An inorganic-organic composite material protective liquid for the reinforcement and protection of earthen ruins

Abstract

The present invention relates to the field of cultural relics protection technology. The invention is formed by uniformly mixing a mixture of an organic fluorine-modified acrylic resin emulsion: an organic fluorine-silicon-modified acrylic resin emulsion: and nano-silicon dioxide in a weight ratio of 1-2:1-2:0.08-0.16. The invention integrates penetration, waterproofing, reinforcement protection, acid, alkali, and salt resistance, and aging resistance. The invention has good stability, low viscosity, and strong fluidity. The invention fully combines the high transparency and good weather resistance of acrylic resin. The fluorine-containing and silicon-containing compounds have the advantages of good water resistance, weather resistance, and stain resistance. In addition, the invention combines the advantages of good dispersibility and ultraviolet absorption of nano-SiO2 to impart certain moisture-proof and waterproof, acid, alkali, and salt resistance, weather resistance, wear resistance, and aging resistance to earthen relics. The invention has good compatibility with earthen relics base materials, effectively enhances the mechanical strength and compressive strength of earthen relics, and the original appearance, glossiness, and weight of the soil sample do not change significantly. The protective film can be removed under conditions of no or minimal damage.

Description

Technical Field

[0001] The invention relates to the technical field of cultural relics protection, and in particular to an inorganic-organic fluorosilicone modified acrylic resin composite material protection liquid for reinforcing and protecting earthen ruins. Background Art

[0002] Earthen sites refer to ancient relics left over from various activities throughout human history, including production and daily life, using earth as the primary building material. my country boasts a large number of these sites, which are widely distributed. However, due to the deterioration of their geographical and ecological environments, climate change, unscientific management, arbitrary trampling, and development, and other factors, these sites are facing various types of damage, including wind erosion, rain erosion, and biological weathering. Earthen sites are a precious part of humanity's cultural heritage, and once damaged, they are irreversible. Appropriate reinforcement and protection methods not only preserve the appearance and color of earthen sites but also effectively slow aging, cracking, pulverization, and weathering. They can also enhance their internal strength, making them tougher, more water-resistant, and weather-resistant. Chemical reinforcement has long been a key challenge in earthen site protection research and is considered the most important reinforcement measure for their long-term preservation. Currently, there are two main categories of materials for the reinforcement and protection of earthen sites: inorganic materials and organic polymers. Inorganic materials include nano-SiO2, sodium silicate, potassium silicate, and lithium silicate, while organic polymers include silicone resins, polyurethane resins, and acrylic resins. Despite extensive research on the reinforcement and protection of earthen sites in China, most current approaches utilize inorganic materials. However, inorganic materials often fail to achieve the desired penetration depth, and the soluble salts in water glass repeatedly dissolve and crystallize in humid environments, damaging cultural relics. While organic materials achieve the desired penetration depth and strength, they reduce the light transmittance of soil samples and lack resistance to high temperatures and hydrolysis. Therefore, developing a novel inorganic-organic composite material for the reinforcement and protection of earthen sites is a promising future direction. Summary of the Invention

[0003] In response to the above situation and to overcome the shortcomings of the prior art, the present invention aims to provide an inorganic-organic fluorine-silicon modified acrylic resin composite material protective solution for the reinforcement and protection of earthen sites. The protective solution produced by the present invention significantly improves the water resistance, acid, alkali and salt resistance of earthen sites, and strengthens the internal structure of earthen sites. Addressing the shortcomings of the prior art, which directly uses expensive double-bonded fluorine-containing acrylic acid as a modification monomer to synthesize fluorine-containing acrylic polymers, the present invention uses inexpensive fluoroalcohols as monomers to first synthesize double-bonded fluorine-containing compounds, and then modifies the acrylic resin, significantly reducing costs. Furthermore, the protective solution, made by mixing organic fluorine-modified acrylic resin and organic fluorine-silicon modified acrylic resin with nano-SiO2, effectively overcomes the drawbacks of using organic materials alone, such as reduced light transmittance, insufficient high temperature resistance and hydrolysis resistance, or insufficient permeability and repeated dissolution and crystallization, caused by using inorganic materials alone.

