CN109667191A - 7-oxa-bicyclo[4.1.0 modification of chitosan for papery protection reinforces liquid and application method - Google Patents
7-oxa-bicyclo[4.1.0 modification of chitosan for papery protection reinforces liquid and application method Download PDFInfo
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- CN109667191A CN109667191A CN201910035634.3A CN201910035634A CN109667191A CN 109667191 A CN109667191 A CN 109667191A CN 201910035634 A CN201910035634 A CN 201910035634A CN 109667191 A CN109667191 A CN 109667191A
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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
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Abstract
The present invention relates to a kind of 7-oxa-bicyclo[4.1.0 modification of chitosan for papery protection to reinforce liquid and application method, by following weight percent meter: chitosan 1%-10%, 7-oxa-bicyclo[4.1.0 5%-20%, organotin catalysts 0.1%-0.3% and diluted acid 50%-93% are made, chitosan is added in diluted acid, at 40-50 DEG C, ultrasound 25-35min under 100-120w, obtain liquid A, organotin catalysts are added in liquid A, it is uniformly dispersed, epoxy-cyclohexane is added under the magnetic agitation of 500-800r/min, 70-80 DEG C, react 6-8h, it is cooled to room temperature, obtain glue liquid B, it is adjusted to PH=7-8, to obtain the final product；Abundant raw material of the present invention, preparation method science, easy to operate, reaction step is few, and the period is short, not only enhances the mechanical strength of paper relics, is alternatively arranged as reactive diluent, is effectively improved glue mobility, economic and social benefit is significant.
Description
Technical field
The present invention relates to macromolecule, it is especially a kind of for papery protection 7-oxa-bicyclo[4.1.0 modification of chitosan reinforce liquid and
Application method.
Background technique
Historical relic books, data using paper as carrier is the propagation of human civilization, social progress and science and technology
The important function for being difficult to substitute is played, but over time, the variation of external environmental condition, these preciousnesses
Paper relics are occurring to change and damage.Wherein quite a few turned to be yellow, gone mouldy, aging brittle failure, some has become
Fragment, gently smear powder, can not browse at all, paper relics are a kind of frivolous, soft, the low intensive materials of quality, once
Protect processing method improper, caused by consequence will be it is crushing and irredeemable, paper document is timely reinforced
Have become an extremely urgent task with protection, therefore it provides a kind of material for papery protection is imperative.
Summary of the invention
It is a kind of for papery protection it is an object of the present invention to provide for the defect for overcoming the prior art for above situation
7-oxa-bicyclo[4.1.0 modification of chitosan reinforce liquid and application method, can effectively solve the problems, such as the reinforcement protection of paper document.
The technical solution that the present invention solves is a kind of 7-oxa-bicyclo[4.1.0 modification of chitosan reinforcing liquid for papery protection,
By following weight percent meter: chitosan 1%-10%, 7-oxa-bicyclo[4.1.0 5%-20%, organotin catalysts 0.1%-
0.3% and diluted acid 50%-93% is made, wherein chitosan is added in diluted acid, the ultrasound 25- at 40-50 DEG C, 100-120w
35min obtains liquid A, and organotin catalysts are added in liquid A, are uniformly dispersed, and adds under the magnetic agitation of 500-800r/min
Enter epoxy-cyclohexane, 70-80 DEG C, reacts 6-8h, be cooled to room temperature, obtain glue liquid B, glue liquid B is adjusted to PH with 0.1mol/L lye
=7-8 reinforces liquid to get epoxy-cyclohexane modification of chitosan；
Deacetylation >=95% of the chitosan, viscosity 100-200mP.s；
The epoxy-cyclohexane is steamed again using preceding, and 130-132 DEG C of boiling point；
The diluted acid is acetic acid diluted, dilute hydrochloric acid or the dust technology of 0.1mol/L；
The organotin catalysts are dibutyl tin dilaurate, dibutyltin diacetate, stannous octoate or two (dodecanes
One of base sulphur) dibutyl tin, purity is 99.9%；
The epoxy-cyclohexane modification of chitosan for papery protection of the invention reinforces the toughness, strong that liquid has enhancing film
Degree is effectively improved the mobility for reinforcing liquid, protects effective for paper relics, and method is will to be used for the epoxy of papery protection
Hexamethylene modification of chitosan reinforces liquid, the 60-80% of original volume concentration is diluted to by diluent, after paper relics are dipped in dilution
Epoxy-cyclohexane modification of chitosan reinforce in liquid, soak and pull out, at room temperature to dry；
The diluent is any in dehydrated alcohol, ethyl acetate, propylene glycol methyl ether acetate or isopropyl acetate
Kind.
