CN110344283A - The preparation and the application in the reparation of aging paper that a kind of cellulose base dispersing agent and preparation method are used for MT treatment fluid with it - Google Patents
The preparation and the application in the reparation of aging paper that a kind of cellulose base dispersing agent and preparation method are used for MT treatment fluid with it Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
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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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/13—Silicon-containing compounds
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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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/25—Cellulose
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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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
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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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
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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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/50—Spraying or projecting
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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
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/04—Physical treatment, e.g. heating, irradiating
- D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
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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
- 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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Abstract
The invention belongs to Rare Book Use technical field, a kind of cellulose base dispersing agent is disclosed and preparation that preparation method is used for MT treatment fluid with it and the application in the reparation of aging paper.The cellulose base dispersing agent, which is reacted by cellulose with silylating reagent, to be prepared.The method that the cellulose base dispersing agent is used for the repair process of aging paper are as follows: aging paper pre-dried, the preparation of MT-x treatment fluid, aging paper are subjected to the processing of MT-x treatment fluid and are placed in draught cupboard to dry, then vacuum drying treatment, the equilibrium water conten in thermostatic constant wet chamber, completion processing.Method of the cellulose base dispersing agent for the repair process of aging paper has the multi-functional treatment effect such as depickling, enhancing, hydrophobic, anti-aging to aging paper.
Description
Technical field
The invention belongs to Rare Book Use technical fields, and in particular to a kind of cellulose base dispersing agent and preparation method are used with it
Preparation in MT treatment fluid and the application in the reparation of aging paper.
Background technique
China is with a long history, and ancient books historical relic is large number of.Ancient books historical relic has history relic, academic information, art
The properties of value such as representativeness.During spreading, since condition of storage is poor or artificial destruction, a large amount of ancient books historical relic can not be kept away
The damage situations such as aging, breakage can occur with exempting from.Therefore, the protection work of ancient books historical relic is particularly significant.The main table of paper aging
Now for paper acidification, paper strength reduce and color yellowing, wherein paper acidification be cause page aging main reason it
One.There are many factor for causing paper to be acidified, and chemistry of lignin's property unstability is oxidized easily and hydrolyzes to form acid
Matter；The residual of trace chloride accelerates alum and goes bad to paper in bleaching process, eventually leads to paper acidification；Pulping and paper-making mistake
Cheng Zhong, the acidic chemical of addition have aggravated the acidification feelings of paper such as acid alum, acid rosin and alum glue material etc.
Condition；In printing process, one of the factor of acid or oxidiferous ink and pigment and paper the acidity enhancing used；Separately
Outside, paper during storage, by sour gas (such as SO in atmosphere2、H2S、NOXDeng) influence and microorganism (metabolism
The organic acid of generation) erosion.In short, the reason of causing paper to be acidified has very much, all kinds of factor is neither independently carried out, and
It is interaction, mutually promotes.After paper acidification, cellulosic acid catalytic hydrolysis reaction can occur under normal temperature conditions, make
Cellulose macromolecule chain shortens, and the degree of polymerization reduces, to reduce the physical strength of paper.In addition, paper is in wet air
Or oxidation reaction can also occur under ultraviolet light, some coloured groups are generated, paper color is deepened, especially existing for the lignin
Under the conditions of, paper yellowing is more obvious.
Foreign countries are more early to aging paper depickling research, since 1970s, have been devoted to grinding for extensive depickling
Study carefully work, the method that there is now practical application has Wei T ' o method, Bookkeeper method, Battle method, Book Saver method etc..
