Multi-component hybrid siloxane, preparation thereof and application of multi-component hybrid siloxane in jade cultural relic protection

Abstract

The invention relates to multi-component hybrid siloxane as well as preparation and application thereof in protection of jade cultural relics. The multi-component hybrid siloxane is constructed by taking a linear skeleton formed by hydrolytic polycondensation of low-functionality siloxane as a basis, combining silicon hydroxyl generated by hydrolysis of high-functionality siloxane to construct a covalent cross-linked network and introducing functional siloxane containing characteristic functional groups as a chelating site. Compared with the prior art, the multi-component hybrid siloxane disclosed by the invention has good fluidity and stability, excellent curing performance and good bonding force with a jade cultural relic body, the jade cultural relic protected by the multi-component hybrid siloxane has small color difference change, and compared with the traditional siloxane, the multi-component hybrid siloxane has a better reinforcing effect; and the protection requirements of jade cultural relics can be met.

Description

Technical Field

[0001] The present invention belongs to the technical field of cultural relic protection materials, and in particular relates to a multi-component hybrid siloxane, its preparation and application in the protection of jade cultural relics. Background Art

[0002] Jade articles are outstanding representatives of Chinese excellent traditional culture and witnesses of China's ten-thousand-year cultural history and five-thousand-year civilization history. They have gone through stages such as beautiful jade, ritual jade, virtuous jade, auspicious jade, civilian jade, and lucky jade, and have continued to this day without interruption. They are regarded as the oldest watershed between Chinese and Western civilizations and are also typical representatives of the path and characteristics of Chinese civilization itself. Since the large-scale use of jadeite dates back to the mid-late Qing Dynasty, ancient Chinese jade articles mainly refer to symbolic utensils made from nephrite materials of tremolite-actinolite through carving techniques. Tremolite-actinolite, with the molecular formula Ca2(Mg,Fe)5[Si4O 11 2(OH)2, belongs to a relatively stable double-chain silicate structure. Generally, jade articles are considered "stable" cultural relics. However, a large number of unearthed jade articles show that affected by the combined effects of human behavior before burial and natural infiltration after burial, various deterioration phenomena will occur to jade articles. Among them, pulverization is the most harmful disease to jade articles and is also known as the "cancer" among jade diseases. Severely pulverized jade articles have become "endangered" cultural relics. If not effectively treated, the degree of pulverization will further spread, causing the overall structure of the jade article to collapse and the artifact to be damaged and disappear, which greatly affects the inheritance of this precious cultural heritage of jade articles. Particularly importantly, jade articles are prone to deteriorate and form pulverization diseases in acidic, neutral, and alkaline burial environments, resulting in a large number of pulverized jade articles that need to be protected. The geographical coverage includes the entire territory of China, and the time span covers from prehistoric to modern times. Therefore, developing suitable protection materials for rescue and preventive reinforcement of pulverized jade articles is of great significance for ensuring the safety of cultural relics and preserving the value of cultural relics.

[0003] Due to the lack of a traditional jade culture abroad, the restoration and protection work of jade cultural relics in the world is only seen in China. However, jade articles are often habitually regarded as "stable" cultural relics, so the protection work of jade cultural relics in China has not been taken seriously. There has been little exploration of protection materials and methods for jade articles. In the past, organic polymer materials (such as acrylic resins) were often used for the protection of jade cultural relics, but organic protection materials usually have problems such as poor durability, incompatibility with the inorganic cultural relic body, and easy color change and loss of adhesion due to the aging of organic functional groups.

[0004] CN118895089A discloses a photo-curable jade adhesive, its preparation method and application. This jade adhesive is prepared by mixing (meth)acrylate monomers, diluent monomers, (meth)acrylate type secondary phosphates, photoinitiators and co-initiators. However, this material needs to be photo-cured to achieve the bonding effect, and most of the raw materials used are organic materials, which are incompatible with the jade cultural relics themselves and have the risk of aging.

