CN109577091B - Paper cultural relic reinforcing liquid - Google Patents
Paper cultural relic reinforcing liquid Download PDFInfo
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- CN109577091B CN109577091B CN201811498286.5A CN201811498286A CN109577091B CN 109577091 B CN109577091 B CN 109577091B CN 201811498286 A CN201811498286 A CN 201811498286A CN 109577091 B CN109577091 B CN 109577091B
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- based polyurethane
- ethyl acetate
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- silicon dioxide
- nano silicon
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- 239000007788 liquid Substances 0.000 title claims abstract description 32
- 230000003014 reinforcing effect Effects 0.000 title claims description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 123
- 239000004814 polyurethane Substances 0.000 claims abstract description 104
- 229920002635 polyurethane Polymers 0.000 claims abstract description 104
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000005543 nano-size silicon particle Substances 0.000 claims description 37
- 235000012239 silicon dioxide Nutrition 0.000 claims description 37
- -1 cyclohexane-epichlorohydrin Chemical compound 0.000 claims description 36
- 239000004593 Epoxy Substances 0.000 claims description 29
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 18
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 18
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 18
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 18
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 18
- 239000013638 trimer Substances 0.000 claims description 12
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005728 strengthening Methods 0.000 claims 7
- 230000004224 protection Effects 0.000 abstract description 11
- 239000000377 silicon dioxide Substances 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000002787 reinforcement Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 3
- 229920001296 polysiloxane Polymers 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000002411 adverse Effects 0.000 abstract 1
- 238000009472 formulation Methods 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 230000002441 reversible effect Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- D21H17/14—Carboxylic acids; Derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- 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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/57—Polyureas; Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及一种用于纸质文物保护的一种纸质文物加固液，可有效解决现有用于纸质文物保护的加固液无法同时增加纸张强度和柔韧性的问题，该加固液是由以下重量百分比计的：纳米二氧化硅基聚氨酯5%‑30%，端羟基环氧环己烷‑环氧氯丙烷基聚氨酯5%‑30%,有机硅基聚氨酯5%‑30%和乙酸乙酯10%‑85%混合均匀制成；本发明组方科学合理，原料丰富，易生产制备，不仅具有普通聚氨酯在纸张强度、耐老化性能等方面的优良性质，又具有较高的透明度，避免了传统树脂加固法在光泽、质感等方面带来的不利影响，具有可逆性，能在无损或微损的条件下除去保护膜，是纸质文物保护加固液上的创新，经济和社会效益巨大。The present invention relates to a kind of reinforcement liquid for paper cultural relics, which can effectively solve the problem that the existing reinforcement liquid used for the protection of paper cultural relics cannot increase the strength and flexibility of paper at the same time. The reinforcement liquid is composed of the following By weight: nano-silica-based polyurethane 5%-30%, hydroxyl-terminated epoxycyclohexane-epichlorohydrin-based polyurethane 5%-30%, silicone-based polyurethane 5%-30% and ethyl acetate 10%-85% mixed uniformly; the formulation of the invention is scientific and reasonable, rich in raw materials, easy to produce and prepare, not only has the excellent properties of ordinary polyurethane in terms of paper strength and aging resistance, but also has high transparency, avoiding the need for The adverse effects of the traditional resin reinforcement method on gloss and texture are reversible, and the protective film can be removed under the condition of no damage or slight damage.
Description
Technical Field
The invention relates to a chemical product, in particular to a paper cultural relic reinforcing liquid for protecting paper cultural relics.
Background
The paper cultural relics are precious historical data and important cultural heritage of ancient art in China, the precious paper cultural relics recording the human cultural relics are continuously damaged, the phenomenon of self-destruction of a large number of books is found in examination of libraries in American national congress and libraries in French national library, China has history of five thousand years civilization, the precious paper historical relics are as large as those in the smoky sea and as inexhaustible enumeration, but with the passing of years, the damage phenomena of yellowing, mildew, pulverization, brittle fracture, rotting, breakage, smudginess and the like are caused by the influence of various factors, so that the development of the paper cultural relic protection work and the research on the reinforcing and protecting materials and the process of the paper cultural relics are very important and urgent tasks. However, since paper is both elastic and plastic, paper having a high tensile strength tends to be more easily broken than paper having a low tensile strength when printed. This indicates that the tensile strength cannot accurately indicate the ability of the paper to resist tensile failure, and the ability of the paper to resist failure is not only expressed by strength, but also expressed by toughness, i.e. has a certain relationship between stress and strain, so that the development of a reinforcing liquid for synchronously enhancing the strength and the flexibility of the paper is a technical problem which needs to be solved.