Methyl carbonic acid magnesium is mainly dissolved in methanol and freon mixed liquor by Wei T ' o method, by being atomized to the paper of aging
Processing, pH is between 7-8 after processing；Bookkeeper method is that MgO molecule is dispersed in perflexane, is used
Sprinkling or impregnation, treatment effeciency is high, and paper pH saves 3-5 times of service life extension between 7-10 after depickling；Battle method
It is to be dissolved in titanium magnesium alkoxide hexamethyldisiloxane (HMDO), after spraying treatment, page deacidification effect is good, while can be reduced to ring
The pollution in border；Book Saver method is that two normal propyl alcohol magnesium carbonate are dissolved in heptafluoro-propane (HFC227), carries out predrying to page
After impregnation, deacidification effect is preferable, safety and environmental protection, while cost is relatively low for depickling.These methods are mainly with ancient books depickling
It is main, but all had certain problems after handling, such as powder deposition, ink blur, other side effects (Cellulose, 2015,
22(5):2859-2897)。
With the development of science and technology, Giorgi et al. starts to propose nanotechnology being used for Rare Book Use, nano particle diameter
It is small, it easily permeates, the problems such as powder deposits (Langmuir, 2002,18 (21): 8198-8203) can be reduced.Giorgi etc. is proposed
Mg (OH) is prepared in precipitation from homogeneous solution reacts with NaOH using magnesium salts2Nano particle, by the Mg (OH) of preparation2Nano particle is equal
In the even mixture for being scattered in isopropanol or fluothane hydrocarbon, it to be used for depickling.The result shows that Mg (OH)2Nano particle can be simply
Paper fiber is penetrated into, deacidification effect is preferable, compared with Wei T ' o method, nanometer Mg (OH)2Deacidification efficiency is higher, and finds de-
Paper after acid has preferable antiageing effect (Langmuir, 2005,21 (18): 8495-8501).Poggi et al. is proposed
A kind of Ca (OH)2The synthetic method of nano particle, for inhibiting the oxidation and acid degradation process of paper fibre.Result of study table
Bright, this method can effectively inhibit acid degradation (the Journal of Cultural of cellulose in aging paper for a long time
Heritage,2016, 18:250-257).Wang Heyun etc. has carried out the research that nano-MgO is applied to paper relics depickling, experiment
Show that there is preferable deacidification effect, but also has and inhibit Cu2+、Fe3+Effect (the China of ion pair cellulose catalytic oxidation
Papermaking, 2012,31 (3): 36-38).Wang Sinong etc. has carried out research of the one-dimensional magnesia for ancient books paper deacidification, preparation
Nanoscale magnesium has preferable deacidification effect, and pH is improved from 4.18 to 8.82 (Fudan Journal (natural sciences after processing
Version), 2016,55 (6): 698-701).Ren Junli etc. has invented a kind of ancient books reparation liquid, mainly by CaO/MgO/TiO2Nanometer
The additional polyethyleneimine (PEI) of grain is scattered in isopropanol as dispersing agent to be prepared, the nano-dispersed sol property of preparation
Stablize, be easy to atomization process, preferable depickling can be reached after processing and deposits alkali, enhancing and other effects, meanwhile, the color difference of generation is less,
(CN201910065834.3) is also had not significant impact to writing ink.
The deacidification agent for being usually used in ancient books reparation is mainly the micro-nano granules of inorganic alkaline, such as Mg (OH)2、 Ca(OH)2、
MgO and CaO etc., but inorganic micro-nano granules there is indissoluble and it is easy to reunite the problems such as, therefore, by micro-nano of inorganic alkaline
Grain is applied to ancient books depickling, is that the suitable solvent of selection and dispersing agent, the difficult point of research are suitable dispersant mainly
Selection and development.
Summary of the invention
For the prior art have the shortcomings that more than and shortcoming, the purpose of the present invention is to provide a kind of cellulose bases
The preparation and the application in the reparation of aging paper that dispersing agent and preparation method are used for MT treatment fluid with it.
The purpose of the present invention is realized at least through one of following technical solution.
Cellulose base dispersing agent (TMSC-x) provided by the invention be by cellulose under given conditions with silylating reagent
A kind of silanized cellulose element being prepared after reaction.
A kind of preparation method of cellulose base dispersing agent (TMSC-x) provided by the invention, including the following steps: will be fine
Dimension element is reacted in DMAc/LiCl system with silylating reagent or is reacted under conditions of chemical vapor deposition, the cellulose
Glucosyl group (AGU) and silylating reagent molar ratio be 1:0.1-1:10, obtain the cellulose base dispersing agent.
Further, the cellulose is one of alpha-cellulose, microcrystalline cellulose and nano-cellulose；The silane
Change reagent is methyltrimethoxysilane (MTMS), trim,ethylchlorosilane (TMCS), octadecyl trichlorosilane alkane (OTMSC), six
One or more of methyl disilazane (HMDS) and silane coupling agent (KH-550) etc..
