Polyethylene glycol composite liquid for reinforcing water-saturated bamboo and wood cultural relics and preparation method of polyethylene glycol composite liquid

Abstract

The invention discloses a polyethylene glycol complex liquid for reinforcing water-saturated bamboo and wood cultural relics and a preparation method of the polyethylene glycol complex liquid. The polyethylene glycol complex liquid is prepared from polyethylene glycol, water-soluble amino siloxane, phenylboronic acid derivatives and a solvent. The total mass percent concentration of the polyethylene glycol and the water-soluble amino siloxane is 10%-60%, and the mass percent concentration of the phenylboronic acid derivative is 0.01%-1%; wherein the mass ratio of the polyethylene glycol to the water-soluble amino siloxane is (1: 1)-(8: 1). According to the method, the size stability of the bamboo-wood cultural relics in the reinforcement treatment process is improved, the shrinkage rate of the reinforced bamboo-wood cultural relics in the natural drying process is greatly reduced, and safe dehydration and shaping of the medium-high-degradation saturated bamboo-wood cultural relics are achieved.

Description

Technical Field

[0001] This invention relates to the field of cultural relic protection technology, specifically to a polyethylene glycol composite liquid for reinforcing waterlogged bamboo and wood cultural relics and its preparation method. Background Technology

[0002] Bamboo and wooden artifacts unearthed or recovered from marine archaeological sites in southern my country are typically in a highly saturated state. Due to microbial degradation, which creates numerous porous structures, and the loss of significant amounts of holocellulose, their structural strength is greatly reduced. During dehydration, they will experience shrinkage, cracking, and deformation. Therefore, saturated bamboo and wooden artifacts must be reinforced with filling materials before dehydration to improve their resistance to shrinkage. For example, CN116810944A discloses a method for shaping and reinforcing wooden artifacts using erythritol; CN117962050A discloses a method for reinforcing waterlogged wooden artifacts using xylitol as the main reagent; CN117186328A discloses a method for dehydrating and shaping waterlogged wooden artifacts using a lignin-like emulsion; CN117186411A discloses a method for dehydrating and shaping waterlogged wooden artifacts using an organosilicon emulsion; CN115805633A discloses a method for reinforcing waterlogged wooden artifacts using polyethylene glycol derivatives; CN117183043A discloses a method for dehydrating waterlogged lacquered wood using a glyoxal composite solution; CN115446937B discloses an atom transfer radical polymerization reinforcement method for wooden artifacts; and CN119017491A discloses a reinforcement method based on water-soluble siloxanes and dialdehydes. Although the aforementioned patents employ a variety of materials for processing, the complexity of the implementation steps and the stringent processing conditions make it difficult to carry out protection work on a large scale.

[0003] Among existing materials for reinforcing waterlogged bamboo and wood artifacts, polyethylene glycol (PEG) is the mainstream and irreplaceable material for the preservation of large bamboo and wood artifacts such as shipwrecks due to its water solubility and ability to be sprayed on a large scale. However, PEG is not effective in reinforcing highly degraded wooden artifacts, and its dimensional stability (i.e., shrinkage resistance) is poor under natural drying conditions. It must be combined with freeze-drying to achieve the desired protective effect. However, freeze-drying is limited by equipment and is not conducive to large-scale and efficient conservation work. Natural drying or controlled humidity drying is the most ideal drying method, but this places higher demands on the performance of the reinforcing material. Summary of the Invention

[0004] The purpose of this invention is to provide a polyethylene glycol composite liquid for reinforcing waterlogged bamboo and wood artifacts and its preparation method. This formula is based on polyethylene glycol, with the addition of a water-soluble organosiloxane coupling agent and a phenylboronic acid derivative to form a ternary composite formula. While maintaining the traditional polyethylene glycol processing methods (immersion, spraying, etc.), it improves dimensional stability and significantly reduces the shrinkage rate of the reinforced bamboo and wood artifacts during the natural drying process, achieving safe dehydration and shaping of medium- to highly degraded waterlogged bamboo and wood artifacts.

[0005] The technical solution adopted by this invention to solve its technical problem is:

[0006] A polyethylene glycol composite solution for reinforcing waterlogged bamboo and wood artifacts is composed of polyethylene glycol, water-soluble aminosiloxane, phenylboronic acid derivative, and solvent; the total mass percentage concentration of polyethylene glycol and water-soluble aminosiloxane is 10%-60%, and the mass percentage concentration of phenylboronic acid derivative is 0.01-1%; wherein the mass ratio of polyethylene glycol to water-soluble aminosiloxane is 1:1 to 8:1.

[0007] Preferably, the molecular weight of the polyethylene glycol is 200-4000.

[0008] Preferably, the water-soluble aminosiloxane includes 3-aminopropyltriethoxysilane (APTES), 3-aminopropyltrimethoxysilane (APTMS), and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (AAPTMS), etc.

[0009] Preferably, the phenylboronic acid derivative includes phenylboronic acid (PBA), 4-trifluoromethylphenylboronic acid (p-TFMPBA), 3-trifluoromethylphenylboronic acid (m-TFMPBA), and 4-nitrophenylboronic acid.

[0010] Preferably, the solvent is water.

[0011] Preferably, the total mass percentage concentration of polyethylene glycol and water-soluble aminosiloxane is 20%-40%, and the mass percentage concentration of phenylboronic acid derivative is 0.5%-1%.

[0012] Preferably, the ratio of polyethylene glycol to water-soluble aminosiloxane is 2-4:1, more preferably 4:1.