Disclosure of Invention
In view of the above situation, in order to overcome the defects of the prior art, the invention aims to provide a paper cultural relic reinforcing liquid for paper cultural relic protection, which can effectively solve the problem that the strength and flexibility of paper cannot be simultaneously increased by the conventional reinforcing liquid for paper cultural relic protection.
The technical scheme of the invention is that a paper cultural relic reinforcing liquid for protecting the paper cultural relics is prepared from the following components in percentage by weight: 5-30% of nano silicon dioxide-based polyurethane, 5-30% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 5-30% of organosilicon-based polyurethane and 10-85% of ethyl acetate are uniformly mixed to prepare the polyurethane;
the nano silicon dioxide-based polyurethane comprises the following components in parts by weight: 40g of hexamethylene diisocyanate trimer, 0.5g of nano silicon dioxide, 0.1g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the nano silicon dioxide is placed in a vacuum drying oven and dried for 10-24h, and moisture is removed to obtain dried nano silicon dioxide; adding hexamethylene diisocyanate trimer into ethyl acetate to obtain mixed solution; adding dried nano silicon dioxide into the mixed solution, adding dibutyltin dilaurate, heating to 70 ℃, reacting, measuring the content of isocyanate group (-NCO) every other hour, stopping the reaction when the content of the isocyanate group (-NCO) is not changed any more, and removing ethyl acetate by reduced pressure distillation to obtain nano silicon dioxide-based polyurethane;
the hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane is prepared from the following components in parts by weight: 5g of hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane copolyether, 40g of hexamethylene diisocyanate tripolymer, 0.1g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane copolyether, the hexamethylene diisocyanate tripolymer and the dibutyltin dilaurate are added into the ethyl acetate, the mixture is heated to 70 ℃ for reaction, the content of isocyanate group (-NCO) is measured every other hour, and when the weight content of the isocyanate group (-NCO) is not changed any more, the reaction is terminated, so that hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane polyurethane is obtained;
the organic silicon-based polyurethane comprises the following components in parts by weight: 30g of hydroxyl-terminated polydimethylsiloxane, 40g of hexamethylene diisocyanate trimer, 0.2g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the hydroxyl-terminated polydimethylsiloxane, the hexamethylene diisocyanate trimer and the dibutyltin dilaurate are added into the ethyl acetate, the mixture is heated to 70 ℃ for reaction, the content of isocyanate group (-NCO) is measured every other hour, when the content of the isocyanate group (-NCO) is not changed any more, the reaction is terminated, and the ethyl acetate is removed through reduced pressure distillation, so that the organosilicon-based polyurethane is obtained.
The paper cultural relic protection material prepared by the invention has reversibility, can remove the protection film under the condition of no damage or slight damage, is an innovation on the protection and solidification liquid of the paper cultural relic, and has great economic and social benefits.
Detailed Description
The following detailed description of specific embodiments of the invention is provided in connection with specific use cases and examples.