[0005] Siloxane materials are considered to be one of the most promising protection materials for silicate cultural relics at present, because they have good durability (high Si-O-Si bond energy), and the cured products have good compatibility with the cultural relics themselves. However, there are two major application limitations when this material is used for the protection of jade cultural relics. One is that the shrinkage stress generated during the gel drying process is easy to cause cracking. The other is that since the Si-OH generated by the hydrolysis of siloxane can only combine with the silanol groups in the cultural relics, there is a lack of effective bonding force for non-silicon components such as calcium and magnesium ions in tremolite-actinolite. These all make it difficult for siloxane materials to effectively protect jade cultural relics.

[0006] Therefore, there is still a need to develop new reinforcement and protection materials suitable for jade cultural relics. Summary of the Invention

[0007] The purpose of the present invention is to provide a multi-component hybrid siloxane, its preparation and application in the protection of jade cultural relics, in order to overcome the defects of the existing cultural relic protection materials, such as incompatibility with the jade cultural relics themselves, easy cracking and poor bonding force.

[0008] The purpose of the present invention can be achieved by the following technical solutions:

[0009] The present invention first provides a multi-component hybrid siloxane, and the multi-component hybrid siloxane has the following general structural formula:

[0010]

[0011] Among them, m is an integer from 1 to 10, n is an integer from 1 to 10, and p is an integer from 1 to 10;

[0012] R1 is one or more of aminopropyl and methyl;

[0013] R2 includes any one or more of ethyl diethylphosphate, mercaptopropyl, and isocyanate propyl.

[0014] The present invention also provides a preparation method of a multi-component hybrid siloxane, including the following steps:

[0015] S1: Dissolve the low-functional siloxane in a solvent, add a hydrolyzing agent, and mix and disperse evenly to obtain a stable solution;

[0016] S2: Add a highly functional siloxane, a siloxane containing a functional group, and a catalyst to the solution, mix evenly and heat to carry out a hydrolysis and polycondensation reaction, thus obtaining the multi-component hybrid siloxane.

[0017] Further, in step S1, the low-functional siloxane includes one or more of 3-aminopropyl dimethoxymethyl siloxane, 3-aminopropyl diethoxymethyl siloxane, and dimethoxydimethyl silane.

[0018] Further, in step S1, the solvent includes one or more of ethanol, ethylene glycol, n-butanol, or isopropanol.

[0019] Further, in step S1, the molar ratio of the hydrolyzing agent to the low-functional siloxane is (5 - 9):1.

[0020] Further, in step S1, the volume ratio of the hydrolyzing agent to the solvent is (0.8 - 1.6):4.

[0021] Further, in step S2, the molar ratio of the low-functional siloxane, the highly functional siloxane, and the siloxane containing a functional group is (0.5 - 1.5):1:(0.5 - 2.0).

[0022] Further, in step S2, the highly functional siloxane includes one or both of tetraethyl orthosilicate or tetramethyl orthosilicate.

[0023] Further, in step S2, the siloxane containing a functional group includes one or more of diethyl phosphoric acid ethyl triethoxysilane, (3-mercaptopropyl) trimethoxysilane, (3-mercaptopropyl) triethoxysilane, and 3-isocyanatopropyl trimethoxysilane.

[0024] Further, in step S2, the catalyst includes one or more of triethylamine, n-octylamine, or ammonia water.

[0025] Further, in step S2, the molar ratio of the catalyst to the highly functional siloxane is (0.3 - 0.6):1.

[0026] Further, in step S2, the temperature of the hydrolysis and polycondensation reaction is 60 - 150 °C.

[0027] Further, in step S2, the time of the hydrolysis and polycondensation reaction is 5 - 10 h.

[0028] The present invention also provides an application of the multi-component hybrid siloxane in the protection of jade cultural relics, and the application includes the following steps:

[0029] Disperse the multi-component hybrid silicone in a solvent to obtain a reinforcing liquid with a solid content of 5-20 wt%; apply the reinforcing liquid to the surface of the jade cultural relics to be reinforced, and form a silicon-oxygen network inside the jade cultural relics after curing at room temperature.

[0030] Furthermore, the application method of the reinforcing liquid is to spray or drop the reinforcing liquid on the surface of the jade cultural relics to be reinforced, or immerse the jade cultural relics to be reinforced in the reinforcing liquid.

[0031] Furthermore, the multi-component hybrid silicone in the reinforcing liquid undergoes bonding with the main body of the jade cultural relics to be reinforced in forms such as ionic bonds, hydrogen bonds, and covalent bonds.

