CN115110340B - Multifunctional protective liquid for paper - Google Patents
Multifunctional protective liquid for paper Download PDFInfo
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- CN115110340B CN115110340B CN202210455543.7A CN202210455543A CN115110340B CN 115110340 B CN115110340 B CN 115110340B CN 202210455543 A CN202210455543 A CN 202210455543A CN 115110340 B CN115110340 B CN 115110340B
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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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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention relates to a macromolecule, in particular to a modified carboxymethyl cellulose protective solution for paper, which is prepared from the following components in parts by weight: berberine grafted methoxybenzyl carboxylated carboxymethyl cellulose: 1-3 parts of modified nano SiO2:27-54 parts of taro starch phosphate: 35-66 parts of the protective liquid are uniformly mixed to prepare the protective liquid, so that the strength and flexibility of paper are improved, certain mildew-proof and antibacterial properties are provided for the paper, the weather resistance and ultraviolet resistance advantages of nano SiO2 inorganic materials are fully utilized, the principle that cultural relics are protected from being repaired and old like new is better reflected in the aspects of paper luster, texture and the like, and the problem that the existing paper cultural relic protective liquid cannot be simultaneously deacidified, reinforced, antibacterial and mildew-proof and ultraviolet-resistant are integrated is effectively solved.
Description
Technical Field
The invention relates to a macromolecule, in particular to a TMP-DCMC-BBR-NH for paper 2 Nano SiO 2 Multifunctional protecting solution of corn starch phosphate.
Background
Paper cultural relics are used as main carriers of human civilization and cultural heritage, and a large amount of precious historical data is recorded. The total number of the existing ancient paper documents in the whole country is more than 3000 ten thousand, and the paper cultural relics are suffered from the pathological changes of aging, oxidization, acidification, microbial degradation and the like along with the storage time. The acid is a main reason for ageing paper, the stronger the acid is, the faster the hydrolysis speed of paper is, the ageing paper macroscopically shows color change and becomes brittle, the microcosmic shows the destruction of cellulose structure, and the mechanical property is reduced. Paper documents or paper art are susceptible to the growth of microorganisms due to their organic components and hygroscopicity, and microorganisms can penetrate into the microstructure of the paper, leading to acid corrosion, enzymatic degradation and irreversible degradation of mechanical properties. At present, although the antibacterial effect of the common antibiotics is remarkable, the antibiotics have different degrees of toxic and side effects on paper materials, cause the problems of double infection, bacterial drug resistance and the like, so that the application of the antibiotics is limited to a certain extent. Therefore, research on the multifunctional paper protective liquid which is nontoxic and environment-friendly and integrates mildew prevention, bacteriostasis, deacidification, reinforcement and ultraviolet resistance has important practical significance.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide a TMP-DCMC-BBR-NH for paper protection to overcome the drawbacks of the prior art 2 Nano SiO 2 The multifunctional protective liquid prepared by the invention can strengthen paper, simultaneously endow the paper with certain mildew-proof and antibacterial properties, and fully utilize nano SiO 2 The inorganic material has the advantage of ultraviolet resistance, and can effectively solve the problem that paper cultural relic protective liquid cannot be deacidified, reinforced, antibacterial, mildew-proof and ultraviolet-resistant at the same time.