Further, reaction is carried out under stirring in the DMAc/LiCl system, the DMAc/LiCl body
The temperature reacted in system is 60-100 DEG C, and the revolving speed of stirring is 200-800r/min, the time reacted in DMAc/LiCl system
For 0.5-1.5h, need to be dried after reacting in DMAc/LiCl system；The temperature of the chemical vapor deposition is
90-120 DEG C, the time of chemical vapor deposition is 3-9h.
Preferably, described be dried is vacuum drying treatment, and the temperature of drying process is 60 DEG C, the time of drying process
For for 24 hours.
The present invention provides a kind of cellulose base dispersing agent as made from above-mentioned preparation method.
The method that a kind of cellulose base dispersing agent provided by the invention is used to prepare MT-x treatment fluid, including walk as follows
It is rapid: it takes metal oxide nanoparticles to be added in hexamethyldisiloxane (HMDO), is uniformly mixed, TMSC-x is then added,
Ultrasonic disperse processing, obtains the MT-x treatment fluid.
Further, the metal oxide nanoparticles are MgO, CaO, TiO2And one or more of ZnO；The gold
The mass volume ratio for belonging to oxide nano particles and HMDO is 1-4g/L；In the MT-x treatment fluid, the concentration of TMSC-x is
0-2.0wt.%；The supersonic frequency of the ultrasonic disperse processing is 50-150KHz, and the time of ultrasonic disperse processing is 30-
60min。
Preferably, in the MT-x treatment fluid, the concentration of TMSC-x is 0.5wt.%.
The present invention provides a kind of MT-x treatment fluid as made from above-mentioned preparation method.
The present invention provides a kind of method that MT-x treatment fluid is used for the repair process of aging paper, includes the following steps:
(1) pre-dried of aging paper: by aging paper after constant temperature and humidity is handled, be put into vacuum dryer into
Row vacuum drying treatment, the aging paper after being dried；
(2) the aging paper after step (1) described drying process is hung in closed box, is carried out with MT-x treatment fluid
Spray treatment is subsequently placed in draught cupboard and carries out air-drying processing, the aging paper that obtains that treated；
(3) by treated described in step (2), aging paper is placed in vacuum dryer is dried, then constant temperature
Equilibrium water conten in constant humidity processing, takes out, and completes the repair process of aging paper.
Further, the temperature of step (1) the constant temperature and humidity processing is 23 ± 1 DEG C, and the humidity of constant temperature and humidity processing is
50 ± 2%, the time of constant temperature and humidity processing is 12-24h, preferably for 24 hours；The vacuum drying temperature is 40-60 DEG C, preferably
It is 50 degrees Celsius, the moisture content of the aging paper after the drying process is 0.5-2wt.%.
Further, the number of step (2) described spray treatment is 1-4 times, by dry weight, the MT-x treatment fluid
Total quantity for spray is the 0.1-2.0% of aging paper quality；Step (3) is described to be dried as vacuum drying, the temperature of drying process
Degree is 40-60 DEG C；The temperature of the constant temperature and humidity processing is 23 ± 1 DEG C, and the humidity of constant temperature and humidity processing is 50 ± 2%, constant temperature
The time of constant humidity processing is 12-24h.
Preferably, by dry weight, total quantity for spray of the MT-x treatment fluid is the 1.0% of aging paper quality.
The degree of substitution of cellulose base dispersing agent TMSC-x prepared by the present invention is not less than 2.68, is dispersed using this cellulose base
The MT-x treatment fluid of agent preparation has preferable dispersion stabilization, and viscosity is not higher than 152mPas, MT-x treatment fluid is used for
Aging paper process, after processing, between 8.5-9.5, alkali residual volume can reach page pH between 140-260mmol/Kg
Alkali effect is deposited in preferable depickling；Page tensile strength improves 10%-30%, and folding strength improves 50%-75%；Whiteness
(R457, D65) is slightly promoted, and color difference △ E fluctuates between 0.5-3, and after processing, page surface is completely smooth, writing ink without
Significant change, in addition, also having the function of centainly hydrophobic and anti-aging.
The present invention mainly carries out a degree of silylating reagent using cellulose, and certain degree of substitution is prepared
TMSC-x, due to the similar principle to mix, TMSC-x can be dissolved in HMDO, simultaneously as TMSC-x is by cellulose derivatization
, have compared with long chain, preferable dispersion effect can be played to HMDO neutral and alkali metal oxide nanoparticles, glue
It spends small, is easy to atomization process, preferable depickling can be played and deposit alkali effect；On the other hand, both with the TMSC-x compared with long chain
Physical crosslinking can be generated with paper surface cellulose, to achieve the purpose that strengthening for paper, also due to the surface TMSC-x exists
Silylation also assigns paper certain hydrophobic performance.