[0032] The working principle of the multi-component hybrid silicone of the present invention as a cultural relic protection material includes the following aspects:

[0033] (1) The multi-component hybrid silicone of the present invention is based on the linear skeleton formed by the hydrolysis and polycondensation of low-functional silicone, combines the silanol groups generated by the hydrolysis of high-functional silicone to construct a covalent cross-linked network, and introduces functionalized silicone containing characteristic functional groups as chelating sites to achieve multi-functional synergistic assembly at the molecular level, and prepares a multi-component hybrid silicone oligomer.

[0034] (2) The multi-component hybrid silicone of the present invention enters the pores inside the cultural relics in the form of oligomers, undergoes a further sol-gel process, and forms a silicon-oxygen network to reinforce the jade cultural relics. The linear silicone skeleton therein provides flexibility, alleviates the cracking problem during the curing process of the material, and effectively bonds with the main body of the jade cultural relics through functionalized functional groups, overcoming the defects such as cracking and poor bonding force with the main body of the cultural relics existing in the previous silicone materials, and can effectively protect the jade cultural relics.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) The present invention is based on the linear skeleton formed by the hydrolysis and polycondensation of low-functional silicone, combines the silanol groups generated by the hydrolysis of high-functional silicone to construct a covalent cross-linked network, and introduces functionalized silicone containing characteristic functional groups as chelating sites to achieve multi-functional synergistic assembly at the molecular level, and constructs a multi-component hybrid silicone. This multi-component hybrid silicone has a good bonding force with the main body of the jade cultural relics and can be applied to the reinforcement and protection of jade cultural relics.

[0037] (2) The multi-component hybrid silicone of the present invention enters the pores inside the cultural relics in the form of oligomers, undergoes a further sol-gel process, and forms a silicon-oxygen network to reinforce the jade cultural relics. The linear silicone skeleton therein provides flexibility, alleviates the cracking problem during the curing process of the material, reduces the protective damage to the cultural relics caused by material shrinkage and cracking, and effectively protects the jade cultural relics.

[0038] (3) The multi-component hybrid silicone of the present invention all uses Si-O-Si as the main chain skeleton. Compared with traditional organic protection materials, it has high chemical bond energy, good weather resistance and good compatibility with the jade cultural relics. The multi-component hybrid silicone contains functionalized functional groups, which bond with calcium and magnesium ions in the jade cultural relics through ionic bonds, hydrogen bonds, covalent bonds, etc., enhancing the adhesion to the jade mineral particles and realizing the effective protection of the jade cultural relics.

[0039] (4) The solid content of the multi-component hybrid silicone of the present invention can be adjusted by changing the solvent content to meet the protection requirements of jade cultural relics with different deterioration degrees, and there is no need for photocuring operation, and the operation is simple.

[0040] (5) The multi-component hybrid silicone of the present invention has a better strengthening effect compared with traditional silicone. The color difference change of the jade cultural relics after protection is small, which can meet the protection requirements of the jade cultural relics. Description of the Drawings

[0041] Figure 1 It is the nuclear magnetic resonance silicon spectrum test result diagram of the xerogel formed after the curing of the multi-component hybrid silicone in Example 1 of the present invention.

[0042] Figure 2 It is the scanning electron microscope diagram of the jade sample after being strengthened by the multi-component hybrid silicone in Example 1 of the present invention. Detailed Embodiments

[0043] The present invention will be described in detail below with reference to the drawings and specific embodiments. This embodiment is implemented on the premise of the technical solution of the present invention, and the detailed implementation manners and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.

[0044] Unless otherwise specified, the reagents, methods, instruments and equipment used in the present invention are conventional reagents, methods, instruments and equipment in the art. Unless otherwise specified, the reagents and materials used in the following examples are all commercially available.

[0045] Based on the linear skeleton formed by the hydrolysis and polycondensation of low-functional silicone, the present invention combines the silicon hydroxyl groups generated by the hydrolysis of high-functional silicone to construct a covalent cross-linked network, and introduces a functionalized silicone containing characteristic functional groups as a chelating site to construct a multi-component hybrid silicone. The multi-component hybrid silicone has the following general structural formula:

[0046]

[0047] Among them, m is an integer from 1 to 10, n is an integer from 1 to 10, and p is an integer from 1 to 10;

[0048] R1 is one or more of aminopropyl and methyl;

[0049] R2 includes any one or more of ethyl diethylphosphate, mercaptopropyl, and isocyanate propyl.