The technical scheme of the invention is that the multifunctional protective liquid for paper comprises the following components in parts by weight: berberine grafted methoxybenzyl carboxylated carboxymethyl cellulose: 1-3 parts of modified nano SiO 2 27-54 parts of corn starch phosphate 35-66 parts of corn starch phosphate are uniformly mixed to prepare the corn starch;
the berberine grafted trimethoprim carboxymethyl cellulose is prepared by the following steps:
mixing berberine hydrochloride (BBR) with 2, 4-dimethoxy benzylamine, magnetically stirring at 120deg.C and 1500r/min for 8 hr, cooling to room temperature to obtain first mixed solution, adding acetone into the first mixed solution, stirring, reacting completely, vacuum filtering the reaction solution, washing, and drying to obtain compound A;
mixing the compound A, methanol and 75% concentrated hydrochloric acid, stirring at room temperature for 5-6h, filtering the reaction solution,washing the precipitate with 80% ethanol, and vacuum drying to obtain BBR-NH 2 ；
Dissolving sodium carboxymethylcellulose (CMC) in one third of first deionized water, magnetically stirring at 35 ℃ under 1500r/min for 11-13h to obtain a second mixed solution, adding 0.11g/mL sodium periodate solution into the second mixed solution to obtain a third mixed solution, regulating the pH of the third mixed solution to 3.0 by using 1mol/L sulfuric acid, stirring at 35 ℃ under 1500r/min under no light for 4h, pouring the product into first absolute ethyl alcohol, precipitating, washing, and freeze-drying for 12h to obtain dialdehyde carboxymethyl cellulose (DCMC);
mixing the prepared DCMC, trimethoprim (TMP) and one third of first deionized water to obtain a fourth mixed solution, regulating the pH of the fourth mixed solution to 5-7 by using 1mol/L strong acid or strong alkali solution, magnetically stirring for 24 hours at 30-50 ℃ under 1500r/min, dialyzing the product for 48 hours, and freeze-drying for 24 hours to obtain trimethoprim carboxymethyl cellulose (TMP-DCMC);
the prepared TMP-DCMC, BBR-NH 2 Mixing the rest first deionized water to obtain a fifth mixed solution, regulating pH of the fifth mixed solution to 4-6 with 1mol/L strong acid or alkali solution, magnetically stirring at 30-50deg.C under 1500r/min for 12 hr, dialyzing the product for 48 hr, and lyophilizing for 24 hr to obtain TMP-DCMC-BBR-NH 2 ；
The berberine hydrochloride (BBR), 2, 4-dimethoxy benzylamine, acetone, compound A, methanol, concentrated hydrochloric acid, sodium carboxymethyl cellulose (CMC), first deionized water, 0.11g/mL sodium periodate solution, first absolute ethyl alcohol, DCMC, trimethoprim (TMP), BBR-NH 2 The weight-to-volume ratio of (2) is as follows: 7.4:15:40-50:3:40-50:3:1:60:10:40-60:0.2:0.19-0.38:0.16-0.28 weight to volume ratio is solid in g and liquid in ml;
the modified nano SiO 2 Is calculated by the following volume ratio: 5-7ml of tetraethyl silicate (TEOS), 50-70ml of second absolute ethyl alcohol, 7-9ml of distilled water, 20-40ml of third absolute ethyl alcohol and 1-2ml of 3- (2-amino ethylamino) propyl triethoxysilane (KH-791);
wherein, tetraethyl silicate (TEOS) and second absolute ethyl alcohol are uniformly mixed to obtain liquida, a; uniformly mixing distilled water and third absolute ethyl alcohol to obtain liquid b, dropwise adding the liquid b into the liquid a at room temperature under magnetic stirring of 1500r/min to obtain a sixth mixed solution, regulating the pH value of the sixth mixed solution to 4 by using 1mol/L hydrochloric acid, stirring for 2h, dropwise adding 3- (2-amino-ethylamino) propyltriethoxysilane (KH-791) into the sixth mixed solution, stirring for 2h at room temperature after the dropwise adding, aging in air to uniform and transparent gel, and freeze-drying for 24h to obtain modified nano SiO 2 A powder;
mixing corn starch phosphate with second deionized water, and gelatinizing for 1h at 60-65 ℃ to obtain liquid c; the weight volume ratio of the corn starch phosphate to the second deionized water is 0.8-1.2:50;
TMP-DCMC-BBR-NH 2 Modified nano SiO 2 Uniformly mixing the third deionized water to obtain liquid d, TMP-DCMC-BBR-NH 2 Modified nano SiO 2 The weight-volume ratio of the third deionized water is 0.02-0.04:0.6-1.0:47.76-48.58 adding liquid d into liquid c under magnetic stirring at room temperature and 800r/min, and stirring to obtain multifunctional protecting liquid, i.e. modified carboxymethyl cellulose/nanometer SiO 2 Taro starch phosphate multifunctional protective liquid.
The multifunctional protective liquid has the advantages of being scientific and reasonable, rich in raw materials, green, environment-friendly, pollution-free, easy to produce and prepare, and integrating deacidification, reinforcement, mildew prevention and bacteriostasis and ultraviolet resistance, has better biocompatibility with paper, can reinforce the paper, simultaneously endow the paper with certain mildew prevention and bacteriostasis performance, and fully utilizes nano SiO (silicon dioxide) 2 The inorganic material has the advantages of ultraviolet resistance, does not influence the original appearance of paper, has reversibility, can remove the protective film under the condition of no damage or little damage, accords with the principle of 'repairing old as new and keeping original appearance', is innovation on paper cultural relics protective liquid, and has remarkable economic and social benefits.