During processing, the acidic-group of paper is neutralized, and final aging page is restored to neutral and alkalescent,
Remaining alkaline matter can also pre- anti-aging paper be further acidified；TMSC-x enhance paper strength while also assign paper compared with
Good hydrophobic performance, extends the holding time of aging paper；In addition, when there is atomization process mode medical fluid to be uniformly dispersed, handle
Between the consumption of short, medical fluid less, it is smaller to paper influences the advantages that, be also suitble to batch processing, therefore, the present invention has in Rare Book Use
There is preferable application value.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that
(1) cellulose base dispersing agent provided by the invention has many advantages, such as that raw material is extensive, cheap, easily prepared, energy
Enough it is mass produced.
(2) repairing liquid (the i.e. described MT treatment fluid) provided by the present invention for the depickling enhancing of aging paper has paper
The multi-functional treatment effect such as depickling, enhancing, hydrophobic, ageing-resistant.
(3) aging paper repair process method provided by the invention by page depickling, page enhancing and ageing-resistant three sections of page
Processing is reduced to one section of processing, hence it is evident that shortens process flow, reduces process cycle, improve treatment effeciency.
Detailed description of the invention
Fig. 1 is the line chart that difference TMSC-x influences MT-x treatment fluid dispersion effect in embodiment 4；
Fig. 2 is the line chart that difference MT-x treatment fluid influences pattern tensile index in embodiment 5；
Fig. 3 is the line chart that difference MT-x treatment fluid influences pattern folding strength in embodiment 5；
Fig. 4 is the line chart that difference MT-x treatment fluid influences pattern hydrophobic effect in embodiment 5.
Specific embodiment
Specific implementation of the invention is described further below in conjunction with attached drawing and example, but implementation and protection of the invention
It is without being limited thereto.If it is existing to be that those skilled in the art can refer to it is noted that there is the not special process of detailed description below
Technology realize or understand.Reagents or instruments used without specified manufacturer, be considered as can by it is commercially available be commercially available it is normal
Advise product.
Embodiment 1
A kind of preparation method of cellulose base dispersing agent, includes the following steps:
(1) preparation of TMSC-x: the alpha-cellulose for weighing 0.4g dissolves spare in DMAc/LiCl system, then presses
AGU/OTMSC is separately added into OTMSC (octadecyl trichlorosilane alkane) with the molar ratio of 1:1,1:5 and 1:10 and is reacted, reaction
Temperature is the glucosyl group that 80 DEG C, revolving speed 500r/min, reaction time 1h, AGU are the alpha-cellulose, is taken out after reaction
Mixture is dried in vacuo for 24 hours under the conditions of 60 DEG C by washing, filtering, and obtains the cellulose base dispersing agent TMSC-x, will
The molar ratio of AGU/OTMSC be respectively TMSC-x made from 1:1,1:5 and 1:10 be respectively designated as TMSC-1, TMSC-2 and
TMSC-3, it is spare.
(2) measurement of degree of substitution: TMSC-x (TMSC-1, TMSC-2 and TMSC-3) made from 50mg step (1) is taken to carry out
Acetylation process is then dissolved in deuterated chloroform (CDCl3) in (50mg/ml), send1H-NMR detection, calculates degree of substitution DS.
(3) dissolubility is tested: taking the TMSC-x (TMSC-1, TMSC-2 and TMSC-3) of 0.25g with the concentration of 0.5wt.%
It is added in HMDO (hexamethyldisiloxane) solvent, is then ultrasonically treated 30min under conditions of frequency is 100KHz, observe
Its dissolubility.
The present embodiment reacts preparation TMSC-x using alpha-cellulose as raw material with OTMSC in DMAc/LiCl system, investigates
The deliquescent influence in HMDO on it of the degree of substitution of TMSC-x, the results are shown in Table 1.
Table 1
The measurement and dissolubility test of degree of substitution are carried out to TMSC-x manufactured in the present embodiment.Measurement result show with
The degree of substitution of the increase of OTMSC additional amount, TMSC-x is gradually increased, after degree of substitution reaches 2.86, TMSC-3 ability in HMDO
It can be completely dissolved.