[0004] The technical solution provided by the present invention is an inorganic-organic fluorosilicone modified acrylic resin composite material protective liquid for the reinforcement and protection of earthen ruins, and the preparation method thereof comprises the following steps:

[0005] 1) Preparation of fluorine-containing compounds

[0006] Fluoroalcohol and isophorone diisocyanate were added to a three-necked flask and mechanically stirred at 85°C and 350 rpm for 2 h. 2-3 drops of dibutyltin dilaurate (DBTDL) were added during stirring as a chain transfer agent. After 2 h, hydroxyethyl methacrylate was slowly added dropwise and the reaction was continued for 2 h. The reaction was completed to obtain a fluorine-containing compound a with a double bond.

[0007] The fluorine-containing compound a is 2-((5-(((2,2,3,4,4,4-hexafluorobutoxy)carbonyl)amino)-1,3,3-trimethylcyclohexyl)methyl)carbamoyl)oxy)propyl methacrylate;

[0008] Wherein, the weight ratio of fluoroalcohol: isophorone diisocyanate: hydroxyethyl methacrylate is: 2-6: 5: 2-6;

[0009] 2) Preparation of organic fluorine-modified acrylic resin emulsion

[0010] A reactive emulsifier, 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate (DNS-86), and first deionized water were placed in a beaker and mechanically stirred at 350 rpm for 20 minutes to obtain an emulsifier aqueous solution A.

[0011] Add fluorinated compound a and acrylic monomers (functional monomers, hard monomers, and soft monomers) into a beaker and stir magnetically for 15 minutes to obtain a mixed solution B;

[0012] Add the initiator to the second deionized water and stir until dissolved to obtain an initiating aqueous solution C;

[0013] Preparation of pre-emulsified emulsion: Add 1 / 2 of the emulsifier aqueous solution A to a three-necked flask equipped with a mechanical stirrer at a stirring speed of 330 rpm. Add the mixed solution B dropwise into the three-necked flask using a dropping funnel at a rate of 1 to 2 seconds per drop. After the addition is complete, continue stirring for 30 minutes to prepare pre-emulsion D.

[0014] Preparation of seed emulsion: Add the remaining 1 / 2 of the emulsifier aqueous solution A to a four-necked flask equipped with a reflux condenser, a mechanical stirrer, a dropping funnel, and a thermometer, add a buffer, and heat in a water bath with stirring maintained at 280-350 rpm. Then, dropwise add 1 / 5 of the pre-emulsion D. After the temperature in the four-necked flask rises to 78-82°C, slowly dropwise add 1 / 5 of the initiator aqueous solution C. After a blue phase appears in the reaction, incubate for 15-30 minutes to obtain the seed emulsion.

[0015] Emulsion polymerization: using two dropping funnels, the remaining pre-emulsion D and the initiator aqueous solution C are added dropwise to the seed emulsion at a constant rate of 6-7 seconds per drop over 3-3.5 hours, ensuring that the addition of the pre-emulsion D is completed earlier than that of the initiator aqueous solution C. After the addition is completed, the mixture is stirred and reacted at 85-90° C. for 1 hour. After the reaction is completed, the reaction solution is cooled to room temperature, and then the pH is adjusted to 7-8 with 20% by mass aqueous ammonia. The material is filtered to obtain an organic fluorine-modified acrylic resin emulsion with a solid content of 32%-33%.

[0016] 3) Preparation of organic fluorine-silicone modified acrylic resin emulsion

[0017] Take the reactive emulsifier DNS-86 and the first deionized water in a beaker, and mechanically stir at 350 rpm for 20 minutes to obtain an emulsifier aqueous solution E;

[0018] Add fluorine-containing compound a, organosilicon, and acrylic monomer (functional monomer, hard monomer, soft monomer) into a beaker and stir magnetically for 15 minutes to obtain a mixed solution F;

[0019] Add the initiator into the second deionized water and stir until dissolved to obtain an initiator aqueous solution G;

[0020] Preparation of pre-emulsified emulsion: Add 1 / 2 of the emulsifier aqueous solution E to a three-necked flask equipped with a mechanical stirrer at a stirring speed of 330 rpm. Add the mixed solution F dropwise into the flask using a dropping funnel at a rate of 1 to 2 seconds per drop. After the addition is complete, continue stirring for 30 minutes to obtain pre-emulsion H.

[0021] Preparation of seed emulsion: Add 1 / 2 of the emulsifier aqueous solution E to a four-necked flask equipped with a reflux condenser, a mechanical stirrer, a dropping funnel, and a thermometer, add a buffer, and heat in a water bath with a stirring speed maintained at 280-350 rpm. Then, dropwise add 1 / 5 of the pre-emulsion H. After the temperature in the four-necked flask rises to 78-82°C, slowly dropwise add 1 / 5 of the initiator aqueous solution G. After the reaction phase appears, keep the temperature for 15-30 minutes to obtain the seed emulsion.