Drawings
FIG. 1 is a diagram showing the reaction mechanism of berberine grafted methoxybenzyl carboxylated carboxymethyl cellulose.
Detailed Description
The following describes the embodiments of the present invention in detail with reference to examples and specific cases.
Example 1
A multifunctional protective liquid for paper protection is prepared from the following components in parts by weight: berberine grafted methoxybenzyl carboxylated carboxymethyl cellulose: 1 part of modified nano SiO 2 27 parts of corn starch phosphate 35 parts are uniformly mixed to prepare the corn starch;
the berberine grafted trimethoprim carboxymethyl cellulose is prepared by the following steps:
mixing berberine hydrochloride (BBR) with 2, 4-dimethoxy benzylamine, magnetically stirring at 120deg.C and 1500r/min for 8 hr, cooling to room temperature to obtain first mixed solution, adding acetone into the first mixed solution, stirring, reacting completely, vacuum filtering the reaction solution, washing, and drying to obtain compound A;
mixing compound A, methanol and 75% concentrated hydrochloric acid, stirring at room temperature for 5-6 hr, vacuum filtering, washing precipitate with 80% ethanol, and vacuum drying to obtain BBR-NH 2 ；
Dissolving sodium carboxymethylcellulose (CMC) in one third of first deionized water, magnetically stirring at 35 ℃ under 1500r/min for 11-13h to obtain a second mixed solution, adding 0.11g/mL sodium periodate solution into the second mixed solution to obtain a third mixed solution, regulating the pH of the third mixed solution to 3.0 by using 1mol/L sulfuric acid, stirring at 35 ℃ under 1500r/min under no light for 4h, pouring the product into first absolute ethyl alcohol, precipitating, washing, and freeze-drying for 12h to obtain dialdehyde carboxymethyl cellulose (DCMC);
mixing the prepared DCMC, trimethoprim (TMP) and one third of first deionized water to obtain a fourth mixed solution, regulating the pH of the fourth mixed solution to 5-7 by using 1mol/L strong acid or strong alkali solution, magnetically stirring for 24 hours at 30-50 ℃ under 1500r/min, dialyzing the product for 48 hours, and freeze-drying for 24 hours to obtain trimethoprim carboxymethyl cellulose (TMP-DCMC);
the prepared TMP-DCMC, BBR-NH 2 Mixing the rest of the first deionized water to obtain a fifth mixed solution, regulating pH of the fifth mixed solution to 4-6 with 1mol/L strong acid or alkali solution, and adding the solution into the solution at 30Magnetically stirring at-50deg.C and 1500r/min for 12 hr, dialyzing the product for 48 hr, and freeze drying for 24 hr to obtain TMP-DCMC-BBR-NH 2 ；
The berberine hydrochloride (BBR), 2, 4-dimethoxy benzylamine, acetone, compound A, methanol, concentrated hydrochloric acid, sodium carboxymethyl cellulose (CMC), first deionized water, 0.11g/mL sodium periodate solution, first absolute ethyl alcohol, DCMC, trimethoprim (TMP), BBR-NH 2 The weight-to-volume ratio of (2) is as follows: 7.4:15:40:3:40:3:1:60:10:40:0.2:0.19:0.16, weight to volume ratio means solids in g and liquids in ml;
the modified nano SiO 2 Is calculated by the following volume ratio: 5ml of tetraethyl silicate (TEOS), 50ml of second absolute ethyl alcohol, 7ml of distilled water, 20ml of third absolute ethyl alcohol and 1ml of 3- (2-amino ethylamino) propyl triethoxysilane (KH-791);
wherein, tetraethyl silicate (TEOS) and second absolute ethyl alcohol are uniformly mixed to obtain a liquid a; uniformly mixing distilled water and third absolute ethyl alcohol to obtain liquid b, dropwise adding the liquid b into the liquid a at room temperature under magnetic stirring of 1500r/min to obtain a sixth mixed solution, regulating the pH value of the sixth mixed solution to 4 by using 1mol/L hydrochloric acid, stirring for 2h, dropwise adding 3- (2-amino-ethylamino) propyltriethoxysilane (KH-791) into the sixth mixed solution, stirring for 2h at room temperature after the dropwise adding, aging in air to uniform and transparent gel, and freeze-drying for 24h to obtain modified nano SiO 2 A powder;
mixing corn starch phosphate with second deionized water, and gelatinizing for 1h at 60-65 ℃ to obtain liquid c; the weight volume ratio of the corn starch phosphate to the second deionized water is 0.8:50;
TMP-DCMC-BBR-NH 2 Modified nano SiO 2 Uniformly mixing the third deionized water to obtain liquid d, TMP-DCMC-BBR-NH 2 Modified nano SiO 2 The weight-volume ratio of the third deionized water is 0.02:0.6:47.76 adding the liquid d into the liquid c under magnetic stirring at room temperature and 800r/min, and stirring to obtain multifunctional protecting liquid, i.e. modified carboxymethyl cellulose/nano SiO 2 Multifunctional protection of taro starch phosphateAnd (3) liquid.