Embodiment 2
A kind of preparation method of cellulose base dispersing agent, includes the following steps:
(1) preparation of TMSC-x: the microcrystalline cellulose for weighing 0.4g dissolves spare in DMAc/LiCl system, then presses
The molar ratio of AGU/HMDS/TMCS is that 1:1:0.1,1:1:10 and 1:10:0.1 are separately added into HMDS (hexamethyldisilazane)
It is reacted with TMCS (trim,ethylchlorosilane), reaction temperature is 80 DEG C, revolving speed 500r/min, reaction time 1h, reaction
After take out mixture, by washing, filtering, be dried in vacuo for 24 hours under the conditions of 60 DEG C, obtain the cellulose base dispersing agent
The molar ratio of AGU/HMDS/TMCS is respectively the difference of TMSC-x made from 1:1:0.1,1:1:10 and 1:10:0.1 by TMSC-x
It is named as TMSC-4, TMSC-5 and TMSC-6, it is spare.
(2) measurement of degree of substitution: taking 50mg TMSC-x (TMSC-4, TMSC-5 and TMSC-6) to carry out acetylation process,
It is then dissolved in deuterated chloroform (CDCl3) in (50mg/ml), send1H-NMR detection, calculates degree of substitution DS.
(3) dissolubility is tested: taking the TMSC-x (TMSC-4, TMSC-5 and TMSC-6) of 0.25g with the concentration of 0.5wt.%
It is added in HMDO (hexamethyldisiloxane) solvent, is then ultrasonically treated 30min under conditions of frequency is 100KHz, observe
Its dissolubility.
The present embodiment reacts preparation TMSC- using microcrystalline cellulose as raw material with HMDS and TMCS in DMAc/LiCl system
X investigates degree of substitution deliquescent influence in HMDO on it of TMSC-x, and the results are shown in Table 2.
Table 2
The measurement and dissolubility test of degree of substitution are carried out to TMSC-x manufactured in the present embodiment.Measurement result, which is shown, works as TMCS
When additional amount is constant, with the increase of HMDS additional amount, the degree of substitution of TMSC-x is gradually increased, after degree of substitution reaches 2.96,
TMSC-6 can be just completely dissolved in HMDO；And when HMDS additional amount is constant, with the increase of TMCS additional amount, TMSC-x's
Degree of substitution is gradually reduced, and TMSC-5 is not dissolved in HMDO.
Embodiment 3
A kind of preparation method of cellulose base dispersing agent, includes the following steps:
(1) preparation of TMSC-x: weighing the nano-cellulose of 0.4g in closed container, then presses mole of AGU/MTMS
Than MTMS (methyltrimethoxysilane) is added into closed container respectively for 1:0.1,1:0.5 and 1:1, pass through chemical gaseous phase
The method of deposition prepares TMSC-x, and reaction temperature is 105 DEG C, reaction time 6h, and nano-cellulose will be housed after reaction
Reactor to be placed in drier cooling spare, be respectively made from 1:0.1,1:0.5 and 1:1 by the molar ratio of AGU/MTMS
TMSC-x is respectively designated as TMSC-7, TMSC-8 and TMSC-9, spare.
(2) it the measurement of degree of substitution: takes 50mg TMSC-x to carry out acetylation process, is then dissolved in deuterated chloroform (CDCl3) in
(50mg/ml), send1H-NMR detection, calculates degree of substitution DS.
(3) dissolubility is tested: being taken the TMSC-x of 0.25g to be added in HMDO solvent with the concentration of 0.5wt.%, is then existed
Frequency is ultrasonically treated 30min under conditions of being 100KHz, observes its dissolubility.
The present embodiment is prepared with MTMS by the method for chemical vapor deposition with the nano-cellulose after vacuum freezedrying
TMSC-x investigates degree of substitution deliquescent influence in HMDO on it of TMSC-x, and the results are shown in Table 3.
Table 3
The measurement and dissolubility test of degree of substitution are carried out to TMSC-x manufactured in the present embodiment.Measurement result show with
The degree of substitution of the increase of MTMS additional amount, TMSC-x is gradually increased, after degree of substitution reaches 2.68, TMSC-9 ability in HMDO
It is completely dissolved.