[0050] The present invention also provides a method for preparing a multi-component hybrid silicone, comprising the following steps:

[0051] S1: Dissolve a low-functional silicone in a solvent, add a hydrolyzing agent, and mix and disperse evenly to obtain a stable solution;

[0052] S2: Add a high-functional silicone, a silicone containing a functional group, and a catalyst to the solution, mix evenly and heat to carry out a hydrolysis and polycondensation reaction, thereby obtaining the multi-component hybrid silicone.

[0053] In some specific embodiments, in step S1, the low-functional silicone includes one or two of 3-aminopropyldimethoxymethylsiloxane, 3-aminopropyldiethoxymethylsiloxane, and dimethoxydimethylsilane.

[0054] In some specific embodiments, in step S1, the solvent includes one or more of ethanol, ethylene glycol, n-butanol, or isopropanol.

[0055] In some specific embodiments, in step S1, the molar ratio of the hydrolyzing agent to the low-functional silicone is (5-8):1, such as 5:1, 6:1, 7:1, or 8:1.

[0056] In some specific embodiments, in step S1, the volume ratio of the hydrolyzing agent to the solvent is (0.8-1.6):4, such as 0.8:4, 1.0:4, 1.2:4, 1.2:4, or 1.6:4.

[0057] In some specific embodiments, in step S2, the molar ratio of the low-functional silicone, the high-functional silicone, and the silicone containing a functional group is (0.5-1.5):1:(0.5-2.0).

[0058] In some specific embodiments, in step S2, the high-functional silicone includes one or two of tetraethyl orthosilicate or tetramethyl orthosilicate.

[0059] In some specific embodiments, in step S2, the silicone containing a functional group includes one or more of ethyl diethylphosphate triethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)triethoxysilane, and 3-isocyanate propyltrimethoxysilane.

[0060] In some specific embodiments, in step S2, the catalyst includes one or more of triethylamine, n-octylamine, or ammonia water.

[0061] In some specific embodiments, in step S2, the molar ratio of the catalyst to the high-functional siloxane is (0.3 - 0.6):1, such as 0.3:1, 0.4:1, 0.5:1, or 0.6:1.

[0062] In some specific embodiments, in step S2, the temperature of the hydrolysis and polycondensation reaction is 60 - 150 °C, such as 60 °C, 80 °C, 100 °C, 120 °C, or 150 °C, and those skilled in the art can flexibly adjust according to the actual reaction conditions.

[0063] In some specific embodiments, in step S2, the time of the hydrolysis and polycondensation reaction is 5 - 10 h, such as 5 h, 6 h, 7 h, 8 h, 9 h, or 10 h, and those skilled in the art can flexibly adjust according to the actual reaction progress.

[0064] The present invention also provides an application of a multi-component hybrid siloxane in the protection of jade cultural relics, and the application includes the following steps:

[0065] Disperse the multi-component hybrid siloxane in a solvent to obtain a reinforcing liquid with a solid content of 5 - 20 wt%; apply the reinforcing liquid to the surface of the jade cultural relic to be reinforced, and after curing at room temperature, a silicon-oxygen network is formed inside the jade cultural relic.

[0066] In some specific embodiments, the application method of the reinforcing liquid is to spray or drop the reinforcing liquid on the surface of the jade cultural relic to be reinforced, or immerse the jade cultural relic to be reinforced in the reinforcing liquid.

[0067] In some specific embodiments, the multi-component hybrid siloxane in the reinforcing liquid is bonded to the jade body to be reinforced through ionic bonds, hydrogen bonds, covalent bonds, etc.

[0068] Each of the above embodiments can be implemented alone, or any two or more of them can be combined for implementation. The following specific examples are used to illustrate the above embodiments in more detail.

