the paper texture of the Yao nationality channel are not uniform, and the Yao nationality channel is broken and obviously used for many times. It may be due to breakage due to multiple uses, the cover of many texts has been dropped and does not exist, or the cover has been replaced with another paper, making it difficult to know the contents at a glance.
In a word, the Yao nationality channel has great historical and practical significance through research, and the Yao nationality channel also has economic and cultural significance which cannot be copied.
Unfortunately, as the Yao nationality channel is born before 1949, the natural passage of time and the browsing of researchers can cause certain damage to the Yao nationality channel. Therefore, a proper special protective agent for repairing and protecting the Yao nationality channel is urgently needed.
Based on paper of Yao nationality channel and the characteristic of long survival time, the existing book protective agent is not well applicable to the Yao nationality channel paper. CN104594120A discloses a book protective agent and a preparation method thereof, the main components of the book protective agent comprise mussel mucin, glycerol, titanium dioxide, water glass and other substances, but the book protective agent is not ideal when being used in Yao nationality channels, can not solve the problems of paper scarification, yellowing and the like of the Yao nationality channels, can not provide enough flexibility and mechanical strength for the Yao nationality channels, can not solve the problems of subsequent use of the Yao nationality channels through protection and repair, and the life value of the Yao nationality channels lies in continuous reading and research of the Yao nationality channels by students, not just a cultural relic per se. In addition, the protective agent disclosed in CN104594120A contains biological protein, is easy to generate peculiar smell and cannot be stored for a long time, and the Yao nationality channel is more easy to mildew and moth after the protective agent is used. CN105851090A discloses a book insect-resist agent and a preparation method thereof, main components of Zanthoxylum bungeanum Maxim, goldthread root, Chinese honeylocust fruit, chinaberry fruit, lemongrass herb, tung oil, preservative and the like have certain insect-resist effect, but the book insect-resist agent is only suitable for preventing new books from insect, has no repair and protection capability on old books which are broken in grains, yellowed and polluted, and cannot enable the repaired books to be used for a long time.
Disclosure of Invention
The invention mainly provides a Yao nationality channel protective agent and a Yao nationality channel protective method. Unless otherwise specified, the percentages of substances referred to in the present invention are percentages by weight and temperatures are given in degrees Celsius, and the experimental procedures are generally carried out at room temperature (15-25 ℃) and normal atmospheric pressure (101 kPa).
The invention comprises the following steps:
1. a compound used as Yao nationality channel protectant is characterized in that the structural formula is NAR1AR2Ar3Wherein Ar is1-Ar3Are both aryl or substituted aryl groups and contain a polymerizable double bond.
2. The compound according to claim 1, which contains a carbazole structure.
3. A compound used as a Yao nationality channel protectant is characterized in that the structural formula is as follows,
Figure GSB0000185187380000021
wherein Ar is1-Ar9Is aryl or substituted aryl, and Ar1Comprising at least one polymerizable double bond.
4. A polymer used for Yao nationality channel protectant is characterized in that the polymer is polymerized by any compound monomer of 1-3, and the number average molecular weight is 2000-.
5. A Yao nationality channel protectant is characterized by comprising 0.1 wt% -2 wt% of 4 polymer, 0.1 wt% -0.5 wt% of cross-linking agent, 1 wt% -5 wt% of glycerol and 0.01 wt% -0.5 wt% of antioxidant.
6. A Yao nationality channel protectant is characterized by comprising 1 wt% of 4 polymer, 0.3 wt% of cross-linking agent, 4 wt% of glycerol and 0.05 wt% of antioxidant.
7. A Yao nationality channel protectant is characterized by comprising 1 wt% of 4 polymer, 0.3 wt% of cross-linking agent, 4 wt% of glycerol, 0.05 wt% of antioxidant and more than three polymerizable double bonds in the cross-linking agent.
8. A Yao nationality channel protection method is characterized in that the protective agent is sprayed on pages of a channel book in a mist form and is dried naturally.
As explained above, the Yao channel protective agent refers to a composition having the ability of protecting or repairing Yao channel and other book data.
The aryl group or substituted aryl group means a group having at least one aromatic ring, preferably at least two aromatic rings, and further preferably 10 or more aromatic rings. May include naphthyl, indolyl, fluorenyl, and the like. The number of carbon atoms of the aromatic ring is preferably 6.
The cross-linking agent is a polymerizable compound with more than three polymerizable double bonds, and has the following structure:
Figure GSB0000185187380000022
the antioxidant is selected from compounds which help the polymer and paper to enhance the antioxidant capacity, preferably phenolic antioxidants, preferably hydroquinone, thiobisphenol, and aminic antioxidants, preferably naphthylamine, diphenylamine, p-phenylenediamine.