Example 2
A multifunctional protective liquid for paper protection is prepared from the following components in parts by weight: berberine grafted methoxybenzyl carboxylated carboxymethyl cellulose: 3 parts of modified nano SiO 2 54 parts of corn starch phosphate 66 parts are uniformly mixed to prepare the corn starch;
the berberine grafted trimethoprim carboxymethyl cellulose is prepared by the following steps:
mixing berberine hydrochloride (BBR) with 2, 4-dimethoxy benzylamine, magnetically stirring at 120deg.C and 1500r/min for 8 hr, cooling to room temperature to obtain first mixed solution, adding acetone into the first mixed solution, stirring, reacting completely, vacuum filtering the reaction solution, washing, and drying to obtain compound A;
mixing compound A, methanol and 75% concentrated hydrochloric acid, stirring at room temperature for 5-6 hr, vacuum filtering, washing precipitate with 80% ethanol, and vacuum drying to obtain BBR-NH 2 ；
Dissolving sodium carboxymethylcellulose (CMC) in one third of first deionized water, magnetically stirring at 35 ℃ under 1500r/min for 11-13h to obtain a second mixed solution, adding 0.11g/mL sodium periodate solution into the second mixed solution to obtain a third mixed solution, regulating the pH of the third mixed solution to 3.0 by using 1mol/L sulfuric acid, stirring at 35 ℃ under 1500r/min under no light for 4h, pouring the product into first absolute ethyl alcohol, precipitating, washing, and freeze-drying for 12h to obtain dialdehyde carboxymethyl cellulose (DCMC);
mixing the prepared DCMC, trimethoprim (TMP) and one third of first deionized water to obtain a fourth mixed solution, regulating the pH of the fourth mixed solution to 5-7 by using 1mol/L strong acid or strong alkali solution, magnetically stirring for 24 hours at 30-50 ℃ under 1500r/min, dialyzing the product for 48 hours, and freeze-drying for 24 hours to obtain trimethoprim carboxymethyl cellulose (TMP-DCMC);
the prepared TMP-DCMC, BBR-NH 2 Mixing the rest of the first deionized water to obtain a fifth mixed solution, regulating pH of the fifth mixed solution to 4-6 with 1mol/L strong acid or alkali solution, magnetically stirring at 30-50deg.C under 1500r/min for 12 hr, dialyzing the product for 48 hr, and lyophilizingDrying for 24h to obtain TMP-DCMC-BBR-NH 2 ；
The berberine hydrochloride (BBR), 2, 4-dimethoxy benzylamine, acetone, compound A, methanol, concentrated hydrochloric acid, sodium carboxymethyl cellulose (CMC), first deionized water, 0.11g/mL sodium periodate solution, first absolute ethyl alcohol, DCMC, trimethoprim (TMP), BBR-NH 2 The weight-to-volume ratio of (2) is as follows: 7.4:15:50:3:50:3:1:60:10:60:0.2:0.38:0.28 weight to volume ratio means solids in g and liquids in ml;
the modified nano SiO 2 Is calculated by the following volume ratio: 7ml of tetraethyl silicate (TEOS), 70ml of second absolute ethyl alcohol, 9ml of distilled water, 40ml of third absolute ethyl alcohol and 2ml of 3- (2-amino ethylamino) propyl triethoxysilane (KH-791);
wherein, tetraethyl silicate (TEOS) and second absolute ethyl alcohol are uniformly mixed to obtain a liquid a; uniformly mixing distilled water and third absolute ethyl alcohol to obtain liquid b, dropwise adding the liquid b into the liquid a at room temperature under magnetic stirring of 1500r/min to obtain a sixth mixed solution, regulating the pH value of the sixth mixed solution to 4 by using 1mol/L hydrochloric acid, stirring for 2h, dropwise adding 3- (2-amino-ethylamino) propyltriethoxysilane (KH-791) into the sixth mixed solution, stirring for 2h at room temperature after the dropwise adding, aging in air to uniform and transparent gel, and freeze-drying for 24h to obtain modified nano SiO 2 A powder;
mixing corn starch phosphate with second deionized water, and gelatinizing for 1h at 60-65 ℃ to obtain liquid c; the weight-volume ratio of the corn starch phosphate to the second deionized water is 1.2:50;
TMP-DCMC-BBR-NH 2 Modified nano SiO 2 Uniformly mixing the third deionized water to obtain liquid d, TMP-DCMC-BBR-NH 2 Modified nano SiO 2 The weight-volume ratio of the third deionized water is 0.04:1.0:48.58 adding the liquid d into the liquid c under magnetic stirring at room temperature and 800r/min, and stirring to obtain multifunctional protecting liquid, i.e. modified carboxymethyl cellulose/nano SiO 2 Taro starch phosphate multifunctional protective liquid.