[0022] Emulsion polymerization reaction: using two dropping funnels, respectively, to drop the remaining pre-emulsion H and the initiator aqueous solution G into the seed emulsion at a rate of 6-7 seconds per drop over 3-3.5 hours, controlling the addition of the pre-emulsion H to be completed earlier than the initiator aqueous solution G. After the addition is completed, the mixture is stirred and reacted at 85-90° C. for 1 hour. After the reaction is completed, the reaction solution is cooled to room temperature, the pH is adjusted to 7-8 with 20% by mass ammonia water, and the material is filtered to obtain an organic fluorine-silicone-modified acrylic resin emulsion with a solid content of 31%-33%.

[0023] 4) Preparation of fluorosilicone modified acrylic resin protective liquid

[0024] The mixture of organic fluorine-modified acrylic resin emulsion: organic fluorine-silicon-modified acrylic resin emulsion: nano-silicon dioxide in a weight ratio of 1-2:1-2:0.08-0.16 was mixed evenly, and stirred evenly under the conditions of room temperature and 800 rpm magnetic stirring to obtain an inorganic-organic fluorine-silicon-modified acrylic resin composite material protective liquid;

[0025] In the preparation process of the organic fluorine-modified acrylic resin emulsion, the weight ratio of the fluorine-containing compound a, the hard monomer, the soft monomer, the functional monomer, the initiator, the reactive emulsifier, the buffer, the first deionized water, and the second deionized water is: 0.6-2.4: 2-20: 2-20: 0.6: 0.15-0.27: 0.6-2.1: 0.25-0.5: 30: 30;

[0026] In the preparation process of the organic fluorine-silicone modified acrylic resin emulsion, the weight ratio of fluorine-containing compound a, organic silicone, hard monomer, soft monomer, functional monomer, initiator, reactive emulsifier, buffer, first deionized water and second deionized water is: 0.6-2.4: 0.6-2.4: 2-20: 2-20: 0.6: 0.15-0.27: 0.6-2.1: 0.25-0.5: 30: 30.

[0027] The hard monomer is one of methyl methacrylate, ethyl methacrylate and styrene.

[0028] The soft monomer is one of butyl acrylate, ethyl acrylate and isooctyl acrylate.

[0029] The functional monomer is one of acrylic acid, methacrylic acid and acrylonitrile.

[0030] The buffer is one of sodium bicarbonate, disodium hydrogen phosphate and potassium dihydrogen phosphate.

[0031] The initiator is one of potassium persulfate, ammonium persulfate and sodium persulfate.

[0032] The fluoroalcohol is one of hexafluorobutanol and decafluoropentanol.

[0033] The organosilicon is one of triethoxy methacrylate silane and methacryloxypropyl trimethoxy silane.

[0034] The present invention is scientific and reasonable, has abundant raw materials, good use effect, pollution-free, environmentally friendly and safe, easy to produce and prepare, and integrates penetration, waterproof and moisture-proof, reinforcement protection, acid, alkali and salt resistance and aging resistance. Simultaneously, the prepared reinforcement protection material has good stability, low viscosity, strong fluidity, fully combines the acrylic resin transparency high, good weather resistance, fluorine-containing and silicon compounds have three advantages such as good water resistance, weather resistance and stain resistance, and combines nano-SiO2 good dispersibility and the advantage of absorbing ultraviolet rays, giving the earthen ruins certain moisture-proof and waterproof, acid, alkali and salt resistance, weather resistance, wear resistance and aging resistance effect. In addition, the protective liquid prepared by the present invention has good compatibility with the earthen ruins base material, can effectively enhance the mechanical strength and compressive strength of the earthen ruins cultural relics, and the original appearance and glossiness and weight change of the soil sample are not obvious, can remove the protective film under the condition of no damage or slight damage, conforms to the principle of "repairing the old as the old, keeping the original appearance", is an innovation in the protection of earthen ruins cultural relics, and has remarkable economic and social benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 The synthetic reaction route of fluorine-containing compound a is shown in FIG.