[0069] Example 1:

[0070] This example provides a multi-component hybrid siloxane, and the reaction equation in its preparation process is specifically as follows:

[0071]

[0072] The specific preparation method of the multi-component hybrid siloxane is as follows:

[0073] (1) Slowly dissolve 3-aminopropyldimethoxymethylsiloxane in ethanol, and add deionized water. The molar ratio of deionized water to 3-aminopropyldimethoxymethylsiloxane is 7:1, and the volume ratio of deionized water to ethanol is 1:4. Stir at room temperature until it becomes colorless and transparent to obtain a stable solution.

[0074] (2) Add tetraethyl orthosilicate, (3-mercaptopropyl)trimethoxysilane and triethylamine to the solution. The molar ratio of 3-aminopropyldimethoxymethylsiloxane, tetraethyl orthosilicate and (3-mercaptopropyl)trimethoxysilane is 1:1:0.5, and the molar ratio of triethylamine to tetraethyl orthosilicate is 0.3:1. Heat to 70 °C under magnetic stirring to promote the hydrolysis and polycondensation reaction. The reaction time is 4 h to obtain a multi-component hybrid siloxane.

[0075] As Figure 1 shown, the characteristic peak of D2-type silicon atoms appears at a chemical shift of -21 ppm, proving the formation of linear siloxane segments. The characteristic peak of T3-type silicon atoms appears at -68 ppm, and the characteristic peaks of Q3 and Q4-type silicon atoms appear at -99 ppm and -109 ppm, proving the further condensation of siloxanes containing functional groups and highly functional siloxanes.

[0076] This example also uses the above multi-component hybrid siloxane to penetrate and reinforce and protect jade cultural relics. The specific steps are as follows:

[0077] Dilute the multi-component hybrid siloxane with ethanol to obtain a reinforcement liquid with a solid content of 5%. Apply the multi-component hybrid siloxane reinforcement liquid to the surface of the powdered tremolite jade in the form of dropping. After the liquid completely wets the sample, transfer the sample to a constant temperature and humidity incubator at 25 °C and 50% Rh and cure for two weeks.

[0078] As Figure 2 shown by the SEM characterization, it can be seen that the multi-component hybrid siloxane in this example uniformly covers the surface of the jade, forms gel connections between the powdered tremolite mineral particles, and plays a good reinforcement effect. The above multi-component hybrid siloxane introduces flexible siloxane segments and functional groups into the rigid siloxane network formed by tetraethyl orthosilicate. Its skeleton is connected by Si-O-Si and has a certain flexibility and chelating ability. Therefore, the above multi-component hybrid siloxane has high weather resistance while having a certain anti-cracking ability and the ability to bond with the cultural relic itself, and can provide an effective reinforcement and protection effect for jade cultural relics.

[0079] Example 2:

[0080] This example provides a multi-component hybrid silicone, which is basically the same as Example 1. The difference lies in that in step (2), the molar ratio of 3-aminopropyldimethoxymethylsiloxane, tetraethyl orthosilicate, and (3-mercaptopropyl)trimethoxysilane is 1:1:1, the molar ratio of triethylamine to tetraethyl orthosilicate is 0.5:1, the heating temperature is 80 °C, and the reaction time is 8 h.

[0081] Example 3:

[0082] This example provides a multi-component hybrid silicone, which is basically the same as Example 1. The difference lies in that in step (2), the molar ratio of 3-aminopropyldimethoxymethylsiloxane, tetraethyl orthosilicate, and (3-mercaptopropyl)trimethoxysilane is 1:1:1.5, the molar ratio of triethylamine to tetraethyl orthosilicate is 0.6:1, the heating temperature is 100 °C, and the reaction time is 10 h.

[0083] Example 4:

[0084] This example provides a multi-component hybrid silicone, which is basically the same as Example 1. The difference lies in that the low-functional silicone used in this example is 3-aminopropyldiethoxymethylsiloxane.

[0085] Example 5:

[0086] This example provides a multi-component hybrid silicone, which is basically the same as Example 1. The difference lies in that the high-functional silicone used in this example is tetramethyl orthosilicate.

[0087] Example 6:

[0088] This example provides a multi-component hybrid silicone, which is basically the same as Example 1. The difference lies in that the silicone containing a functional functional group used in this example is 3-isocyanatopropyltrimethoxysilane.

[0089] Example 7:

[0090] This example provides a multi-component hybrid silicone, which is basically the same as Example 1. The difference lies in that the silicone containing a functional functional group used in this example is diethylphosphate ethyltriethoxysilane.