Example 3
A multifunctional protective liquid for paper protection is prepared from the following components in parts by weight: berberine grafted methoxybenzyl carboxylated carboxymethyl cellulose: 2 parts of modified nano SiO 2 40 parts of corn starch phosphate 50 parts are uniformly mixed to prepare the corn starch;
the berberine grafted trimethoprim carboxymethyl cellulose is prepared by the following steps:
mixing berberine hydrochloride (BBR) with 2, 4-dimethoxy benzylamine, magnetically stirring at 120deg.C and 1500r/min for 8 hr, cooling to room temperature to obtain first mixed solution, adding acetone into the first mixed solution, stirring, reacting completely, vacuum filtering the reaction solution, washing, and drying to obtain compound A;
mixing compound A, methanol and 75% concentrated hydrochloric acid, stirring at room temperature for 5-6 hr, vacuum filtering, washing precipitate with 80% ethanol, and vacuum drying to obtain BBR-NH 2 ；
Dissolving sodium carboxymethylcellulose (CMC) in one third of first deionized water, magnetically stirring at 35 ℃ under 1500r/min for 11-13h to obtain a second mixed solution, adding 0.11g/mL sodium periodate solution into the second mixed solution to obtain a third mixed solution, regulating the pH of the third mixed solution to 3.0 by using 1mol/L sulfuric acid, stirring at 35 ℃ under 1500r/min under no light for 4h, pouring the product into first absolute ethyl alcohol, precipitating, washing, and freeze-drying for 12h to obtain dialdehyde carboxymethyl cellulose (DCMC);
mixing the prepared DCMC, trimethoprim (TMP) and one third of first deionized water to obtain a fourth mixed solution, regulating the pH of the fourth mixed solution to 5-7 by using 1mol/L strong acid or strong alkali solution, magnetically stirring for 24 hours at 30-50 ℃ under 1500r/min, dialyzing the product for 48 hours, and freeze-drying for 24 hours to obtain trimethoprim carboxymethyl cellulose (TMP-DCMC);
the prepared TMP-DCMC, BBR-NH 2 Mixing the rest first deionized water to obtain a fifth mixed solution, regulating pH of the fifth mixed solution to 4-6 with 1mol/L strong acid or alkali solution, magnetically stirring at 30-50deg.C under 1500r/min for 12 hr, dialyzing the product for 48 hr, and lyophilizing for 24 hr to obtain TMP-DCMC-BBR-NH 2 ；
The berberine hydrochloride (BBR), 2, 4-dimethoxy benzylamine, acetone, compound A, methanol, concentrated hydrochloric acid, sodium carboxymethyl cellulose (CMC), first deionized water, 0.11g/mL sodium periodate solution, first absolute ethyl alcohol, DCMC, trimethoprim (TMP), BBR-NH 2 The weight-to-volume ratio of (2) is as follows: 7.4:15:45:3:45:3:1:60:10:45:0.2:0.29:0.22 weight to volume ratio means solids in g and liquids in ml;
the modified nano SiO 2 Is calculated by the following volume ratio: 6ml of tetraethyl silicate (TEOS), 60ml of second absolute ethyl alcohol, 8ml of distilled water, 30ml of third absolute ethyl alcohol and 1.5ml of 3- (2-amino ethylamino) propyl triethoxysilane (KH-791);
wherein, tetraethyl silicate (TEOS) and second absolute ethyl alcohol are uniformly mixed to obtain a liquid a; uniformly mixing distilled water and third absolute ethyl alcohol to obtain liquid b, dropwise adding the liquid b into the liquid a at room temperature under magnetic stirring of 1500r/min to obtain a sixth mixed solution, regulating the pH value of the sixth mixed solution to 4 by using 1mol/L hydrochloric acid, stirring for 2h, dropwise adding 3- (2-amino-ethylamino) propyltriethoxysilane (KH-791) into the sixth mixed solution, stirring for 2h at room temperature after the dropwise adding, aging in air to uniform and transparent gel, and freeze-drying for 24h to obtain modified nano SiO 2 A powder;