[0036] Figure 2 This is the reaction route for the synthesis of organic fluorine-modified acrylic resin;

[0037] Figure 3 This is the reaction route of organic fluorine-silicon modified acrylic resin. DETAILED DESCRIPTION

[0038] The following is a detailed description of the specific embodiments of the present invention in conjunction with the examples and specific circumstances. It should be understood that these examples are used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0039] Example 1

[0040] An inorganic-organic fluorosilicone modified acrylic resin composite material protective liquid for reinforcing and protecting earthen ruins, the preparation method of which comprises the following steps:

[0041] 1) Preparation of fluorine-containing compounds

[0042] 4 g of fluoroalcohol and 5 g of isophorone diisocyanate were weighed and added to a three-necked flask. The mixture was mechanically stirred at 85°C and 350 rpm for 2 h. 2-3 drops of dibutyltin dilaurate (DBTDL) were added as a chain transfer agent during stirring. After 2 h, 4 g of hydroxyethyl methacrylate was slowly added dropwise. The reaction was continued for 2 h. The reaction was completed to obtain a fluorinated compound a with a double bond.

[0043] The fluorine-containing compound a is 2-((5-(((2,2,3,4,4,4-hexafluorobutoxy)carbonyl)amino)-1,3,3-trimethylcyclohexyl)methyl)carbamoyl)oxy)propyl methacrylate;

[0044] 2) Preparation of organic fluorine-modified acrylic resin emulsion

[0045] 1.5 g of reactive emulsifier 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate (DNS-86) and 30 g of first deionized water were weighed in a beaker and mechanically stirred at 350 rpm for 20 minutes to obtain an emulsifier aqueous solution A;

[0046] 1.5 g of fluorinated compound a and acrylic monomer (0.6 g of functional monomer, 13.95 g of hard monomer, and 13.95 g of soft monomer) were weighed and added to a 100 mL beaker and magnetically stirred for 15 minutes to obtain a mixed solution B;

[0047] Weigh 0.27 g of initiator and add it into 30 g of second deionized water and stir until dissolved to obtain initiator aqueous solution C;

[0048] Preparation of pre-emulsified emulsion: Add 1 / 2 of the emulsifier aqueous solution A to a 100 mL three-necked flask equipped with a mechanical stirrer at a stirring speed of 330 rpm. Add the mixed solution B dropwise into the three-necked flask using a dropping funnel at a rate of 1 to 2 seconds per drop. After the addition is complete, continue stirring for 30 minutes to prepare pre-emulsion D.

[0049] Preparation of seed emulsion: Add the remaining 1 / 2 of the emulsifier aqueous solution A to a 250 mL four-necked flask equipped with a reflux condenser, mechanical stirrer, dropping funnel, and thermometer, add 0.3 g of buffer, and heat in a water bath with stirring maintained at 280-350 rpm. Add 1 / 5 of the pre-emulsion D dropwise. After the temperature in the four-necked flask rises to 78-82°C, slowly add 1 / 5 of the initiator aqueous solution C dropwise. After the reaction phase appears blue, keep the temperature for 15-30 minutes to obtain the seed emulsion.

[0050] Emulsion polymerization: using two dropping funnels, the remaining pre-emulsion D and the initiator aqueous solution C are added dropwise to the seed emulsion at a constant rate of 6-7 seconds per drop over 3-3.5 hours, ensuring that the addition of the pre-emulsion D is completed earlier than that of the initiator aqueous solution C. After the addition is completed, the mixture is stirred and reacted at 85-90° C. for 1 hour. After the reaction is completed, the reaction solution is cooled to room temperature, and then the pH is adjusted to 7-8 with 20% by mass aqueous ammonia. The material is filtered to obtain an organic fluorine-modified acrylic resin emulsion with a solid content of 32%-33%.

[0051] 3) Preparation of organic fluorine-silicone modified acrylic resin emulsion

[0052] 1.5 g of reactive emulsifier DNS-86 and 30 g of first deionized water were weighed in a beaker and mechanically stirred at 350 rpm for 20 minutes to obtain an emulsifier aqueous solution E;

[0053] 1.5 g of fluorinated compound a, 1.2 g of organosilicon, and acrylic monomer (0.6 g of functional monomer, 13.35 g of hard monomer, and 13.35 g of soft monomer) were weighed and added to a 100 mL beaker and magnetically stirred for 15 minutes to obtain a mixed solution F;

[0054] Weigh 0.27 g of initiator and add it into 30 g of second deionized water and stir until dissolved to obtain initiator aqueous solution G;

[0055] Preparation of pre-emulsified emulsion: Add 1 / 2 of the emulsifier aqueous solution E to a 100 mL three-necked flask equipped with a mechanical stirrer at a stirring speed of 330 rpm. Add the mixed solution F dropwise into the flask using a dropping funnel at a rate of 1 to 2 seconds per drop. After the addition is complete, continue stirring for 30 minutes to prepare pre-emulsion H.

