CN115110340A - Multifunctional protective liquid for paper - Google Patents
Multifunctional protective liquid for paper Download PDFInfo
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- CN115110340A CN115110340A CN202210455543.7A CN202210455543A CN115110340A CN 115110340 A CN115110340 A CN 115110340A CN 202210455543 A CN202210455543 A CN 202210455543A CN 115110340 A CN115110340 A CN 115110340A
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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 trimethoprim carboxymethylcellulose: 1-3 parts of modified nano SiO 2: 27-54 parts of taro starch phosphate: the paper protection solution prepared by the invention not only increases the strength and flexibility of paper, but also endows the paper with certain mildew-proof and bacteriostatic properties, fully utilizes the advantages of weather resistance and ultraviolet resistance of nano SiO2 inorganic material, better reflects the principle of cultural relic protection on the aspects of paper luster, texture and the like as new, and can effectively solve the problem that the existing paper cultural relic protection solution can not simultaneously perform paper deacidification, reinforcement, bacteriostasis, mildew prevention and ultraviolet resistance.
Description
Technical Field
The invention relates to a macromolecule, in particular to TMP-DCMC-BBR-NH for paper 2 Nano SiO 2 Corn starch phosphate multifunctional protective solution.
Background
The paper cultural relics are used as main carriers of human civilization and cultural inheritance, and a large amount of precious historical data are recorded. According to statistics, the total number of the existing ancient paper documents in China exceeds 3000 thousands, and the paper cultural relics are suffering from pathological changes such as aging, oxidation, acidification, microbial degradation and the like along with the lapse of storage time. The acid is the main reason of paper aging, the stronger the acid, the faster the hydrolysis speed of the paper, the paper aging macroscopically shows discoloration and brittleness, and microscopically shows damage of cellulose structure, and the mechanical performance is reduced. Due to the organic components and moisture absorption of paper documents or paper artworks, microorganisms are easy to breed, and can penetrate into the microstructure of paper, so that acid corrosion, enzyme degradation and irreversible reduction of mechanical properties are caused. Although the antibacterial action of the conventional antibiotics is obvious, the antibiotics have the problems of toxic and side effects of different degrees, causing superinfection, bacterial drug resistance and the like on paper materials, so that the application of the antibiotics is limited to a certain extent. Therefore, the research on the multifunctional paper protective solution which is nontoxic and environment-friendly and integrates mildew prevention, bacteria inhibition, deacidification, reinforcement and ultraviolet resistance has important practical significance.
Disclosure of Invention
In view of the above situation, the present invention is directed to overcoming the drawbacks of the prior art and providing a TMP-DCMC-BBR-NH for paper protection 2 Nano SiO 2 The multifunctional protective liquid prepared by the invention strengthens paper, endows the paper with certain mildew-proof and bacteriostatic properties, and fully utilizes nano SiO 2 The inorganic material has the advantage of ultraviolet resistance, and can effectively protect paper cultural relicsThe problem that the protective solution can not simultaneously perform deacidification, reinforcement, bacteriostasis, mildew prevention and ultraviolet resistance of paper.