Abundant raw material of the present invention, preparation method science, easy to operate, reaction step is few, and the period is short, effective for protecting papery
Historical relic not only enhances the mechanical strength of paper relics, is alternatively arranged as reactive diluent, is effectively improved glue mobility, be papery
Historical relic reinforces the innovation on liquid, and economic and social benefit is significant.
Detailed description of the invention
Fig. 1 is the reaction mechanism figure of 7-oxa-bicyclo[4.1.0 modification of chitosan (derivative) of the present invention.
Specific embodiment
Specific embodiments of the present invention will be described in detail with concrete condition with reference to embodiments.
Embodiment 1: a kind of 7-oxa-bicyclo[4.1.0 modification of chitosan for papery protection of the present invention reinforces liquid, by 1g chitosan
It is added in 80ml diluted acid, the ultrasound 30min at 45 DEG C, 100w, the liquid A that chitosan concentration is 12.5mg/ml is obtained, by 0.1g
Dibutyltin dilaurate catalyst is added in liquid A, is uniformly dispersed, is warming up to 70 DEG C, under the magnetic agitation of 800r/min
10g epoxy-cyclohexane is added, reacts 7h, is cooled to room temperature, obtains glue liquid B, glue liquid B is adjusted to PH=7-8 with 0.1mol/L lye,
Liquid is reinforced up to epoxy-cyclohexane modification of chitosan；Its application method is the modified shell of 7-oxa-bicyclo[4.1.0 that will be used for papery protection
Glycan reinforces liquid, and the 60-80% of original volume concentration is diluted to by diluent, and paper relics are dipped in the epoxy-cyclohexane after dilution
Modification of chitosan is reinforced in liquid, is soaked and is pulled out, at room temperature to dry.
Embodiment 2: a kind of 7-oxa-bicyclo[4.1.0 modification of chitosan for papery protection of the present invention reinforces liquid, by 1.25g shell
Glycan is added in 90ml diluted acid, the ultrasound 30min at 45 DEG C, 100w, obtains the liquid A that chitosan concentration is 13.9mg/ml, will
0.1g dibutyltin dilaurate catalyst is added in liquid A, is uniformly dispersed, is warming up to 80 DEG C, stirs in the magnetic force of 500r/min
Lower addition 8g epoxy-cyclohexane is mixed, 6.5h is reacted, is cooled to room temperature, obtains glue liquid B, glue liquid B is adjusted to PH with 0.1mol/L lye
=7-8 reinforces liquid to get epoxy-cyclohexane modification of chitosan, uses same embodiment 1.
Embodiment 3: a kind of 7-oxa-bicyclo[4.1.0 modification of chitosan for papery protection of the present invention reinforces liquid, by 1.25g shell
Glycan is added in 90ml diluted acid, the ultrasound 30min at 45 DEG C, 100w, obtains the liquid A that chitosan concentration is 13.9mg/ml, will
0.1g dibutyltin dilaurate catalyst is added in liquid A, is uniformly dispersed, is warming up to 75 DEG C, stirs in the magnetic force of 650r/min
Lower addition 8g epoxy-cyclohexane is mixed, 7.5h is reacted, is cooled to room temperature, obtains glue liquid B, glue liquid B is adjusted to PH with 0.1mol/L lye
=7-8 reinforces liquid to get epoxy-cyclohexane modification of chitosan；Application method is the same as embodiment 1.
Chitosan is uniformly dispersed in diluted acid by the reaction under ultrasound condition, and under organotin catalyzed effect, shell is poly-
The ternary epoxy group of active amido attack 7-oxa-bicyclo[4.1.0 in sugar minor structure, 7-oxa-bicyclo[4.1.0 open loop are grafted on chitosan point
Sub- long-chain and obtain.