[0056] Preparation of seed emulsion: Add 1 / 2 of the emulsifier aqueous solution E to a 250 mL four-necked flask equipped with a reflux condenser, mechanical stirrer, dropping funnel, and thermometer, add 0.3 g of buffer, and heat in a water bath with stirring maintained at 280-350 rpm. Add 1 / 5 of the pre-emulsion H dropwise. After the temperature in the four-necked flask rises to 78-82°C, slowly add 1 / 5 of the initiator aqueous solution G dropwise. After a blue phase appears in the reaction, keep the temperature for 15-30 minutes to obtain the seed emulsion.

[0057] Emulsion polymerization reaction: using two dropping funnels, respectively, to drop the remaining pre-emulsion H and the initiator aqueous solution G into the seed emulsion at a rate of 6-7 seconds per drop over 3-3.5 hours, controlling the addition of the pre-emulsion H to be completed earlier than the initiator aqueous solution G. After the addition is completed, the mixture is stirred and reacted at 85-90° C. for 1 hour. After the reaction is completed, the reaction solution is cooled to room temperature, the pH is adjusted to 7-8 with 20% by mass ammonia water, and the material is filtered to obtain an organic fluorine-silicone-modified acrylic resin emulsion with a solid content of 31%-33%.

[0058] 4) Preparation of fluorosilicone modified acrylic resin protective liquid

[0059] A mixture of organic fluorine-modified acrylic resin emulsion: organic fluorine-silicon-modified acrylic resin emulsion: nano-silicon dioxide in a weight ratio of 1:1:0.08 was evenly mixed, and the mixture was evenly stirred at room temperature and 800 rpm with magnetic stirring to obtain an inorganic-organic fluorine-silicon-modified acrylic resin composite material protective liquid.

[0060] Example 2:

[0061] The difference between this embodiment and embodiment 1 is that: during the preparation of the organic fluorine-modified acrylic resin emulsion, the weight ratio of the fluorine-containing compound a, the hard monomer, the soft monomer, the functional monomer, the initiator, the reactive emulsifier, the buffer, the first deionized water, and the second deionized water is: 1.2:14.1:14.1:0.6:0.27:1.5:0.3:30:30;

[0062] In the preparation process of the organic fluorine-silicone modified acrylic resin emulsion, the weight ratio of the fluorine-containing compound a, organic silicone, hard monomer, soft monomer, functional monomer, initiator, reactive emulsifier, buffer, first deionized water, and second deionized water is: 1.5:0.9:13.5:13.5:0.6:0.27:1.5:0.3:30:30;

[0063] The weight ratio of organic fluorine modified acrylic resin emulsion: organic fluorine silicone modified acrylic resin emulsion: nano silicon dioxide is 1:2:0.16.

[0064] Example 3:

[0065] The difference between this embodiment and embodiment 1 is that: during the preparation of the organic fluorine-modified acrylic resin emulsion, the weight ratio of the fluorine-containing compound a, the hard monomer, the soft monomer, the functional monomer, the initiator, the reactive emulsifier, the buffer, the first deionized water, and the second deionized water is: 1.8:13.8:13.8:0.6:0.27:1.5:0.3:30:30;

[0066] In the preparation process of the organic fluorine-silicone modified acrylic resin emulsion, the weight ratio of the fluorine-containing compound a, organic silicone, hard monomer, soft monomer, functional monomer, initiator, reactive emulsifier, buffer, first deionized water, and second deionized water is: 1.5:1.5:13.2:13.2:0.6:0.27:1.5:0.3:30:30;

[0067] The weight ratio of organic fluorine modified acrylic resin emulsion: organic fluorine silicone modified acrylic resin emulsion: nano silicon dioxide is: 2:1:0.08.

[0068] When in use, dilute the protective liquid and water in a volume ratio of 1:5 and mix them to conduct penetration reinforcement on the earthen ruins. Perform penetration reinforcement every 2 hours until the emulsion is completely penetrated and a film is formed on the surface of the soil sample. After the soil sample reinforcement is completed, it can be dried naturally at room temperature.