mixing corn starch phosphate with second deionized water, and gelatinizing for 1h at 60-65 ℃ to obtain liquid c; the weight-volume ratio of the corn starch phosphate to the second deionized water is 1.0:50;
TMP-DCMC-BBR-NH 2 Modified nano SiO 2 Uniformly mixing the third deionized water to obtain liquid d, TMP-DCMC-BBR-NH 2 Modified nano SiO 2 The weight-volume ratio of the third deionized water is 0.03:0.8:48.17 adding the liquid d into the liquid c under magnetic stirring at room temperature and 800r/min, and stirring to obtain multifunctional protecting liquid, i.e. modified carboxymethyl cellulose/nano SiO 2 Taro starch phosphate multifunctional protective liquid.
Wherein:
the concentrated hydrochloric acid is common commercial hydrochloric acid, and the mass concentration of the concentrated hydrochloric acid is 36% -38%;
TMP is trimethoprim lactate, and the purity of TMP is 98%;
the strong acid or alkali solution is 1mol/L hydrochloric acid or 1mol/L sodium hydroxide solution;
sodium carboxymethylcellulose with a viscosity of 300-800mpa.s;
berberine hydrochloride with purity of 98%;
2, 4-dimethoxybenzyl amine with a purity of 98% and a colorless liquid;
the purity of the tetraethyl silicate is 99.7 percent, and the liquid is colorless and transparent;
3- (2-amino ethylamino) propyl triethoxysilane, having a purity of 96%, a pale yellow transparent liquid;
corn starch phosphate, ds=0.054;
the TMP-DCMC-BBR-NH for paper protection provided by the invention 2 Nano SiO 2 The corn starch phosphate multifunctional protective solution not only can enhance the mechanical strength and ageing resistance of paper, but also fully has the characteristics of all raw materials, and berberine is a traditional Chinese medicine monomer in China, is used as a natural antibiotic, is difficult to generate drug resistance by bacteria, has abundant natural reserves and simple extraction process, and does not generate secondary pollution after being used; TMP is a high-efficiency broad-spectrum antibacterial agent, is an antimicrobial class A in the national basic medical insurance drug catalogue, has synergistic effect with berberine, and obviously enhances the antibacterial effect of berberine. The carboxymethyl cellulose has the characteristics of salt resistance, regeneration, biodegradability and the like, has a structure similar to that of cellulose in paper, and has good biocompatibility with the cellulose. In addition, CMC can be added into paper pulp to strengthen the mechanical strength and fiber uniformity of paper and improve the bonding effect among fibers; nano KH-791-SiO 2 The monomer has good dispersibility and ultraviolet absorption characteristics, and the amino group of KH-791 can accept protons and has certain alkalinity, so that the multifunctional protective liquid can deacidify and delay the ageing of paper while reinforcing the paper; the corn starch phosphate is an anionic starch derivative, and has the advantages of transparent paste, good dispersibility, ageing resistance and obvious effect of improving the strength of paper.