7-oxa-bicyclo[4.1.0 modification of chitosan of the invention reinforces liquid, and preparation process is simple, is swift in response.7-oxa-bicyclo[4.1.0
Easily with the amido on chitosan ring-opening reaction occurs for the active ternary epoxy group in molecular structure, and in chitosan molecule structure
Due to the introducing of rigid hexatomic ring, greatly enhance toughness, the intensity of film；In addition, 7-oxa-bicyclo[4.1.0 is reactive diluent again,
Not only enhance the mechanical strength of paper, it is also effective to improve the mobility for reinforcing liquid, it avoids making on paper relics surface and inside
At concentration gradient, to delay, prevent paper relics aging.Related testing data is as follows:
Replace ancient times pattern with modern calligraphy rice paper, using the method for heat ageing, i.e., sample place 72 in baking oven ±
1h, temperature are controlled at 105 ± 2 DEG C, carry out primary simulation senile experiment to sample, using this treated sample as plain pape
Sample.The epoxy-cyclohexane modification of chitosan of the method for the present invention preparation is reinforced into liquid and is diluted to 60%-80%, prepares two complete phases
With pallet, the epoxy-cyclohexane modification of chitosan in one of pallet first uniformly after one layer of dilution of paving reinforces liquid, will be by mark
The epoxy-cyclohexane modification of chitosan of wherein one side after dilution for the blank pattern that standard is cut out, which is reinforced in liquid, to be impregnated 5-10 minutes,
Then the epoxy-cyclohexane modification of chitosan after uniformly spreading one layer of dilution identical with volume in aforementioned pallet in another pallet
Liquid is reinforced, the another side for testing pattern is impregnated 5-10 minutes.Experiment pattern is taken out to put naturally in the stable environment of epidemic disaster
It sets to its natural drying.It is right in aforementioned manners to the product of the embodiment of the present invention respectively in order to verify using effect of the invention
Rice paper carries out consolidation process, tensile strength, folding strength, paper tear degree, sheet gloss and the paper of rice paper before and after test processes
Zhang Baidu the results are shown in Table 1.Wherein, paper tensile strength test is measured according to China's standard GB/T/T12914-2008；
Paper folding test is measured according to China's standard GB/T/T457-2008；Paper tear degree is according to China's national standard
GB/455-2002 is measured；Sheet gloss is measured according to China's standard GB/T/T 8941-2013；Paper White Degree
It is measured according to China's standard GB/T/T7974-2002.
Table 1:
The design feature of paper fibre macromolecular makes its molecule have multiple moving cell, therefore, under external force
Mechanical behavior is a loose process, and paper fibre is being generated extension by the responsive to axial force gradually increased, until most
It cuts off and splits.Tensile strength is a component part of bursting strength, folding strength and anti-tear power etc..The bond strength of fiber, fiber
Average length and its interior tissue direction, fiber degree of interlocking have a major impact paper tensile strength, and intensity most can direct table
The degree of aging and inspection consolidation effect of existing paper can be showed intuitively by comparing the variation of paper fibre tensile strength
The variation for reinforcing front and back intensity, is measured paper tensile strength according to national standard GB/T12914-2008.
The twofold number that can bear before pattern fracture, indicates the folding ability of paper, with folding strength tester
It measures pattern twofold number, the effect that glue reinforces pattern is evaluated with this, is measured according to national standard GB/T457-2008.
Sheet gloss refers to the mirror-reflection degree of paper, and actually paper surface is in addition to there is also unrestrained anti-for mirror-reflection
It penetrates, according to the requirement of paper relics protection " restoring the old as the old, keep original appearance ", glossiness before and after measurement experiment pattern processe is commented
Its vivid appearance characteristics of valence are measured glossiness according to national standard GB/T 8941-2013, according to China's standard GB/T/
T7974-2002 is measured Paper White Degree.
The natural macromolecular material chitosan that the present invention uses has the properity of similar paper fibre element for raw material,
Have good biocompatibility, affinity with paper fiber, can build bridge between fiber and to paper fibre have good permeability,
Wellability, structure free amino has a preferable bacteriostasis property more in molecule, while the raw material sources are abundant, nontoxic no dirt
Dye, invertibity are strong；7-oxa-bicyclo[4.1.0 used in the present invention is a kind of ring with hexa-atomic alicyclic group and ternary epoxy group
Oxygen compound, the mechanical strength of paper relics not only can be enhanced in the reinforcing liquid thus prepared, but also itself has stronger
Solvability can be used as reactive diluent, improves glue mobility, avoids causing concentration gradient on paper relics surface and inside
It is the innovation that paper relics are reinforced on liquid to delay paper relics aging, economic and social benefit is significant.
Claims (5)
1. a kind of 7-oxa-bicyclo[4.1.0 modification of chitosan for papery protection reinforces liquid, it is characterized in that: by following weight percent
Meter: chitosan 1%-10%, 7-oxa-bicyclo[4.1.0 5%-20%, organotin catalysts 0.1%-0.3% and diluted acid 50%-93% are made,
In, chitosan is added in diluted acid, ultrasound 25-35min, obtains liquid A at 40-50 DEG C, 100-120w, by organotin catalysts
It is added in liquid A, is uniformly dispersed, epoxy-cyclohexane is added under the magnetic agitation of 500-800r/min, 70-80 DEG C, reacts 6-
8h is cooled to room temperature, and obtains glue liquid B, and glue liquid B is adjusted to PH=7-8 with 0.1mol/L lye and is gathered to get the modified shell of epoxy-cyclohexane
Sugar reinforces liquid；
Deacetylation >=95% of the chitosan, viscosity are 100-200 mP.s；
The epoxy-cyclohexane is steamed again using preceding, and 130-132 DEG C of boiling point；
The diluted acid is acetic acid diluted, dilute hydrochloric acid or the dust technology of 0.1mol/L；
The organotin catalysts are dibutyl tin dilaurate, dibutyltin diacetate, stannous octoate or two (dodecyls
One of sulphur) dibutyl tin, purity is 99.9%.