[0069] The present invention prepares an inorganic-organic fluorine-silicon modified acrylic resin composite material protective liquid for the reinforcement and protection of earthen ruins, which combines the excellent properties of acrylates, organosilicon, organofluorine, and inorganic materials. The main chains of each acrylate monomer are composed of C-C bonds, and the side chains are polar groups such as carboxylate groups. The resulting liquid has strong light transmittance, good film-forming properties, strong adhesion, and excellent oxidation and fungus resistance. The organosilicon coupling agent's molecular structure contains alkyl groups and silanol chains, which combine the flexibility and water resistance of polymers with the aging resistance and weather resistance of inorganic polymers. It also has good permeability and is adaptable to earthen ruins of various porosities. The high electronegativity of the fluorine atoms and the high C-F bond energy significantly reduce the surface tension of water, resulting in excellent hydrophobicity. Furthermore, the modified material has excellent self-cleaning properties, which can prevent atmospheric dust from damaging earthen ruins. By introducing a certain number of organofluorine-silicon groups into the acrylic resin structure for modification, the resulting resin combines the advantages of all three resins while compensating for their respective deficiencies. Siloxanes with reactive groups can form a network of hydrophobic siloxane films through the interaction of the reactive groups. This film can be evenly distributed on the micropore walls of porous earthen substrates, thereby providing protection. Furthermore, the protective fluid has the advantages of low viscosity and good permeability, without damaging the original appearance of earthen sites or blocking the internal pore structure. Furthermore, the protective material can also fall off or dissolve in an acetone / ethyl acetate mixed solvent, showing a certain degree of reversibility, making it effective for the reinforcement and protection of cultural relics at earthen sites.

[0070] When the present invention is used, a tablet compactor is used to press the soil sample into a cylindrical reshaped soil with a size of 20 mm in height and 50 mm in diameter. The reinforcement method is to use a dropwise method for reinforcement. The protective liquid prepared in the embodiment of the present invention and water are diluted and mixed in a volume ratio of 1:5. Then, the earthen ruins are subjected to infiltration reinforcement, and the infiltration reinforcement is performed once every 2 hours until the emulsion is completely penetrated and a film is formed on the surface of the soil sample. After the soil sample is reinforced, it is naturally dried at room temperature for about a week before the performance is measured. Using the same method, a blank control is made with a soil sample without the addition of the protective liquid. In order to verify the effectiveness of the present invention, the soil samples were treated with the above method using the products of the embodiment of the present invention respectively, and the hydrolysis resistance, acid and alkali resistance, weight change, water absorption, freeze-thaw resistance, and air permeability of the soil samples before and after the treatment were tested. The results are shown in the table below. Among them, the weight of earthen sites is measured in accordance with my country's national standard GB / T50123-1999; the hydrolysis resistance of earthen sites is measured in accordance with my country's national standard GB / T457-2008; the acid, alkali and salt resistance of earthen sites is measured in accordance with my country's national standard GB / 455-2002; the water absorption of earthen sites is measured in accordance with my country's national standard GB / T8941-2013; the air permeability of earthen sites is measured in accordance with GB / T 17146-2015; the freeze-thaw resistance of earthen sites is measured according to the test method in the "Testing Procedures for Stone Materials for Highway Engineering" T 021194;

[0071] The comparison of the performance index test results of the protective liquid prepared by the methods of Examples 1, 2, and 3 of the present invention on the reinforced soil samples is shown in the following table:

[0072] Table 1 Weight change determination

[0073]

[0074]

[0075] Table 2 Determination of water resistance, acid, alkali and salt resistance of reinforced soil samples

[0076]

[0077] Table 3 Determination of water absorption of reinforced soil samples

[0078]

[0079] Table 4 Determination of freeze-thaw resistance of soil samples reinforced with reinforcement liquid

[0080]

[0081]

[0082] Table 5 Air permeability determination of reinforced soil samples

[0083]

[0084] The above tests show that compared with blank soil samples, the weight change of the protective liquid prepared by the method of the present invention when used to reinforce the soil samples is not obvious compared with the original soil samples. The hydrolysis resistance, acid, alkali and salt resistance, and water resistance of the reinforced soil samples are significantly better than those of the blank soil samples. In addition, the freeze-thaw resistance and air permeability of the reinforced soil samples are significantly improved, indicating that the reinforcement liquid enhances the stability of the soil samples and improves the physical properties of the soil samples.