When the protective liquid provided by the invention is specifically used, modern calligraphy rice paper is used as a simulated paper sample, and the paper is cut into 297mm multiplied by 210mm according to the standard. Soaking the cut paper patterns in the prepared multifunctional protective liquid for 5-10 minutes, taking out the paper patterns, and naturally drying at room temperature; the cut pattern was soaked with deionized water in the same manner as a blank. In order to verify the use effect of the invention, the product of the embodiment of the invention is used for processing the rice paper by the method, the tensile strength, the folding endurance, the tearing strength, the glossiness and the whiteness of the rice paper before and after the processing are tested, and meanwhile, the product of the embodiment of the invention is used for carrying out antibacterial and mildew-proof measurement on the rice paper by the method, and the result is shown in table 1. Wherein, the tensile strength test of the paper is measured according to national standard GB/T12914-2008; the paper folding endurance is measured according to national standard GB/T457-2008; the paper tear degree is measured according to national standard GB/455-2002; the glossiness of the paper is measured according to national standard GB/T8941-2013; paper whiteness is measured according to national standard GB/T7974-2002 of China
The comparison of the performance index results of the paper treated by the multifunctional protective liquid prepared in the embodiments 1, 2 and 3 is shown in Table 1:
table 1:
the invention has scientific and reasonable formula, rich raw materials, environment protection and easy production and preparation. The prepared multifunctional protective liquid can strengthen paper and simultaneously endow the paper with certain mildew-proof and antibacterial properties; and combines with nano KH-791-SiO 2 The inorganic material has the advantages of good dispersibility and ultraviolet absorption, and the amino group of KH-791 can accept protons and has certain alkalinity, so that the multifunctional protective liquid has certain deacidification and ultraviolet resistance effects; at the same time, corn starch phosphate is used as an anionic starchThe powder derivative has the advantages of transparent paste, good dispersibility and anti-aging capability, and has obvious effect on improving the strength of paper. The multifunctional protective liquid prepared by the invention has better biocompatibility with paper, can effectively enhance the mechanical strength of the paper, has insignificant change of whiteness and glossiness, can remove the protective film under the condition of no damage or little damage, accords with the principle of 'old repair and original appearance maintenance', is innovation on paper cultural relics protective liquid, and has remarkable economic and social benefits.
Claims (11)
1. A multifunctional protective liquid for paper is prepared from the following components in parts by weight: berberine grafted methoxybenzyl carboxylated carboxymethyl cellulose: 1-3 parts of modified nano SiO 2 27-54 parts of corn starch phosphate 35-66 parts of corn starch phosphate are uniformly mixed to prepare the corn starch;
the berberine grafted trimethoprim carboxymethyl cellulose is prepared by the following steps:
mixing berberine hydrochloride BBR with 2, 4-dimethoxy benzylamine, magnetically stirring at 120deg.C and 1500r/min for 8-h, cooling to room temperature to obtain first mixed solution, adding acetone into the first mixed solution, stirring, reacting completely, vacuum filtering the reaction solution, washing, and drying to obtain compound A;
mixing compound A, methanol and 75% concentrated hydrochloric acid, stirring at room temperature for 5-6h, vacuum filtering, washing precipitate with 80% ethanol, and vacuum drying to obtain BBR-NH 2 ；
Dissolving sodium carboxymethylcellulose CMC in one third of first deionized water, magnetically stirring at 35 ℃ under 1500r/min for 11-13h to obtain a second mixed solution, adding 0.11g/mL sodium periodate solution into the second mixed solution to obtain a third mixed solution, regulating the pH value of the third mixed solution to 3.0 by using 1mol/L sulfuric acid, stirring at 35 ℃ under 1500r/min under no light for 4h, pouring the product into first absolute ethyl alcohol for precipitation, washing, and freeze-drying for 12h to obtain the dialdehyde carboxymethyl cellulose DCMC;
mixing the prepared DCMC, trimethoprim TMP and one third of first deionized water to obtain a fourth mixed solution, regulating the pH of the fourth mixed solution to 5-7 by using 1mol/L strong acid or strong alkali solution, magnetically stirring 24-h at 30-50 ℃ and 1500r/min, dialyzing the product to 48-h, and freeze-drying to 24-h to obtain the trimethoprim carboxymethyl cellulose TMP-DCMC;