The technical scheme of the invention is that the multifunctional protective solution for paper is prepared from the following components in parts by weight: berberine grafted trimethoprim carboxymethyl cellulose: 1-3 parts of modified nano SiO 2 27-54 parts of corn starch phosphate and 35-66 parts of corn starch phosphate are uniformly mixed to prepare the corn starch phosphate;
the berberine grafted trimethoprim carboxymethyl cellulose is prepared by the following steps:
mixing berberine hydrochloride (BBR) and 2, 4-dimethoxybenzylamine, magnetically stirring for 8h at 120 ℃ and 1500r/min, cooling to room temperature to obtain a first mixed solution, adding acetone into the first mixed solution, stirring, reacting completely, filtering the reaction solution, washing, and drying to obtain a compound A;
mixing the compound A, methanol and 75% concentrated hydrochloric acid, stirring at room temperature for 5-6h, vacuum 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 for 11-13h at 35 ℃ and 1500r/min to obtain a second mixed solution, adding 0.11g/mL sodium periodate solution into the second mixed solution to obtain a third mixed solution, adjusting the pH of the third mixed solution to 3.0 by using 1mol/L sulfuric acid, stirring for 4h at 35 ℃, 1500r/min and no light, pouring a product into first absolute ethyl alcohol for precipitation and washing, and freeze-drying for 12h to obtain dialdehyde carboxymethyl cellulose (DCMC);
mixing the prepared DCMC, Trimethoprim (TMP) and one third of the first deionized water to obtain a fourth mixed solution, adjusting the pH of the fourth mixed solution to 5-7 by using 1mol/L strong acid or strong base solution, magnetically stirring for 24 hours at 30-50 ℃ and 1500r/min, dialyzing the product for 48 hours, and freeze-drying for 24 hours to obtain trimethoprim carboxymethyl cellulose (TMP-DCMC);
the obtained TMP-DCMC and BBR-NH are mixed 2 Mixing the rest first deionized water to obtain fifth mixed solution, and adjusting pH of the fifth mixed solution to 1mol/L strong acid or strong base solution4-6, magnetically stirring at 30-50 ℃ for 12h under 1500r/min, dialyzing the product for 48h, and freeze-drying for 24h to obtain TMP-DCMC-BBR-NH 2 ；
The berberine hydrochloride (BBR), 2, 4-dimethoxybenzylamine, acetone, a 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 volume ratio of: 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 means solid in g and liquid in ml;
the modified nano SiO 2 Is measured 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) propyltriethoxysilane (KH-791);
wherein, tetraethyl silicate (TEOS) and second absolute ethyl alcohol are uniformly mixed to obtain liquid a; uniformly mixing distilled water and third absolute ethyl alcohol to obtain liquid b, dropwise adding the liquid b into the liquid a under magnetic stirring of 1500r/min at room temperature, after the dropwise adding is finished, obtaining sixth mixed liquid, adjusting the pH of the sixth mixed liquid to 4 by using 1mol/L hydrochloric acid, stirring for 2 hours, dropwise adding 3- (2-aminoethylamino) propyl triethoxysilane (KH-791) into the sixth mixed liquid, after the dropwise adding is finished, stirring for 2 hours at room temperature, placing in the air, aging to obtain uniform and transparent gel, and freeze-drying for 24 hours to obtain modified nano SiO 2 Powder;
mixing the corn starch phosphate with second deionized water, and gelatinizing at 60-65 ℃ for 1h to obtain liquid c; the weight volume ratio of the corn starch phosphate to the second deionized water is 0.8-1.2: 50;
adding TMP-DCMC-BBR-NH 2 Modified nano SiO 2 And the third deionized water is mixed evenly to obtain liquid d, TMP-DCMC-BBR-NH 2 Modified nano SiO 2 And the weight volume ratio of the third deionized water is 0.02-0.04: 0.6-1.0: 47.76-48.58, adding the liquid d into the liquid c under the magnetic stirring of 800r/min at room temperature, and uniformly stirring to obtain the multifunctional protective liquid, namely the modified carboxymethylCellulose/nano SiO 2 A multifunctional protective solution of starch phosphate of rhizoma Steudnerae Henryanae.
The multifunctional protective liquid provided by the invention is scientific and reasonable, has rich raw materials, is green and environment-friendly, has no pollution, is easy to produce and prepare, integrates deacidification, reinforcement, mould prevention, bacteriostasis and ultraviolet resistance into a whole, has better biocompatibility with paper, endows the paper with certain mould prevention and bacteriostasis properties while reinforcing the paper, and fully utilizes the nano SiO 2 The inorganic material has the advantage of ultraviolet resistance, does not influence the original appearance of paper, has reversibility, can remove a protective film under the condition of no damage or slight damage, conforms to the principle of 'repairing old as new and keeping the original appearance', is an innovation on paper cultural relic protective solution, and has remarkable economic and social benefits.
Drawings
FIG. 1 is a reaction mechanism diagram of berberine grafted trimethoprim carboxymethyl cellulose of the present invention.
Detailed Description
The following detailed description of the embodiments of the present invention will be given with reference to examples and specific cases.