Embodiment 4
A kind of method that cellulose base dispersing agent is used to prepare MT-x treatment fluid, includes the following steps:
(1) TMSC-x of 0.5wt.% (quality based on HMDO) preparation of MT-x treatment fluid: is added (in embodiment 1
TMSC-3, the TMSC-6 in embodiment 2 and the TMSC-9 in embodiment 3) in HMDO solvent, ultrasonic dissolution；Then it is added
MgO nano particle is configured to 3 parts of compositional liquor that mass concentration is 4g/L, ultrasonic disperse, supersonic frequency 100KHz, ultrasonic time
For 30min, the MT-x treatment fluid is obtained, the TMSC-3 in embodiment 1, TMSC-6 and reality in embodiment 2 will be utilized respectively
MT-x treatment fluid made from the TMSC-9 in example 3 is applied, MT-1, MT-2 and MT-3 are named as；
(2) measurement of dispersion effect: by step (1) prepare MT-x treatment fluid stand respectively 0h, 0.5h, 1h, 2h, 3h,
With UV- visible spectrophotometer in wavelength X it is to measure its transmitance (T) between 200-900 after 6h and 12h, passes through analysis λ
The variation of T value characterizes treatment fluid dispersion stability at=810nm；
(3) it handles the measurement of fluid viscosity: the MT-x treatment fluid prepared is measured into its viscosity with Digital Viscometer respectively.
The present embodiment investigate MT-x treatment fluid in TMSC-x to MgO nano particle dispersion effect and the shadow of viscosity in HMDO
It rings, as a result as shown in Fig. 1 and table 4.
Table 4
The measurement of dispersion effect and viscosity is carried out to MT-x treatment fluid manufactured in the present embodiment.Measurement result shows (4 He of table
Fig. 1), it will be seen from figure 1 that after MT-x treatment fluid just prepares, all have compared with low transmission, show that it has preferable dispersion
The transmitance of stability, but as time of repose increases, the treatment fluid of different TMSC-x preparations all becomes larger, but TMSC-3 and
Transmitance variation is smaller after MT-1 the and MT-2 treatment fluid that TMSC-6 is prepared respectively stands 12h, illustrates TMSC-3 and TMSC-6 couples
Treatment fluid dispersion effect is preferable；From table 4, it can be seen that at the beginning of MT-2 the and MT-3 treatment fluid that TMSC-6 and TMSC-9 are prepared respectively
Beginning viscosity all very littles illustrate that it is easy to atomization process, and the MT-1 treatment fluid initial viscosity of TMSC-3 preparation is larger, peak viscosity
For 152mPas, illustrate that it is not easy to atomization process, is suitble to spray treatment.TMSC-x effect made from other embodiments with it is upper
The TMSC-x (TMSC-3 in embodiment 1, the TMSC-6 in embodiment 2 and the TMSC-9 in embodiment 3) for stating citing is similar, can
Referring to Fig.1 with table 4.
Embodiment 5
A kind of method that MT-x treatment fluid is used for the repair process of aging paper, includes the following steps:
(1) aging paper first pattern pre-dried: is placed in thermostatic constant wet chamber's equilibrium water conten, the temperature of constant temperature and humidity processing
It is 23 ± 1 DEG C, the humidity of constant temperature and humidity processing is 50 ± 2%, and the time of constant temperature and humidity processing is for 24 hours；It then takes out and is put into very
In empty drying equipment, 50 DEG C of dry 12h, so that the moisture content of paper is lower than 2.0wt.%；
(2) preparation of MT-x treatment fluid: by TMSC-6 in embodiment 2 respectively with 0.1wt.%, 0.5wt.%,
The concentration of 1.0wt.%, 2.0wt.% (quality based on HMDO) are added in HMDO solvent, ultrasonic dissolution；Then MgO is added
It is 4 parts of compositional liquor of 4g/L that nano particle, which is configured to mass concentration, ultrasonic disperse, supersonic frequency 100KHz, and ultrasonic time is
30min obtains the MT-x treatment fluid, and will be utilized respectively concentration is 0.1wt.%, 0.5wt.%, 1.0wt.%, 2.0wt.%
TMSC-6 made from MT-x treatment fluid, be named as MT-4, MT-5, MT-6 and MT-7；
(3) the MT-x treatment fluid prepared in embodiment 2 is passed through into spraying equipment to the aging pattern in step (1) respectively
Spray treatment is carried out, the equal spray treatment of every batch of pattern 4 times, by dry weight, total quantity for spray of the MT-x treatment fluid are aging paper
The 1.0% of sample quality；
(4) paper is dried: step (3) processed pattern first being hung on and air-dries 60min in draught cupboard, then will
It is placed in vacuum dryer, 50 DEG C of dry 12h, and taking-up is placed on thermostatic constant wet chamber's equilibrium water conten, constant temperature and humidity processing
Temperature is 23 ± 1 DEG C, and the humidity of constant temperature and humidity processing is 50 ± 2%, and the time of constant temperature and humidity processing is for 24 hours, then to carry out paper
Sample performance test.The pH value of pattern be according to ISO 6588-1:2012 standard test, the measurement of pattern alkali reserved according to
ISO 10716:1994 standard test, the measurement of pattern whiteness and color difference is using L&w whiteness instrument referring to ISO 11467:
2000 standard test.