2. the 7-oxa-bicyclo[4.1.0 modification of chitosan according to claim 1 for papery protection reinforces liquid, it is characterized in that: will
1g chitosan is added in 80ml diluted acid, the ultrasound 30min at 45 DEG C, 100w, obtains the liquid A that chitosan concentration is 12.5mg/ml,
0.1g dibutyltin dilaurate catalyst is added in liquid A, is uniformly dispersed, is warming up to 70 DEG C, in the magnetic force of 800r/min
It is added with stirring 10g epoxy-cyclohexane, 7h is reacted, is cooled to room temperature, obtains glue liquid B, glue liquid B is adjusted to PH with 0.1mol/L lye
=7-8 reinforces liquid to get epoxy-cyclohexane modification of chitosan.
3. the 7-oxa-bicyclo[4.1.0 modification of chitosan according to claim 1 for papery protection reinforces liquid, it is characterized in that: will
1.25g chitosan is added in 90ml diluted acid, the ultrasound 30min at 45 DEG C, 100w, obtains the liquid that chitosan concentration is 13.9mg/ml
0.1g dibutyltin dilaurate catalyst is added in liquid A, is uniformly dispersed, 80 DEG C is warming up to, 500r/min's by body A
8g epoxy-cyclohexane is added under magnetic agitation, reacts 6.5h, is cooled to room temperature, obtains glue liquid B, with 0.1mol/L lye by glue liquid B
It is adjusted to PH=7-8 and reinforces liquid to get epoxy-cyclohexane modification of chitosan.
4. the 7-oxa-bicyclo[4.1.0 modification of chitosan according to claim 1 for papery protection reinforces liquid, it is characterized in that: will
1.25g chitosan is added in 90ml diluted acid, the ultrasound 30min at 45 DEG C, 100w, obtains the liquid that chitosan concentration is 13.9mg/ml
0.1g dibutyltin dilaurate catalyst is added in liquid A, is uniformly dispersed, 75 DEG C is warming up to, 650r/min's by body A
8g epoxy-cyclohexane is added under magnetic agitation, reacts 7.5h, is cooled to room temperature, obtains glue liquid B, with 0.1mol/L lye by glue liquid B
It is adjusted to PH=7-8 and reinforces liquid to get epoxy-cyclohexane modification of chitosan.
5. the 7-oxa-bicyclo[4.1.0 modification of chitosan described in claim 1-4 for papery protection is reinforced liquid and is protected in paper relics
In application, method is, the 7-oxa-bicyclo[4.1.0 modification of chitosan that will be used for papery protection reinforces liquid, is diluted to substance by diluent
Paper relics are dipped in the epoxy-cyclohexane modification of chitosan after dilution and reinforced in liquid, soaked and pull out by the 60-80% of product concentration,
Room temperature is down toward dry；
The diluent is any one of dehydrated alcohol, ethyl acetate, propylene glycol methyl ether acetate or isopropyl acetate.
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Cited By (4)
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| CN111270554A (en) * | 2020-03-19 | 2020-06-12 | 郑州大学 | Amphipathic cationic chitosan-phosphate starch composite strengthening liquid for paper protection |
| CN111303353A (en) * | 2020-03-19 | 2020-06-19 | 郑州大学 | Chitosan/nano TiO for paper protection2Acrylate reinforcing liquid and application thereof |
| CN111424464A (en) * | 2020-03-19 | 2020-07-17 | 郑州大学 | Preparation method and application of modified chitosan/silicon composite reinforcement liquid for paper protection |
| CN116463885A (en) * | 2023-03-29 | 2023-07-21 | 郑州大学 | CS-FEC/CS-Arg-FEC multifunctional protection liquid for protecting paper cultural relics |
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| CN111303353B (en) * | 2020-03-19 | 2022-06-24 | 郑州大学 | Chitosan/nano TiO for paper protection2Acrylate reinforcing liquid and application thereof |
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| CN116463885B (en) * | 2023-03-29 | 2024-04-05 | 郑州大学 | CS-FEC/CS-Arg-FEC multifunctional protection liquid for protecting paper cultural relics |
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| CN109667191B (en) | 2021-03-05 |
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