Example 1
A multifunctional protective solution for paper protection is prepared from the following components in parts by weight: berberine grafted trimethoprim carboxymethylcellulose: 1 part of modified nano SiO 2 27 parts of corn starch phosphate and 35 parts of corn starch phosphate are uniformly mixed to prepare the corn starch phosphate;
the berberine grafted trimethoprim carboxymethyl cellulose is prepared by the following steps:
mixing berberine hydrochloride (BBR) and 2, 4-dimethoxybenzylamine, magnetically stirring for 8h at 120 ℃ and 1500r/min, cooling to room temperature to obtain a first mixed solution, adding acetone into the first mixed solution, stirring, reacting completely, filtering the reaction solution, washing, and drying to obtain a compound A;
mixing the compound A, methanol and 75% concentrated hydrochloric acid, stirring at room temperature for 5-6h, vacuum 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 for 11-13h at 35 ℃ and 1500r/min to obtain a second mixed solution, adding 0.11g/mL sodium periodate solution into the second mixed solution to obtain a third mixed solution, adjusting the pH of the third mixed solution to 3.0 by using 1mol/L sulfuric acid, stirring for 4h at 35 ℃, 1500r/min and no light, pouring a product into first absolute ethyl alcohol for precipitation and washing, and freeze-drying for 12h to obtain dialdehyde carboxymethyl cellulose (DCMC);
mixing the prepared DCMC, Trimethoprim (TMP) and one third of the first deionized water to obtain a fourth mixed solution, adjusting the pH of the fourth mixed solution to 5-7 by using 1mol/L strong acid or strong base solution, magnetically stirring for 24 hours at 30-50 ℃ and 1500r/min, dialyzing the product for 48 hours, and freeze-drying for 24 hours to obtain trimethoprim carboxymethyl cellulose (TMP-DCMC);
the obtained TMP-DCMC and BBR-NH are mixed 2 Mixing the rest first deionized water to obtain fifth mixed solution, adjusting pH of the fifth mixed solution to 4-6 with 1mol/L strong acid or strong base solution, magnetically stirring at 30-50 deg.C and 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-dimethoxybenzylamine, acetone, a 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 volume ratio of: 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 measured 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-aminoethylamino) propyltriethoxysilane (KH-791);
wherein, tetraethyl silicate (TEOS) and second absolute ethyl alcohol are uniformly mixed to obtain liquid a; uniformly mixing distilled water and third absolute ethyl alcohol to obtain liquid b, and dropwise adding the liquid b under magnetic stirring at room temperature of 1500r/minAdding the mixture into the liquid a, after the dropwise addition, obtaining a sixth mixed solution, adjusting the pH of the sixth mixed solution to 4 by using 1mol/L hydrochloric acid, stirring for 2 hours, dropwise adding 3- (2-aminoethylamino) propyltriethoxysilane (KH-791) into the sixth mixed solution, after the dropwise addition, stirring for 2 hours at room temperature, placing the mixture in the air, aging to form uniform and transparent gel, and freeze-drying for 24 hours to obtain the modified nano SiO 2 Powder;
mixing the corn starch phosphate with second deionized water, and gelatinizing at 60-65 ℃ for 1h to obtain liquid c; the weight volume ratio of the corn starch phosphate to the second deionized water is 0.8: 50;
adding TMP-DCMC-BBR-NH 2 Modified nano SiO 2 And the third deionized water is mixed evenly to obtain liquid d, TMP-DCMC-BBR-NH 2 Modified nano SiO 2 And 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 the magnetic stirring of 800r/min at room temperature, and uniformly stirring to obtain the multifunctional protective liquid, namely the modified carboxymethyl cellulose/nano SiO 2 A multifunctional protective solution of starch phosphate of rhizoma Steudnerae Henryanae.