Example 1: a paper cultural relic reinforcing liquid comprises the following components in percentage by weight: 10% of nano silicon dioxide-based polyurethane, 10% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 10% of organosilicon-based polyurethane and 70% of ethyl acetate are uniformly mixed to prepare the polyurethane adhesive;
the nano silicon dioxide-based polyurethane comprises the following components in parts by weight: 40g of hexamethylene diisocyanate trimer, 0.5g of nano silicon dioxide, 0.1g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the nano silicon dioxide is placed in a vacuum drying oven and dried for 10-24h, and moisture is removed to obtain dried nano silicon dioxide; adding hexamethylene diisocyanate trimer into ethyl acetate to obtain mixed solution; adding dried nano silicon dioxide into the mixed solution, adding dibutyltin dilaurate, heating to 70 ℃, reacting, measuring the content of isocyanate group (-NCO) every other hour, stopping the reaction when the content of the isocyanate group (-NCO) is not changed any more, and removing ethyl acetate by reduced pressure distillation to obtain nano silicon dioxide-based polyurethane;
the hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane is prepared from the following components in parts by weight: 5g of hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane copolyether, 40g of hexamethylene diisocyanate tripolymer, 0.1g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane copolyether, the hexamethylene diisocyanate tripolymer and the dibutyltin dilaurate are added into the ethyl acetate, the mixture is heated to 70 ℃ for reaction, the content of isocyanate group (-NCO) is measured every other hour, and when the weight content of the isocyanate group (-NCO) is not changed any more, the reaction is terminated, so that hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane polyurethane is obtained;
the organic silicon-based polyurethane comprises the following components in parts by weight: 30g of hydroxyl-terminated polydimethylsiloxane, 40g of hexamethylene diisocyanate trimer, 0.2g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the hydroxyl-terminated polydimethylsiloxane, the hexamethylene diisocyanate trimer and the dibutyltin dilaurate are added into the ethyl acetate, the mixture is heated to 70 ℃ for reaction, the content of isocyanate group (-NCO) is measured every other hour, when the content of the isocyanate group (-NCO) is not changed any more, the reaction is terminated, and the ethyl acetate is removed through reduced pressure distillation, so that the organosilicon-based polyurethane is obtained.
Example 2: a paper cultural relic reinforcing liquid comprises the following components in percentage by weight: 10% of nano silicon dioxide-based polyurethane, 15% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 15% of organosilicon-based polyurethane and 60% of ethyl acetate are uniformly mixed to prepare the polyurethane; the preparation methods of the nano-silica-based polyurethane, the hydroxyl-terminated epoxycyclohexane-epichlorohydrin-based polyurethane and the organosilicon-based polyurethane are the same as in example 1.
Example 3: a paper cultural relic reinforcing liquid comprises the following components in percentage by weight: 10% of nano silicon dioxide-based polyurethane, 20% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 20% of organosilicon-based polyurethane and 50% of ethyl acetate are uniformly mixed to prepare the polyurethane adhesive; the preparation methods of the nano-silica-based polyurethane, the hydroxyl-terminated epoxycyclohexane-epichlorohydrin-based polyurethane and the organosilicon-based polyurethane are the same as in example 1.
Example 4: a paper cultural relic reinforcing liquid comprises the following components in percentage by weight: 15% of nano silicon dioxide-based polyurethane, 10% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 15% of organosilicon-based polyurethane and 60% of ethyl acetate are uniformly mixed to prepare the polyurethane; the preparation methods of the nano-silica-based polyurethane, the hydroxyl-terminated epoxycyclohexane-epichlorohydrin-based polyurethane and the organosilicon-based polyurethane are the same as in example 1.
Example 5: a paper cultural relic reinforcing liquid comprises the following components in percentage by weight: the nano silicon dioxide-based polyurethane is prepared by uniformly mixing 15% of nano silicon dioxide-based polyurethane, 15% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 20% of organosilicon-based polyurethane and 50% of ethyl acetate; the preparation methods of the nano-silica-based polyurethane, the hydroxyl-terminated epoxycyclohexane-epichlorohydrin-based polyurethane and the organosilicon-based polyurethane are the same as in example 1.
Example 6: a paper cultural relic reinforcing liquid comprises the following components in percentage by weight: 15% of nano silicon dioxide-based polyurethane, 20% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 10% of organosilicon-based polyurethane and 55% of ethyl acetate are uniformly mixed to prepare the polyurethane adhesive; the preparation methods of the nano-silica-based polyurethane, the hydroxyl-terminated epoxycyclohexane-epichlorohydrin-based polyurethane and the organosilicon-based polyurethane are the same as in example 1.
Example 7: a paper cultural relic reinforcing liquid comprises the following components in percentage by weight: 20% of nano silicon dioxide-based polyurethane, 10% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 20% of organosilicon-based polyurethane and 50% of ethyl acetate are uniformly mixed to prepare the polyurethane adhesive; the preparation methods of the nano-silica-based polyurethane, the hydroxyl-terminated epoxycyclohexane-epichlorohydrin-based polyurethane and the organosilicon-based polyurethane are the same as in example 1.
When the paper is used specifically, the cut paper (210mm multiplied by 297mm) is soaked in the reinforcing liquid provided by the invention (or the reinforcing liquid provided by the invention is sprayed on the paper) for 2-15min, and then the paper is taken out and dried naturally.