the prepared TMP-DCMC, BBR-NH 2 Mixing the rest first deionized water to obtain a fifth mixed solution, regulating pH of the fifth mixed solution to 4-6 with 1mol/L strong acid or alkali solution, magnetically stirring at 30-50deg.C and 1500r/min for 12h, dialyzing the product for 48h, and lyophilizing for 24h to obtain TMP-DCMC-BBR-NH 2 ；
The berberine hydrochloride BBR, 2, 4-dimethoxy benzylamine, acetone, compound A, methanol, concentrated hydrochloric acid, sodium carboxymethylcellulose CMC, first deionized water, 0.11g/mL sodium periodate solution, first absolute ethyl alcohol, DCMC, trimethoprim TMP, BBR-NH 2 The weight-to-volume ratio of (2) is as follows: 7.4:15:40-50:3:40-50:3:1:60:10:40-60:0.2:0.19-0.38:0.16-0.28 weight to volume ratio is solid in g and liquid in ml;
the modified nano SiO 2 Is calculated by the following volume ratio: 5-7ml of tetraethyl silicate TEOS, 50-70ml of second absolute ethyl alcohol, 7-9ml of distilled water, 20-40ml of third absolute ethyl alcohol and 1-2ml of 3- (2-aminoethylamino) propyl triethoxysilane KH-791;
the preparation method comprises the steps of uniformly mixing tetraethyl silicate TEOS and second absolute ethyl alcohol to obtain a liquid a; uniformly mixing distilled water and third absolute ethyl alcohol to obtain liquid b, dropwise adding the liquid b into the liquid a at room temperature under magnetic stirring of 1500r/min to obtain a sixth mixed solution, regulating the pH value of the sixth mixed solution to 4 by using 1mol/L hydrochloric acid, stirring 2h, dropwise adding 3- (2-amino-ethylamino) propyl triethoxysilane KH-791 into the sixth mixed solution, stirring 2h at room temperature after the dropwise addition, aging in air to uniform and transparent gel, and freeze-drying 24h to obtain the modified nano SiO 2 A powder;
mixing corn starch phosphate with second deionized water, and gelatinizing for 1h at 60-65 ℃ to obtain liquid c; the weight volume ratio of the corn starch phosphate to the second deionized water is 0.8-1.2:50;
TMP-DCMC-BBR-NH 2 Modified nano SiO 2 Uniformly mixing the third deionized water to obtain liquid d, TMP-DCMC-BBR-NH 2 Modified nano SiO 2 The weight-volume ratio of the third deionized water is 0.02-0.04:0.6-1.0:47.76-48.58 adding liquid d into liquid c under magnetic stirring at room temperature and 800r/min, and stirring to obtain multifunctional protecting liquid, i.e. modified carboxymethyl cellulose/nanometer SiO 2 Multifunctional protecting solution of corn starch phosphate.
2. The multifunctional protective liquid for paper according to claim 1, characterized in that: the weight portions are as follows: berberine grafted methoxybenzyl carboxylated carboxymethyl cellulose: 1 part of modified nano SiO 2 :27 parts of corn starch phosphate: and (5) uniformly mixing 35 parts.
3. The multifunctional protective liquid for paper according to claim 1, characterized in that: the weight portions are as follows: berberine grafted methoxybenzyl carboxylated carboxymethyl cellulose: 3 parts of modified nano SiO 2 :54 parts of corn starch phosphate: 66 parts of the components are uniformly mixed to prepare the product.
4. The multifunctional protective liquid for paper according to claim 1, characterized in that: the weight portions are as follows: berberine grafted methoxybenzyl carboxylated carboxymethyl cellulose: 2 parts of modified nano SiO 2 :40 parts of corn starch phosphate: 50 parts of the components are uniformly mixed to prepare the product.
5. The multifunctional protective liquid for paper according to claim 1, characterized in that: the concentrated hydrochloric acid is commercial hydrochloric acid, and the mass concentration of the concentrated hydrochloric acid is 36-38%.
6. The multifunctional protective liquid for paper according to claim 1, characterized in that: the viscosity of the sodium carboxymethyl cellulose is 300-800 mPa.s.
7. The multifunctional protective liquid for paper according to claim 1, characterized in that: the purity of the berberine hydrochloride is 98%.
8. The multifunctional protective liquid for paper according to claim 1, characterized in that: the purity of the 2, 4-dimethoxy benzyl amine is 98 percent, and the 2, 4-dimethoxy benzyl amine is colorless liquid.
9. The multifunctional protective liquid for paper according to claim 1, characterized in that: the purity of the absolute ethyl alcohol is 99.7 percent.
10. The multifunctional protective liquid for paper according to claim 1, characterized in that: the purity of the tetraethyl silicate is 99.7 percent, and the tetraethyl silicate is colorless transparent liquid.
11. The multifunctional protective liquid for paper according to claim 1, characterized in that: the purity of the 3- (2-amino ethylamino) propyl triethoxysilane is 96%, and the 3- (2-amino ethylamino) propyl triethoxysilane is light yellow transparent liquid.
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