Example 2
A multifunctional protective solution for paper protection is prepared from the following components in parts by weight: berberine grafted trimethoprim carboxymethyl cellulose: 3 parts of modified nano SiO 2 54 parts of corn starch phosphate and 66 parts of corn starch phosphate are uniformly mixed to prepare the corn starch phosphate;
the berberine grafted trimethoprim carboxymethyl cellulose is prepared by the following steps:
mixing berberine hydrochloride (BBR) and 2, 4-dimethoxybenzylamine, magnetically stirring for 8h at 120 ℃ and 1500r/min, cooling to room temperature to obtain a first mixed solution, adding acetone into the first mixed solution, stirring, reacting completely, filtering the reaction solution, washing, and drying to obtain a compound A;
mixing the compound A, methanol and 75% concentrated hydrochloric acid, stirring at room temperature for 5-6h, vacuum 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 for 11-13h at 35 ℃ and 1500r/min to obtain a second mixed solution, adding 0.11g/mL sodium periodate solution into the second mixed solution to obtain a third mixed solution, adjusting the pH of the third mixed solution to 3.0 by using 1mol/L sulfuric acid, stirring for 4h at 35 ℃, 1500r/min and under the condition of no light, pouring a product into first absolute ethyl alcohol for precipitation and washing, and freeze-drying for 12h to obtain dialdehyde carboxymethyl cellulose (DCMC);
mixing the prepared DCMC, Trimethoprim (TMP) and one third of the first deionized water to obtain a fourth mixed solution, adjusting the pH of the fourth mixed solution to 5-7 by using 1mol/L strong acid or strong base solution, magnetically stirring for 24 hours at 30-50 ℃ and 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 and BBR-NH 2 Mixing the rest first deionized water to obtain fifth mixed solution, adjusting pH of the fifth mixed solution to 4-6 with 1mol/L strong acid or strong base solution, magnetically stirring at 30-50 deg.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-dimethoxybenzylamine, acetone, a 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 volume ratio of: 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, liquids in ml;
the modified nano SiO 2 Is measured 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-aminoethylamino) propyltriethoxysilane (KH-791);
wherein, tetraethyl silicate (TEOS) and second absolute ethyl alcohol are uniformly mixed to obtain 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 at 1500r/min, and after dropwise adding, obtaining a sixth mixed solution, and adding 1mol/L saltAdjusting the pH value of the sixth mixed solution to 4 by acid, stirring for 2h, dropwise adding 3- (2-aminoethylamino) propyltriethoxysilane (KH-791) into the sixth mixed solution, stirring for 2h at room temperature after dropwise adding, aging in air to obtain uniform and transparent gel, and freeze-drying for 24h to obtain modified nano SiO 2 Powder;
mixing the corn starch phosphate with second deionized water, and gelatinizing at 60-65 ℃ for 1h to obtain liquid c; the weight volume ratio of the corn starch phosphate to the second deionized water is 1.2: 50;
adding TMP-DCMC-BBR-NH 2 Modified nano SiO 2 And the third deionized water is mixed evenly to obtain liquid d, TMP-DCMC-BBR-NH 2 Modified nano SiO 2 And 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 the magnetic stirring of 800r/min at room temperature, and uniformly stirring to obtain the multifunctional protective liquid, namely the modified carboxymethyl cellulose/nano SiO 2 A multifunctional protective solution of starch phosphate of rhizoma Steudnerae Henryanae.