The molecular weight of the polymer is preferably 2000-5000, more preferably 2000-4000. The polymerization process is preferably a free radical solution polymerization.
The protective agent contains a polymer with excellent mechanical property, and a layer of protective film is formed on the surface of the Yao nationality channel, so that the flexibility of the Yao nationality channel can be effectively improved, the paper of the Yao nationality channel cannot become brittle due to the increase of the thickness, the protective agent has excellent brittleness resistance, is convenient for researchers to browse and arrange, cannot damage the paper after being browsed for countless times, and greatly improves the use value of the Yao nationality channel. Due to the nature of the polymer and the fact that the polymer is diluted by using the mist spray and the tetrahydrofuran solvent, the polymer has strong wettability, so that the polymer enters the interior of paper and is tightly combined with the paper, and the strength of the Yao nationality channel is integrally improved. And because the polymer of the invention is a synthetic polymer rather than a biological polymer, the polymer is not easy to decay and has longer service life. The polymer disclosed by the invention has charge transfer capacity, can prevent static accumulation, has higher safety efficiency, and has great display significance for protecting precious Yao nationality channel. The polymer has good anti-tarnish capability, and the Yao nationality channels repaired by the protective agent are not easy to mildew and moth. The selection of molecular weight is particularly important, permeability is insufficient when the molecular weight is too large, mechanical strength is deficient when the molecular weight is too small, and the molecular weight range of the polymer can achieve good protection effect. The selection of the cross-linking agent of the protective agent is particularly important, and the cross-linking agent used in the conventional book protective agent cannot meet the requirement. By adopting the cross-linking agent with the specific structure, the protective agent is cross-linked with residual double bonds in the polymer under the condition of receiving a large amount of or trace illumination, on one hand, the energy of radiation can be actively absorbed, and the damage of the light radiation to the paper can be avoided; on the other hand, the crosslinking is generated after the energy is absorbed, so that the mechanical property, the corrosion resistance and the mildew resistance of the crosslinked polymer can be improved and ensured; in addition, the specific chemical structure of the cross-linking agent can form a conjugated structure with the polymer, so that the stability is enhanced, and the cross-linking agent has good resistance to ultraviolet rays and chemical corrosion.
Detailed Description
Synthesis example 1
Synthesis of 4- (3, 6-bis (4- ([ 2-methyl-1, 1' -biphenyi ] -4-yl (9, 9-dimethyl-9H-fluoren-2-yl) amino) phenyl) -9H-carbazol-9-yl) benzaldehyde: 5g of the starting compound 1 was reacted with 15g of the starting compound 2 in a mixed solvent of 100ml of tetrahydrofuran and 20ml of water in the presence of 0.90g of Pd (PPh3)3 and 7.70g of potassium carbonate under nitrogen at 75 ℃ for 8 hours. After the reaction is finished, the reaction product is cooled to room temperature, the solvent is removed by rotary evaporation in vacuum, and then the compound 3 is obtained by extracting with chloroform.
Synthesis of 4- (3, 6-bis (4- ([ 2-methyl-1, 1' -biphenyi ] -4-yl (9, 9-dimethyl-9H-fluoren-2-yl) amino) phenyl) -9H-carbazol-9-yl) styrene: 4g of intermediate 3 to 350ml of tetrahydrofuran solvent were added 2.8g of PPh3CMeBr and 1.5g t-BuOK, and the mixture was stirred in an ice-water bath under nitrogen for 3 hours, followed by slow neutralization with dilute hydrochloric acid. After the reaction is finished, chloroform is used for extraction, drying and filtration are carried out, and the crude product is obtained through concentration and crystallization. The crude product was recrystallized from a mixture of ethyl acetate and chloroform to give compound 4 with a purity of 99.9%.
Figure GSB0000185187380000031
Synthesis example 2
1g of the monomer compound 4 was dissolved in 100ml of a tetrahydrofuran solution, and the resulting solution was poured into a three-necked flask and purged with nitrogen. Weighing 0.02g of azodiisobutyronitrile, dissolving in 5 ml of tetrahydrofuran to prepare an initiator solution, slowly injecting the initiator solution into a three-neck flask, quickly heating to 60 ℃ after the injection is finished, polymerizing for 3 hours, and cooling to obtain a polymer solution. The number average molecular weight of the product was 3953 and the molecular weight distribution was 2.35 as determined by liquid chromatography.