The results of the performance indexes of the paper treated by the reinforcing liquid prepared by the methods of examples 1, 2, 3, 4, 5, 6 and 7 of the invention are shown in Table 1:
table 1:
the tensile strength test of the paper in the table is determined according to national standard GB/T12914-2008; the folding endurance of the paper is determined according to national standard GB/T457-2008; the tearing degree of the paper is measured according to the national standard GB/455-2002 of 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 of China.
Aging test: the comparison of the performance indexes of the paper treated by the reinforcing liquid of the invention and the blank paper before and after aging is shown in Table 2:
table 2:
the aging experiments in the above table were determined according to national standard GB/T464-2008.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the nano silicon dioxide-based polyurethane has the effects of absorbing and shielding ultraviolet rays of 200-400 nm and simultaneously has the effects of enhancing and toughening, so that the mechanical property can be enhanced and the ultraviolet resistance of the cultural relics can be improved by over 50% by adding the nano silicon dioxide-based polyurethane into a reinforcing liquid.
2. The polyurethane prepared by synthesizing the epoxy cyclohexane-epoxy chloropropane copolyether polyurethane has small molecular weight, good permeability and colorless and transparent appearance, and can improve the mechanical property of paper and keep good glossiness by more than 40 percent when being applied to the reinforcement protection of paper cultural relics;
3. the organosilicon-based polyurethane contains Si-O bonds with high bond energy (422.2kJ/m O l) on organosilicon, and the unimolecular volume of the organosiloxane is large, and the cohesive energy density is low, so that the organosiloxane is introduced to the main chain or the side chain of the polyurethane molecule, and the tolerance performance of the product can be improved. The invention combines the advantages of polysiloxane and polyurethane to obtain the paper reinforcing material with excellent performance, and particularly, the folding resistance of the paper is obviously improved, and the folding resistance times can be improved by more than 2 times.
4. The invention has scientific and reasonable formula, rich raw materials, easy production and preparation and good use effect. The paper has the advantages of enhancing the tensile strength of the paper, keeping the flexibility of the paper, having higher transparency, avoiding the defect that the traditional reinforcing material can only enhance the single performance of the paper, prolonging the preservation life of the paper cultural relics by more than 3 times, having strong ageing resistance and improving the ornamental and research values of the paper cultural relics. The paper cultural relic protection material prepared by the invention has reversibility, can remove the protection film under the condition of no damage or slight damage, is an innovation on paper cultural relic protection, and has great economic and social benefits.
Claims (8)
1. A paper cultural relic reinforcing liquid is characterized in that: the reinforcing liquid is prepared from the following components in percentage by weight: 5-30% of nano silicon dioxide-based polyurethane, 5-30% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 5-30% of organosilicon-based polyurethane and 10-85% of ethyl acetate are uniformly mixed to prepare the polyurethane;
the nano silicon dioxide-based polyurethane comprises the following components in parts by weight: 40g of hexamethylene diisocyanate trimer, 0.5g of nano silicon dioxide, 0.1g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the nano silicon dioxide is placed in a vacuum drying oven and dried for 10-24h, and moisture is removed to obtain dried nano silicon dioxide; adding hexamethylene diisocyanate trimer into ethyl acetate to obtain mixed solution; adding dried nano silicon dioxide into the mixed solution, adding dibutyltin dilaurate, heating to 70 ℃, reacting, measuring the content of isocyanate group (-NCO) every other hour, stopping the reaction when the content of the isocyanate group (-NCO) is not changed any more, and removing ethyl acetate by reduced pressure distillation to obtain nano silicon dioxide-based polyurethane;
the hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane is prepared from the following components in parts by weight: 5g of hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane copolyether, 40g of hexamethylene diisocyanate tripolymer, 0.1g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane copolyether, the hexamethylene diisocyanate tripolymer and the dibutyltin dilaurate are added into the ethyl acetate, the mixture is heated to 70 ℃ for reaction, the content of isocyanate group (-NCO) is measured every other hour, and when the weight content of the isocyanate group (-NCO) is not changed any more, the reaction is terminated, so that hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane polyurethane is obtained;
the organic silicon-based polyurethane comprises the following components in parts by weight: 30g of hydroxyl-terminated polydimethylsiloxane, 40g of hexamethylene diisocyanate trimer, 0.2g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the hydroxyl-terminated polydimethylsiloxane, the hexamethylene diisocyanate trimer and the dibutyltin dilaurate are added into the ethyl acetate, the mixture is heated to 70 ℃ for reaction, the content of isocyanate group (-NCO) is measured every other hour, when the content of the isocyanate group (-NCO) is not changed any more, the reaction is terminated, and the ethyl acetate is removed through reduced pressure distillation, so that the organosilicon-based polyurethane is obtained.