Example 3
A multifunctional protective solution for paper protection is prepared from the following components in parts by weight: berberine grafted trimethoprim carboxymethyl cellulose: 2 parts of modified nano SiO 2 40 parts of corn starch phosphate and 50 parts of corn starch phosphate are uniformly mixed to prepare the corn starch phosphate;
the berberine grafted trimethoprim carboxymethyl cellulose is prepared by the following steps:
mixing berberine hydrochloride (BBR) and 2, 4-dimethoxybenzylamine, magnetically stirring for 8h at 120 ℃ and 1500r/min, cooling to room temperature to obtain a first mixed solution, adding acetone into the first mixed solution, stirring, reacting completely, filtering the reaction solution, washing, and drying to obtain a compound A;
mixing the compound A, methanol and 75% concentrated hydrochloric acid, stirring at room temperature for 5-6h, vacuum 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 for 11-13h at 35 ℃ and 1500r/min to obtain a second mixed solution, adding 0.11g/mL sodium periodate solution into the second mixed solution to obtain a third mixed solution, adjusting the pH of the third mixed solution to 3.0 by using 1mol/L sulfuric acid, stirring for 4h at 35 ℃, 1500r/min and under the condition of no light, pouring a product into first absolute ethyl alcohol for precipitation and washing, and freeze-drying for 12h to obtain dialdehyde carboxymethyl cellulose (DCMC);
mixing the prepared DCMC, Trimethoprim (TMP) and one third of the first deionized water to obtain a fourth mixed solution, adjusting the pH of the fourth mixed solution to 5-7 by using 1mol/L strong acid or strong base solution, magnetically stirring for 24 hours at 30-50 ℃ and 1500r/min, dialyzing the product for 48 hours, and freeze-drying for 24 hours to obtain trimethoprim carboxymethyl cellulose (TMP-DCMC);
the obtained TMP-DCMC and BBR-NH are mixed 2 Mixing the rest first deionized water to obtain fifth mixed solution, adjusting pH of the fifth mixed solution to 4-6 with 1mol/L strong acid or strong base solution, magnetically stirring at 30-50 deg.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-dimethoxybenzylamine, acetone, a 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 volume ratio of: 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, liquids in ml;
the modified nano SiO 2 Is measured 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-aminoethylamino) propyltriethoxysilane (KH-791);
wherein, tetraethyl silicate (TEOS) and second absolute ethyl alcohol are uniformly mixed to obtain 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 at 1500r/min, obtaining a sixth mixed solution after dropwise adding, adjusting the pH of the sixth mixed solution to 4 by using 1mol/L hydrochloric acid, stirring for 2h, and adding the sixth mixed solutionDropwise adding 3- (2-aminoethylamino) propyl triethoxysilane (KH-791) into the mixture, stirring at room temperature for 2 hr, aging in air to obtain uniform and transparent gel, and freeze drying for 24 hr to obtain modified nanometer SiO 2 Powder;
mixing the corn starch phosphate with second deionized water, and gelatinizing at 60-65 ℃ for 1h to obtain liquid c; the weight volume ratio of the corn starch phosphate to the second deionized water is 1.0: 50;
adding TMP-DCMC-BBR-NH 2 Modified nano SiO 2 And the third deionized water is mixed evenly to obtain liquid d, TMP-DCMC-BBR-NH 2 Modified nano SiO 2 And 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 uniformly to obtain the multifunctional protective liquid, namely the modified carboxymethyl cellulose/nano SiO 2 A multifunctional protecting liquid containing starch phosphate of rhizoma Steudnerae Henryanae is provided.
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 the TMP is 98%;
the strong acid or strong base solution is 1mol/L hydrochloric acid or 1mol/L sodium hydroxide solution;
sodium carboxymethylcellulose with a viscosity of 300-800 mPa.s;
berberine hydrochloride with a purity of 98%;
2, 4-dimethoxybenzylamine with a purity of 98% as a colorless liquid;
tetraethyl silicate with the purity of 99.7 percent is colorless transparent liquid;
3- (2-aminoethylamino) propyltriethoxysilane with a purity of 96%, 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 multifunctional protective liquid of corn starch phosphate not only can enhance the mechanical strength and the aging resistance of paper, but also fully has the characteristics of various raw materials,the berberine is a traditional Chinese medicine monomer in China, is used as a natural antibiotic, is difficult to generate drug resistance by bacteria, has rich natural reserves and simple extraction process, and does not generate secondary pollution after being used; TMP is an efficient and broad-spectrum antibacterial drug, is an antimicrobial class A variety in the 'national basic medical insurance drug catalogue', has a synergistic effect when being compatible with berberine, and has an obviously enhanced antibacterial effect of berberine. The carboxymethyl cellulose has the characteristics of salt resistance, reproducibility, 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 the paper pulp to enhance 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, has certain alkalinity, so that the multifunctional protective solution can deacidify and delay paper aging while reinforcing paper; the corn starch phosphate is an anionic starch derivative, has transparent paste liquid, good dispersibility and ageing resistance, and has obvious effect of improving the strength of paper.