Example 1
Taking 100ml of the solution, adding 0.3g of cross-linking agent, 5g of glycerol and 0.05g of hydroquinone, uniformly stirring, spraying the mixture on Yao nationality channel pages with the history of more than 70 years, naturally drying, placing the Yao nationality channel pages in the sun for 10 days, and observing the flexibility, the strength, the brittleness degree and the color change of the Yao nationality channel pages. Naturally placing the exposed Yao nationality road in an old warehouse in a humid environment, and storing at room temperature for 30 days to observe the condition of worm damage and mildew.
Comparative example 1
Adding 5g of glycerol and 0.05g of hydroquinone into 100ml of tetrahydrofuran, uniformly stirring, spraying the mixture on a Yao nationality channel page in a mist form, naturally drying, placing the Yao nationality channel page in the sun for 10 days, and observing the flexibility, the strength, the brittleness degree and the color change of the Yao nationality channel page. Naturally placing the exposed Yao nationality road in an old warehouse in a humid environment, and storing at room temperature for 30 days to observe the condition of worm damage and mildew.
Comparative example 2
Adding 5g of mussel mucin, 5g of glycerol, 5g of titanium dioxide and 2g of water glass into 83g of purified water, stirring uniformly at 50 ℃, cooling, spraying on the channel pages of Yao nationality, naturally drying, placing in the sun for 10 days, and observing the flexibility, strength, brittleness degree and color change. Naturally placing the exposed Yao nationality road in an old warehouse in a humid environment, and storing at room temperature for 30 days to observe the condition of worm damage and mildew.
Comparative example 3
The polymer molecular weight was replaced with 8600 and the rest of the conditions were the same as in example 1.
In the test data results, the flexibility, the strength and the brittle deformation resistance are divided into four grades, I, II, III and IV, wherein I represents the best performance, and IV represents the worst performance.
Flexibility Strength of Embrittlement resistance Color change Is eaten by worms Mildew of
Example 1 I I I No color change Without being damaged by worms Without mildew
Comparative example 1 III IV IV Yellowing of Is eaten by insects Has mildew
Comparative example 2 III II III Slight yellowing Is eaten by insects Has mildew
Comparative example 3 III II III Slight yellowing Without being damaged by worms Without mildew

Claims (4)

1. A Yao nationality channel protectant is characterized by comprising 0.1 wt% -2 wt% of polymer, 0.1 wt% -0.5 wt% of cross-linking agent, 1 wt% -5 wt% of glycerol and 0.01 wt% -0.5 wt% of antioxidant, wherein the polymer has the number average molecular weight of 2000-5000 and is formed by polymerizing compound monomers with the following structures:
Figure FSB0000185187370000011
wherein Ar is1-Ar9Is aryl or substituted aryl, and Ar1Comprising at least one polymerizable double bond.
2. The Yao nationality channel protectant of claim 1, comprising 1 wt% of the polymer, further comprising 0.3 wt% of a cross-linking agent, comprising 4 wt% glycerol, and comprising 0.05 wt% of an antioxidant.
3. The Yao nationality channel protectant of claim 2, wherein the crosslinker has the following structure:
Figure FSB0000185187370000012
4. a Yao nationality channel protection method, which is characterized in that the protective agent of one of claims 1 to 3 is atomized and sprayed on pages of a warp book and naturally dried.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102001989A (en) * 2009-08-28 2011-04-06 三星移动显示器株式会社 Heteroarylamine compounds, organic light-emitting devices and panel display devices
CN103373928A (en) * 2012-04-17 2013-10-30 三星显示有限公司 Compound for organic light-emitting diode, organic light-emitting diode including the same and flat panel display device
CN103956436A (en) * 2014-05-09 2014-07-30 江西冠能光电材料有限公司 Organic semiconductor hole transport material
CN105384679A (en) * 2015-12-24 2016-03-09 河南省科学院化学研究所有限公司 N,N'-diphenyl-N,N'-di(9,9-dimethyl fluorene-2-yl)-N-hexyl-(4,4'-diamine phenyl) carbazole and synthetic method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102001989A (en) * 2009-08-28 2011-04-06 三星移动显示器株式会社 Heteroarylamine compounds, organic light-emitting devices and panel display devices
CN103373928A (en) * 2012-04-17 2013-10-30 三星显示有限公司 Compound for organic light-emitting diode, organic light-emitting diode including the same and flat panel display device
CN103956436A (en) * 2014-05-09 2014-07-30 江西冠能光电材料有限公司 Organic semiconductor hole transport material
CN105384679A (en) * 2015-12-24 2016-03-09 河南省科学院化学研究所有限公司 N,N'-diphenyl-N,N'-di(9,9-dimethyl fluorene-2-yl)-N-hexyl-(4,4'-diamine phenyl) carbazole and synthetic method thereof

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