[0091] Example 8:

[0092] This example provides a multi-component hybrid silicone, which is basically the same as Example 1. The difference lies in that the silicone containing a functional functional group used in this example is (3-mercaptopropyl)triethoxysilane.

[0093] Comparative Example 1:

[0094] This comparative example uses a two-component hybrid silicone, which is basically the same as Example 1. The difference is that (3-mercaptopropyl)trimethoxysilane is not added. The specific preparation method is as follows:

[0095] (1) Slowly dissolve 3-aminopropyldimethoxymethylsilane in ethanol, and add deionized water. The molar ratio of deionized water to 3-aminopropyldimethoxymethylsilane is 7:1, and the volume ratio of deionized water to ethanol is 1:4. Stir at room temperature until it becomes colorless and transparent to obtain a stable solution.

[0096] (2) Add tetraethyl orthosilicate and triethylamine to the solution. The molar ratio of 3-aminopropyldimethoxymethylsilane to tetraethyl orthosilicate is 1:1, and the molar ratio of triethylamine to tetraethyl orthosilicate is 0.3:1. Heat to 70 °C under magnetic stirring to promote the hydrolysis and polycondensation reaction. The reaction time is 4 h to obtain a two-component hybrid silicone.

[0097] The two-component hybrid silicone prepared in this comparative example is used for the reinforcement of jade cultural relics, and the operation process is the same as that in Example 1.

[0098] Comparative Example 2:

[0099] This comparative example uses a traditional single-component polysiloxane with tetraethyl orthosilicate as the main component. The specific preparation method is as follows:

[0100] Disperse tetraethyl orthosilicate and triethylamine in a mixed solvent of deionized water and ethanol. The molar ratio of triethylamine to tetraethyl orthosilicate is 0.3:1. Heat to 70 °C under magnetic stirring to promote the hydrolysis and polycondensation reaction. The reaction time is 4 h to obtain a single-component hybrid silicone.

[0101] The single-component hybrid silicone prepared in this comparative example is used for the reinforcement of jade cultural relics, and the operation process is the same as that in Example 1.

[0102] The present invention conducts the following performance tests on the above examples and comparative examples:

[0103] (1) Color difference test: Use a 3nh YS3060 spectrophotometer to measure the color difference of the jade before and after protection.

[0104] (2) Hardness test: Use a Leeb 180D Leeb hardness tester to measure the hardness of the jade before and after protection.

[0105] (3) Peel strength test: Use the tape method to measure the peel strength of the jade before and after protection.

[0106] The above performance test results are summarized in Table 1.

[0107] Table 1 Summary of Performance Test Results

[0108]

[0109]

[0110] As can be seen from the above table, the color difference test shows that the color difference change ΔE of the jade articles samples protected by the multi-component hybrid silicone prepared in Examples 1-3 of the present invention does not exceed 4, and the color difference change is within the acceptable range, indicating that the cultural relic reinforcement and protection material of the present invention has good color fidelity. The color difference change of the single-component silicone in Comparative Example 2 can be as high as 4.65, and it does not have good color fidelity.

[0111] The hardness test shows that the hardness of the jade article sample before protection is 84.8 HL, and the hardness of the jade article sample after being protected by the multi-component hybrid silicone of the present invention is increased to as high as 212.6 HL. On the contrary, the hardness of the single-component silicone in Comparative Example 2 is only 128.3 HL, and the hardness of the two-component hybrid silicone in Comparative Example 1 is only increased to 163.0 HL, both of which have significant differences from the hardness in the examples of the present invention.

[0112] The anti-peeling strength test shows that the mass loss of the jade article sample before protection is 22.5 mg / cm 2 , and the peeling mass loss of the jade article sample after being protected by the multi-component hybrid silicone of the present invention is reduced to 7.6 mg / cm 2 . The above results are all better than those of Comparative Example 1 and Comparative Example 2, indicating that the introduction of the functional silicone has improved the bonding force of the material to the jade articles and achieved a better protection effect. The result obtained in Comparative Example 1 is better than that in Comparative Example 2 because tetraethyl orthosilicate has suffered from dry shrinkage and cracking problems and cannot effectively protect the jade articles. The introduction of low-functional silicone can alleviate the occurrence of cracking problems and improve the protection effect of the material.