When the protective solution provided by the invention is used specifically, modern calligraphy rice paper is used as a simulation paper sample, and the paper is cut into 297mm multiplied by 210mm according to the standard. Soaking the cut paper pattern in the prepared multifunctional protective solution for 5-10 minutes, taking out the paper pattern, and naturally drying at room temperature; cut paper samples soaked in deionized water were used as blank controls in the same manner. In order to verify the using effect of the invention, the products of the invention are respectively treated on the rice paper by the method, the tensile strength, the folding strength, the tearing strength, the glossiness and the whiteness of the rice paper before and after treatment are tested, meanwhile, the products of the invention are subjected to bacteriostatic and mildewproof measurement on the rice paper by the method, and the results are shown in table 1. Wherein, the tensile strength test of the paper is determined according to national standard GB/T12914-2008 of China; the folding endurance of the paper is measured according to the national standard GB/T457-2008 of China; the tearing degree of the paper is measured according to the national standard GB/455-2002 in China; the glossiness of the paper is measured according to the national standard GB/T8941-2013; the whiteness of the paper is measured according to the national standard GB/T7974-2002
The comparison of the performance index results of the paper treated by the multifunctional protective solution prepared in the embodiments 1, 2 and 3 of the invention is shown in the table 1:
table 1:
the invention has scientific and reasonable formula, rich raw materials, environmental protection and easy production and preparation. The prepared multifunctional protective solution also endows the paper with certain mildew-proof and bacteriostatic properties while reinforcing the paper; and combined with nano KH-791-SiO 2 The inorganic material has good dispersibility and ultraviolet absorption advantages, and the amino group of KH-791 can accept proton and has certain alkalinity, so that the multifunctional protective solution has certain deacidification and ultraviolet resistance effects; meanwhile, the corn starch phosphate serving as an anionic starch derivative has the advantages of transparent paste, good dispersibility, ageing resistance and obvious effect of 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 unobvious change of whiteness and glossiness of the paper, can remove a protective film under the condition of no damage or slight damage, accords with the principle of 'repairing old as old and keeping original appearance', is an innovation on paper cultural relic protective liquid, and has remarkable economic and social benefits.
Claims (11)
1. A multifunctional protective solution for paper is prepared from the following components in parts by weight: berberine grafted trimethoprim carboxymethyl cellulose: 1-3 parts of modified nano SiO 2 27-54 parts of corn starch phosphate and 35-66 parts of corn starch phosphate are uniformly mixed to prepare the corn starch phosphate;
the berberine grafted trimethoprim carboxymethyl cellulose is prepared by the following steps:
mixing berberine hydrochloride (BBR) and 2, 4-dimethoxybenzylamine, magnetically stirring for 8h at 120 ℃ and 1500r/min, cooling to room temperature to obtain a first mixed solution, adding acetone into the first mixed solution, stirring, reacting completely, filtering the reaction solution, washing, and drying to obtain a compound A;
mixing the compound A, methanol and 75% concentrated hydrochloric acid, stirring at room temperature for 5-6h, vacuum 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 for 11-13h at 35 ℃ and 1500r/min to obtain a second mixed solution, adding 0.11g/mL sodium periodate solution into the second mixed solution to obtain a third mixed solution, adjusting the pH of the third mixed solution to 3.0 by using 1mol/L sulfuric acid, stirring for 4h at 35 ℃, 1500r/min and under the condition of no light, pouring a product into first absolute ethyl alcohol for precipitation and washing, and freeze-drying for 12h to obtain dialdehyde carboxymethyl cellulose (DCMC);
mixing the prepared DCMC, Trimethoprim (TMP) and one third of the first deionized water to obtain a fourth mixed solution, adjusting the pH of the fourth mixed solution to 5-7 by using 1mol/L strong acid or strong base solution, magnetically stirring for 24 hours at 30-50 ℃ and 1500r/min, dialyzing the product for 48 hours, and freeze-drying for 24 hours to obtain trimethoprim carboxymethyl cellulose (TMP-DCMC);