The present embodiment inquires into different MT-x treatment fluids to pattern performance (pH value, residual alkali amount, whiteness (R457 D65), color difference
△ E) influence, the results are shown in Table 5, and the influence to pattern tensile index and folding strength is as shown in Figures 2 and 3.
Table 5
By 5 result of table as it can be seen that difference MT-x treatment fluid to aging pattern processe after, the pH value of paper becomes alkali from acidity
Property, pH value maintain between 8.5-9.5, and alkali reserved maintains 200 ± 20mmol/Kg, illustrates MT-x treatment fluid to aging paper
Sample has preferable depickling to deposit alkali effect, can prevent pattern and further be acidified；Whiteness before and after pattern processe is not much different, and ties up
It holds 30 ± 2 or so, maximum aberration 2.41 after this illustrates MT treatment fluid to pattern processe, does not show it that pattern generates
It significantly affects.From figures 2 and 3, it will be seen that the tensile index and folding strength of aging pattern are first to increase to reduce afterwards, work as processing
When liquid is MT-6, tensile index and folding strength the promotion amplitude of pattern are maximum, and respectively 26.09% and 75%, this explanation
It is best that the TMSC-6 of 1.0wt.% promotes effect to the strength character of pattern.TMSC-x effect made from other embodiments and implementation
The TMSC-6 of example 2 is similar, can refer to shown in Fig. 2, Fig. 3 and table 5.
The paper of the present invention after processing carries out the detection of hydrophobic and anti-aging property:
Processed pattern carries out contact angle and antiageing effect test in Example 5.The test method of contact angle is
The scraps of paper of treated pattern is cut into 2cm × 2cm are pasted on glass slide, the objective table for being placed on static contact angle instrument is enterprising
Row contact angle test.By ultrapure water droplet that a drop volume is 5 μ L on the scraps of paper, then, suitable baseline is selected to carry out contact angle
Measurement and record, test results are shown in figure 4.The method of burn-in test is hydrothermal aging method, and aging condition is T=80 DEG C,
Humidity RH=65%, ageing time 72h, reference standard GB/T22894-2008.Test result is as shown in table 6.
Table 6
Note: the promotion amplitude of tensile strength and folding strength is calculated based on untreated pattern.
From fig. 4, it can be seen that untreated pattern is 60.4 ° to the surface contact angle of water, when MT-x is to pattern processe
Afterwards, pattern shows preferable hydrophobic performance, and surface contact angle is generally greater than 120 °, wherein when treatment fluid is MT-7,
Surface contact angle is up to 134.7 °, illustrates the increase with TMSC-6 additional amount, and treated that pattern has more for treatment fluid
Good hydrophobic performance.By 6 result of table as it can be seen that when will treated pattern carry out damp and hot accelerated ageing after, find pattern whiteness,
Color difference, tensile index, folding strength and pH value are substantially reduced.Compared to untreated pattern, treated for MT-x treatment fluid
The tensile index of pattern and folding strength are to reduce amplitude after the processing of the hydrothermal aging of 72h less than normal, wherein at MT-5 and MT-6
Folding strength after the pattern aging of reason still keeps the amplitude of having a distinct increment；The pH of pattern is still in alkalinity before and after aging, maintains 8.0
More than, MT-x treatment fluid to after aging pattern processe have preferable anti-aging property.The effect of TMSC-x made from other embodiments
Fruit is similar to the TMSC-6 of embodiment 2, can refer to shown in Fig. 4 and table 6.