[0113] In summary, the multi-component hybrid silicone protection material of the present invention has a good reinforcement and protection effect on jade articles. After protection, the color difference change of the jade article sample is within the acceptable range, and the hardness and anti-peeling strength parameter indexes of the jade article sample have been significantly improved.

[0114] The above description of the embodiments is to enable those of ordinary skill in the art to understand and use the invention. Obviously, those familiar with the technology can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative labor. Therefore, the present invention is not limited to the above embodiments, and all improvements and modifications made by those skilled in the art without departing from the scope of the present invention according to the disclosure of the present invention should be within the protection scope of the present invention.

Claims

1. A multi-component hybrid siloxane, characterized in that, The multi-component hybrid silicone has the following structural general formula: wherein, m is an integer from 1 to 10, n is an integer from 1 to 10, and p is an integer from 1 to 10; R1 is one or more of aminopropyl and methyl; R2 includes any one or more of ethyl diethylphosphate, mercaptopropyl, and isocyanate propyl.

2. A method for preparing the multi-component hybrid silicone oxide according to claim 1, characterized in that, It includes the following steps: S1: Dissolve the low-functional silicone in a solvent, add a hydrolyzing agent, and mix and disperse evenly to obtain a stable solution; S2: Add a high-functional silicone, a silicone containing a functional group, and a catalyst to the solution, mix evenly and heat to carry out a hydrolysis and polycondensation reaction, and thus obtain the multi-component hybrid silicone.

3. The preparation method of the multi-component hybrid silicone according to claim 2, characterized in that, In step S1, the low-functional silicone includes one or more of 3-aminopropyldimethoxymethylsiloxane, 3-aminopropyldiethoxymethylsiloxane, and dimethoxydimethylsilane.

4. The preparation method of the multi-component hybrid silicone according to claim 2, wherein In step S1, the solvent includes one or more of ethanol, ethylene glycol, n-butanol, or isopropanol; The molar ratio of the hydrolyzing agent to the low-functional silicone is (5-9):1, and the volume ratio of the hydrolyzing agent to the solvent is (0.8-1.6):

4.

5. The preparation method of the multi-component hybrid silicone according to claim 2, wherein, In step S2, the molar ratio of the low-functional silicone, the high-functional silicone, and the silicone containing a functional group is (0.5-1.5):1:(0.5-2.0).

6. The preparation method of the multi-component hybrid silicone oxide according to claim 2, characterized in that, In step S2, the high-functional silicone includes one or two of tetraethyl orthosilicate or tetramethyl orthosilicate; The silicone containing a functional group includes one or more of ethyl diethylphosphate triethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)triethoxysilane, and 3-isocyanate propyltrimethoxysilane.

7. The preparation method of the multi-component hybrid siloxane according to claim 2, wherein In step S2, the catalyst includes one or more of triethylamine, n-octylamine, or ammonia water; The molar ratio of the catalyst to the high-functional silicone is (0.3-0.6):

1.

8. The preparation method of the multi-component hybrid silicone according to claim 2, characterized in that, In step S2, the temperature of the hydrolysis and polycondensation reaction is 60-150°C, and the time of the hydrolysis and polycondensation reaction is 5-10 h.

9. Use of the multi-component hybrid silicone as described in claim 1 in the protection of jade cultural relics, characterized in that, The application includes the following steps: Disperse the multi-component hybrid silicone in a solvent to obtain a reinforcing liquid with a solid content of 5-20 wt%; Apply the reinforcing liquid to the surface of the jade cultural relic to be reinforced, and after curing at room temperature, a silicone network is formed inside the jade cultural relic.

10. The application of the multi-component hybrid silicone in the protection of jade cultural relics according to claim 9, characterized in that, The way of applying the reinforcing liquid is to spray or drop the reinforcing liquid on the surface of the jade cultural relic to be reinforced, or soak the jade cultural relic to be reinforced in the reinforcing liquid; The multi-component hybrid silicone in the reinforcing liquid is bonded to the main body of the jade cultural relic to be reinforced in the forms of ionic bonds, hydrogen bonds, covalent bonds, etc.

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