the obtained TMP-DCMC and BBR-NH are mixed 2 Mixing the rest first deionized water to obtain fifth mixed solution, adjusting pH of the fifth mixed solution to 4-6 with 1mol/L strong acid or strong base solution, magnetically stirring at 30-50 deg.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-dimethoxybenzylamine, acetone, a 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 volume ratio of: 7.4: 15: 40-50: 3: 40-50: 3: 1: 60: 10: 40-60: 0.2: 0.19-0.38: 0.16-0.28, wherein the weight volume ratio refers to solid in g and liquid in ml;
the modified nano SiO 2 Is measured 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) propyltriethoxysilane (KH-791);
wherein, tetraethyl silicate (TEOS) and second absolute ethyl alcohol are uniformly mixed to obtain liquid a; uniformly mixing distilled water and third absolute ethyl alcohol to obtain a liquid b, dropwise adding the liquid b into the liquid a at room temperature under magnetic stirring of 1500r/min, after the dropwise adding is finished, obtaining a sixth mixed solution, adjusting the pH of the sixth mixed solution to 4 by using 1mol/L hydrochloric acid, stirring for 2 hours, dropwise adding 3- (2-aminoethylamino) propyl triethoxysilane (KH-791) into the sixth mixed solution, after the dropwise adding is finished, stirring for 2 hours at room temperature, placing the mixture in air, aging to obtain uniform and transparent gel, and freeze-drying for 24 hours to obtain the modified nano SiO 2 Powder;
mixing the corn starch phosphate with second deionized water, and gelatinizing at 60-65 ℃ for 1h to obtain liquid c; the weight volume ratio of the corn starch phosphate to the second deionized water is 0.8-1.2: 50;
adding TMP-DCMC-BBR-NH 2 Modified nano SiO 2 And the third deionized water is mixed evenly to obtain liquid d, TMP-DCMC-BBR-NH 2 Modified nano SiO 2 And the weight volume ratio of the third deionized water is 0.02-0.04: 0.6-1.0: 47.76-48.58, adding the liquid d into the liquid c under the magnetic stirring of 800r/min at room temperature, and uniformly stirring to obtain the multifunctional protective liquid, namely the modified carboxymethyl cellulose/nano SiO 2 A multifunctional protective solution of starch phosphate of rhizoma Steudnerae Henryanae.
2. The multifunctional protective solution for paper according to claim 1, characterized in that: the composition is prepared from the following components in parts by weight: berberine grafted trimethoprim carboxymethylcellulose: 1 part of modified nano SiO 2 : 27 parts, phosphate starch: and 35 parts of the components are uniformly mixed to prepare the feed.
3. The multifunctional protective solution for paper according to claim 1, characterized in that: the composition is characterized by comprising the following components in parts by weight: berberine grafted trimethoprim carboxymethyl fiberElement: 3 parts of modified nano SiO 2 : 54 parts, phosphate starch: and 66 parts of the components are uniformly mixed to prepare the feed.
4. The multifunctional protective solution for paper according to claim 1, characterized in that: the composition is prepared from the following components in parts by weight: berberine grafted trimethoprim carboxymethyl cellulose: 2 parts of modified nano SiO 2 : 40 parts, phosphate starch: 50 parts of the components are uniformly mixed to prepare the feed.
5. The multifunctional protective solution for paper according to claim 1, characterized in that: the concentrated hydrochloric acid is commercially available hydrochloric acid, and the mass concentration of the concentrated hydrochloric acid is 36-38%.
6. The multifunctional protective solution 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 solution for paper according to claim 1, characterized in that: the purity of the berberine hydrochloride is 98%.
8. The multifunctional protective solution for paper according to claim 1, characterized in that: the purity of the 2, 4-dimethoxybenzylamine is 98%, and the 2, 4-dimethoxybenzylamine is colorless liquid.
9. The multifunctional protective solution for paper according to claim 1, characterized in that: the purity of the absolute ethyl alcohol is 99.7%.
10. The multifunctional protective solution for paper according to claim 1, characterized in that: the purity of the tetraethyl silicate is 99.7%, and the tetraethyl silicate is colorless transparent liquid.
11. The multifunctional protective solution for paper according to claim 1, characterized in that: the purity of the 3- (2-aminoethylamino) propyltriethoxysilane is 96%, and the product is pale yellow transparent liquid.
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