[0085] The method of the present invention is scientific and reasonable, with abundant raw materials. The solvent used is water, which is pollution-free, environmentally friendly, safe, and easy to produce. The prepared reinforcement and protection material has good stability, low viscosity, and strong fluidity. It fully combines the high transparency and good weather resistance of acrylic ester, the water resistance, weather resistance, and stain resistance of organic fluorine monomer, and the heat resistance of organic silicon. It is not easily decomposed by ultraviolet light. In addition, due to the advantages of easy hydrolysis of -OH in organic silicon and easy combination with nano-SiO2, the hydrophobic effect is enhanced, so it has good hydrophobicity, high and low temperature resistance, and weather resistance. In addition, the prepared protection liquid has certain moisture-proof, waterproof, acid, alkali, and salt resistance properties for earthen ruins, and has a significant effect on the reinforcement and protection of earthen ruins. The reinforcement and protection liquid prepared by the present invention has good compatibility with the earthen site base material, can effectively enhance the freeze-thaw resistance and air permeability of the earthen site cultural relics, and the original appearance, glossiness and weight of the soil sample do not change significantly. The protective film can be removed under non-destructive or minimally damaging conditions, which complies with the principle of "repairing the old as it is and maintaining the original appearance". It is an innovation in the protection liquid for earthen site cultural relics and has significant economic and social benefits.

Claims

1. An inorganic-organic composite material protective liquid for the reinforcement and protection of earthen ruins, characterized by: The preparation method comprises the following steps: 1) Preparation of fluorinated compounds Fluoroalcohol and isophorone diisocyanate were added to a three-necked flask and mechanically stirred at 85°C and 350 rpm for 2 h. 2-3 drops of dibutyltin dilaurate were added as a chain transfer agent during stirring. After 2 h, hydroxyethyl methacrylate was slowly added dropwise and the reaction was continued for 2 h. The reaction was completed to obtain a fluorine-containing compound a with a double bond. The fluorine-containing compound a is 2-((5-(((2,2,3,4,4,4-hexafluorobutoxy)carbonyl)amino)-1,3,3-trimethylcyclohexyl)methyl)carbamoyl)oxy)propyl methacrylate; Wherein, the weight ratio of fluoroalcohol: isophorone diisocyanate: hydroxyethyl methacrylate is: 2-6: 5: 2-6; 2) Preparation of organic fluorine-modified acrylic resin emulsion Take the reactive emulsifier 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate and the first deionized water in a beaker, and mechanically stir at 350 rpm for 20 minutes to obtain an emulsifier aqueous solution A; Add fluorinated compound a, functional monomer, hard monomer, and soft monomer into a beaker and stir magnetically for 15 minutes to obtain a mixed solution B; Add the initiator to the second deionized water and stir until dissolved to obtain an initiating aqueous solution C; Preparation of pre-emulsified emulsion: Add 1 / 2 of the emulsifier aqueous solution A to a three-necked flask equipped with a mechanical stirrer at a stirring speed of 330 rpm. Add the mixed solution B dropwise into the three-necked flask using a dropping funnel at a rate of 1-2 seconds per drop. After the addition is complete, continue stirring for 30 minutes to prepare pre-emulsion D. Preparation of seed emulsion: Add the remaining 1 / 2 of the emulsifier aqueous solution A to a four-necked flask equipped with a reflux condenser, mechanical stirrer, dropping funnel, and thermometer. Add a buffer and heat in a water bath with stirring maintained at 280-350 rpm. Add 1 / 5 of the pre-emulsion D dropwise. When the temperature in the four-necked flask rises to 78-82°C, slowly add 1 / 5 of the initiator aqueous solution C dropwise. After a blue phase appears in the reaction, incubate for 15-30 minutes to obtain the seed emulsion. Emulsion polymerization: using two dropping funnels, the remaining pre-emulsion D and initiator aqueous solution C are added dropwise to the seed emulsion at a constant rate of 6-7 seconds per drop over 3-3.5 hours, ensuring that the addition of pre-emulsion D is completed earlier than that of initiator aqueous solution C. After the addition is completed, the mixture is stirred and reacted at 85-90°C for 1 hour. After the reaction is completed, the reaction solution is cooled to room temperature, and then the pH is adjusted to 7-8 with 20% by mass aqueous ammonia. The material is filtered to obtain an organic fluorine-modified acrylic resin emulsion with a solid content of 32%-33%. 3) Preparation of organic fluorine-silicone modified acrylic resin emulsion Take the reactive emulsifier DNS-86 and the first deionized water in a beaker, and mechanically stir at 350 rpm for 20 minutes to obtain an emulsifier aqueous solution E; Add fluorine-containing compound a, organosilicon, functional monomer, hard monomer, and soft monomer into a beaker and stir magnetically for 15 minutes to obtain a mixed solution F; Add the initiator into the second deionized water and stir until dissolved to obtain an initiator aqueous solution G; Preparation of pre-emulsified emulsion: Add 1 / 2 of the emulsifier aqueous solution E to a three-necked flask equipped with a mechanical stirrer at a stirring speed of 330 rpm. Add the mixed solution F dropwise into the flask using a dropping funnel at a rate of 1-2 seconds per drop. After the addition is complete, continue stirring for 30 minutes to obtain pre-emulsion H. Preparation of seed emulsion: Add 1 / 2 of the emulsifier aqueous solution E to a four-necked flask equipped with a reflux condenser, mechanical stirrer, dropping funnel, and thermometer. Add a buffer and heat in a water bath with stirring maintained at 280-350 rpm. Add 1 / 5 of the pre-emulsion H dropwise. When the temperature in the four-necked flask rises to 78-82°C, slowly add 1 / 5 of the initiator aqueous solution G dropwise. After a blue phase appears in the reaction, incubate for 15-30 minutes to obtain the seed emulsion. Emulsion polymerization reaction: using two dropping funnels, the remaining pre-emulsion H and initiator aqueous solution G are added dropwise to the seed emulsion at a rate of 6-7 seconds per drop over 3-3.5 hours, ensuring that the addition of the pre-emulsion H is completed earlier than that of the initiator aqueous solution G. After the addition is completed, the mixture is stirred and heated at 85-90°C for 1 hour. After the reaction is completed, the reaction solution is cooled to room temperature, the pH is adjusted to 7-8 with 20% by mass ammonia water, and the material is filtered to obtain an organic fluorine-silicone-modified acrylic resin emulsion with a solid content of 31%-33%. 4) Preparation of inorganic-organic composite material protective solution for earthen site reinforcement and protection A mixture of an organic fluorine-modified acrylic resin emulsion: an organic fluorine-silicon-modified acrylic resin emulsion: nano-silica in a weight ratio of 1-2:1-2:0.08-0.16 is mixed evenly, and the mixture is stirred evenly at room temperature and 800 rpm with magnetic stirring to obtain an inorganic-organic composite material protective liquid for earthen site reinforcement and protection; In the preparation process of the organic fluorine-modified acrylic resin emulsion, the weight ratio of the fluorine-containing compound a, the hard monomer, the soft monomer, the functional monomer, the initiator, the reactive emulsifier, the buffer, the first deionized water, and the second deionized water is: 0.6-2.4: 2-20: 2-20: 0.6: 0.15-0.27: 0.6-2.1: 0.25-0.5: 30: 30; In the preparation process of the organic fluorine-silicone modified acrylic resin emulsion, the weight ratio of the fluorine-containing compound a, organic silicone, hard monomer, soft monomer, functional monomer, initiator, reactive emulsifier, buffer, first deionized water, and second deionized water is: 0.6-2.4: 0.6-2.4: 2-20: 2-20: 0.6: 0.15-0.27: 0.6-2.1: 0.25-0.5: 30: 30; The hard monomer is one of methyl methacrylate, ethyl methacrylate, and styrene, and the soft monomer is one of butyl acrylate, ethyl acrylate, and isooctyl acrylate; The functional monomer is one of acrylic acid, methacrylic acid and acrylonitrile; The fluoroalcohol is hexafluorobutanol; The organosilicon is one of triethoxysilane methacrylate or methacryloxypropyltrimethoxysilane.