Above embodiments are only preferrred embodiment of the present invention, for explaining only the invention, are not intended to limit the present invention, this
Field technical staff should belong to guarantor of the invention without departing from change made under spirit of the invention, replacement, modification etc.
Protect range.
Claims (10)
1. a kind of preparation method of cellulose base dispersing agent, which comprises the steps of: by cellulose and silanization
Reagent is reacted in DMAc/LiCl system or is reacted under conditions of chemical vapor deposition, the glucosyl group of the cellulose with
The molar ratio of silylating reagent is 1:0.1-1:10, obtains the cellulose base dispersing agent.
2. preparation method according to claim 1, which is characterized in that the cellulose is alpha-cellulose, microcrystalline cellulose
And one of nano-cellulose；The silylating reagent is methyltrimethoxysilane, trim,ethylchlorosilane, octadecyl three
One or more of chlorosilane, hexamethyldisilazane and silane coupling agent.
3. preparation method according to claim 1, which is characterized in that reaction is to stir in the DMAc/LiCl system
It is carried out under state, the temperature reacted in the DMAc/LiCl system is 60-100 DEG C, and the revolving speed of stirring is 200-800r/
The time reacted in min, DMAc/LiCl system is 0.5-1.5h, needs to be dried place after reacting in DMAc/LiCl system
Reason；The temperature of the chemical vapor deposition is 90-120 DEG C, and the time of chemical vapor deposition is 3-9h.
4. a kind of cellulose base dispersing agent as made from claim 1-3 described in any item preparation methods.
5. a kind of method that cellulose base dispersing agent is used to prepare MT-x treatment fluid described in claim 4, which is characterized in that including
Following steps: taking metal oxide nanoparticles to be added in HMDO, is uniformly mixed, and the cellulose base dispersion is then added
Agent, ultrasonic disperse processing, obtains the MT-x treatment fluid.
6. the method that cellulose base dispersing agent according to claim 5 is used to prepare MT-x treatment fluid, which is characterized in that institute
Stating metal oxide nanoparticles is MgO, CaO, TiO2And one or more of ZnO；The metal oxide nanoparticles with
The mass volume ratio of HMDO is 1-4g/L；In the MT-x treatment fluid, the concentration of TMSC-x is 0-2.0wt.%；The ultrasound
The supersonic frequency of decentralized processing is 50-150KHz, and the time of ultrasonic disperse processing is 30-60min.
7. a kind of MT-x treatment fluid as made from claim 5-6 described in any item preparation methods.
8. the method that MT-x treatment fluid described in a kind of claim 7 is used for the repair process of aging paper, which is characterized in that including as follows
Step:
(1) pre-dried of aging paper: by aging paper after constant temperature and humidity is handled, vacuum drying treatment obtains dry place
Aging paper after reason；
(2) the aging paper after step (1) described drying process is hung in closed box, is carried out at spraying with MT-x treatment fluid
Reason is subsequently placed in draught cupboard and carries out air-drying processing, the aging paper that obtains that treated；
(3) by treated described in step (2), aging paper is dried, and then constant temperature and humidity is handled, and is taken out, and is completed old
Change the repair process of paper.
9. the method that MT-x treatment fluid according to claim 8 is used for the repair process of aging paper, which is characterized in that step
(1) temperature of the constant temperature and humidity processing is 23 ± 1 DEG C, and the humidity of constant temperature and humidity processing is 50 ± 2%, constant temperature and humidity processing
Time is 12-24h；The vacuum drying temperature is 40-60 DEG C, and the moisture content of the aging paper after the drying process is
0.5-2wt.%。
10. the method that MT-x treatment fluid according to claim 8 is used for the repair process of aging paper, which is characterized in that step
(2) number of the spray treatment is 1-4 times, and by dry weight, total quantity for spray of the MT-x treatment fluid is aging paper quality
0.1-2.0%；Step (3) is described to be dried to be dried in vacuo, and the temperature of drying process is 40-60 DEG C；The constant temperature and humidity
The temperature of processing is 23 ± 1 DEG C, and the humidity of constant temperature and humidity processing is 50 ± 2%, and the time of constant temperature and humidity processing is 12-24h.
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| CN115874485A (en) * | 2021-09-28 | 2023-03-31 | 华南理工大学 | Organic phase deacidification enhancement repair liquid and preparation method and application thereof |
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