2. The paper cultural relic-strengthening liquid as claimed in claim 1, which is characterized in that: the weight percentages are as follows: 10% of nano silicon dioxide-based polyurethane, 10% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 10% of organosilicon-based polyurethane and 70% of ethyl acetate.
3. The paper cultural relic-strengthening liquid as claimed in claim 1, which is characterized in that: comprises the following components in percentage by weight: 10% of nano silicon dioxide-based polyurethane, 15% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 15% of organosilicon-based polyurethane and 60% of ethyl acetate.
4. The paper cultural relic-strengthening liquid as claimed in claim 1, which is characterized in that: the weight percentages are as follows: 10% of nano silicon dioxide-based polyurethane, 20% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 20% of organosilicon-based polyurethane and 50% of ethyl acetate.
5. The paper cultural relic-strengthening liquid as claimed in claim 1, which is characterized in that: the weight percentages are as follows: 15% of nano silicon dioxide-based polyurethane, 10% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 15% of organosilicon-based polyurethane and 60% of ethyl acetate.
6. The paper cultural relic-strengthening liquid as claimed in claim 1, which is characterized in that: the weight percentages are as follows: 15% of nano silicon dioxide-based polyurethane, 15% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 20% of organosilicon-based polyurethane and 50% of ethyl acetate.
7. The paper cultural relic-strengthening liquid as claimed in claim 1, which is characterized in that: the weight percentages are as follows: 15% of nano silicon dioxide-based polyurethane, 20% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 10% of organosilicon-based polyurethane and 55% of ethyl acetate.
8. The paper cultural relic-strengthening liquid as claimed in claim 1, which is characterized in that: the weight percentages are as follows: 20% of nano silicon dioxide-based polyurethane, 10% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 20% of organosilicon-based polyurethane and 50% of ethyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811498286.5A CN109577091B (en) | 2018-12-08 | 2018-12-08 | Paper cultural relic reinforcing liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811498286.5A CN109577091B (en) | 2018-12-08 | 2018-12-08 | Paper cultural relic reinforcing liquid |
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| CN109577091A CN109577091A (en) | 2019-04-05 |
| CN109577091B true CN109577091B (en) | 2021-04-06 |
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| CN201811498286.5A Expired - Fee Related CN109577091B (en) | 2018-12-08 | 2018-12-08 | Paper cultural relic reinforcing liquid |
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|---|---|---|---|---|
| CN111424464B (en) * | 2020-03-19 | 2022-06-24 | 郑州大学 | Preparation method and application of modified chitosan/silicon composite reinforcement liquid for paper protection |
| CN111270554B (en) * | 2020-03-19 | 2021-12-07 | 郑州大学 | Amphipathic cationic chitosan-phosphate starch composite strengthening liquid for paper protection |
| CN113774708B (en) * | 2021-07-16 | 2023-09-19 | 浙江理工大学 | Preparation and application methods of paper cultural relic protection liquid |
| CN115110340B (en) * | 2022-04-24 | 2023-04-28 | 郑州大学 | A multifunctional protective solution for paper |
| CN116556107A (en) * | 2023-03-29 | 2023-08-08 | 郑州大学 | Protective liquid for protecting paper cultural relics |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19847615A1 (en) * | 1997-10-17 | 1999-04-22 | Graphische Sammlung Albertina | Laminated compress for separating material bonded to sheet, for conservation of graphic material |
| CN103224408A (en) * | 2013-04-22 | 2013-07-31 | 中国科学院上海硅酸盐研究所 | Reinforcement material for preservation of cultural relics, and preparation method and application thereof |
| CN108221482B (en) * | 2018-01-29 | 2020-07-10 | 郑州博物馆 | Reinforcing liquid for protecting paper cultural relics |
| CN108440736B (en) * | 2018-03-27 | 2020-09-25 | 郑州博物馆 | A transparent polyurethane reinforcement liquid for the protection of paper cultural relics |
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