2. The inorganic-organic composite material protective liquid for reinforcing and protecting earthen ruins according to claim 1 is characterized by: The weight ratio of organic fluorine modified acrylic resin emulsion: organic fluorine silicone modified acrylic resin emulsion: nano silicon dioxide is: 1:1:0.

08.

3. The inorganic-organic composite material protective liquid for reinforcing and protecting earthen ruins according to claim 1 is characterized in that: The weight ratio of organic fluorine modified acrylic resin emulsion: organic fluorine silicone modified acrylic resin emulsion: nano silicon dioxide is 1:2:0.

16.

4. The inorganic-organic composite material protective liquid for reinforcing and protecting earthen ruins according to claim 1 is characterized by: The weight ratio of organic fluorine modified acrylic resin emulsion: organic fluorine silicone modified acrylic resin emulsion: nano silicon dioxide is: 2:1:0.

08.

5. The inorganic-organic composite material protective liquid for reinforcing and protecting earthen ruins according to claim 1 is characterized by: The buffer is one of sodium bicarbonate, disodium hydrogen phosphate and potassium dihydrogen phosphate.

6. The inorganic-organic composite material protective liquid for reinforcing and protecting earthen ruins according to claim 1 is characterized by: The initiator is one of potassium persulfate, ammonium persulfate and sodium persulfate.

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