[0013] As another objective of this invention, this invention also provides a method for preparing the above-mentioned polyethylene glycol composite liquid, comprising the following steps:

[0014] (1) Dissolve polyethylene glycol and water-soluble aminosiloxane in solvents respectively to prepare a solution with a total mass percentage concentration of 10%-60%, wherein the ratio of polyethylene glycol to water-soluble aminosiloxane is 1:1 to 8:1;

[0015] (2) Add the phenylboronic acid derivative in proportion under rapid stirring and stir until uniform to obtain the product.

[0016] As another objective of this invention, this invention also provides a method for reinforcing waterlogged bamboo and wood artifacts using the above-mentioned polyethylene glycol composite solution, comprising the following steps:

[0017] (1) Immerse the water-saturated bamboo and wood artifacts in the prepared polyethylene glycol composite liquid, or keep the artifacts in the polyethylene glycol composite liquid environment at all times through a circulating spraying method, and the treatment time is 7 days or more.

[0018] (2) Place the treated cultural relics in a room temperature environment with constant temperature and humidity to dry naturally.

[0019] Preferably, in step (1), the volume of the solution is more than 5 times the volume of the artifact; in step (2), the natural drying is carried out under the conditions of temperature 5-25℃ and humidity 60-95% RH.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] (1) Only conventional solvents, such as water, are used, which is safe, environmentally friendly and highly feasible.

[0022] (2) Compared with the polyethylene glycol single-component formulation widely used in large bamboo and wood artifacts such as shipwrecks, under natural drying conditions, the present invention can make bamboo and wood artifacts have a significantly lower shrinkage rate and a wooden artifact appearance that is closer to the ideal state.

[0023] (3) Compared with polyethylene glycol alone, the artifacts have lower hygroscopicity after being reinforced with the composite liquid of the present invention. Attached Figure Description

[0024] Figure 1 Experiment 1 compares the volume shrinkage rate of Chinese tallow wood artifacts under different formulation conditions during natural drying;

[0025] Figure 2 This study compares the volume shrinkage rates of *Sapium sebiferum* artifacts reinforced with ternary formulations and those reinforced with polyethylene glycol at different concentrations in Experiment Example 1.

[0026] Figure 3 This is a comparison of the volume shrinkage rates of *Pinus massoniana* artifact samples reinforced with ternary formulations and polyethylene glycol at different concentrations in Experiment Example 2.

[0027] Figure 4 For the comparison of equilibrium moisture content of Masson pine cultural relics samples reinforced with ternary formulation and polyethylene glycol under different relative humidity conditions in Experiment Example 2;

[0028] Figure 5Comparison of appearance after reinforcement and drying of the composite liquid in Experiment Example 2 (a: unreinforced and naturally dried, b: reinforced with 20% PEG2000 and naturally dried, c: unreinforced and freeze-dried, d: reinforced with 10% composite liquid formulation and naturally dried, e: reinforced with 20% composite liquid formulation and naturally dried, f: reinforced with 30% composite liquid formulation and naturally dried). Detailed Implementation

[0029] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] Experimental Example 1

[0031] The logs recovered from the Nanhai No. 1 shipwreck (Chinese tallow tree, absolute moisture content 862.7%, basic density 0.109 g / cm³) 3 Using this as the subject of the experiment, the same wooden block was cut into several sample pieces for comparative testing. Polyethylene glycol (PEG400, PEG2000, and PEG4000 were compared separately) and 3-aminopropyltriethoxysilane (APTES) were dissolved in water to prepare solutions with a total mass percentage concentration of 20%-60%, wherein the ratio of polyethylene glycol to water-soluble aminosiloxane was 1:1 to 8:1. A 1% mass percentage of phenylboronic acid derivative was added under rapid stirring. In this experimental example, phenylboronic acid (PBA), 4-trifluoromethylphenylboronic acid (p-TFMPBA), 3-trifluoromethylphenylboronic acid (m-TFMPBA), and 4-nitrophenylboronic acid (p-NPBA) were compared. In this formulation, the actual content of the phenylboronic acid derivative was ≤1% and controlled by its solubility. In addition, 20%, 40%, and 60% polyethylene glycol 2000 solutions were prepared as comparative examples. The waterlogged wooden artifact samples were soaked in solutions with different conditions for 7 days and then dried at 25±3℃ and 65±5%RH.

[0032] Implementation results, for example Figure 1 As shown, the volume shrinkage rate of the sample reinforced with 20% polyethylene glycol decreased from 87.7% to 71.8% in the unreinforced sample; the shrinkage rate of the sample treated with 20% PEG+TFMPBA decreased to 65.6%; the volume shrinkage rate of the sample treated with 10% PEG+10% APTES decreased to 63.9%; and the volume shrinkage rate of the sample treated with 10% PEG+10% APTES+TFMPBA decreased to 60.8%.

[0033] The above examples demonstrate that the ternary compound formulation of the present invention is superior to the binary formulation and the single PEG formulation in reducing shrinkage. The results of ternary formulation examples with different PEG / APTES ratios (e.g.) Figure 1 As shown in b), under the conditions of 2:1 to 4:1, the cultural relic samples showed the lowest shrinkage rate and the best effect in improving dimensional stability. Comparative examples of different phenylboronic acid derivatives (e.g. Figure 1 As shown in c), the lowest volume shrinkage rate of the artifact was observed when PEG, APTES, and p-TFMPBA were combined. Comparative examples using ternary formulations with different molecular weight PEGs (…) Figure 1 d) indicates that molecular weight had no significant effect, with PEG4000 showing slightly better results. Increasing the concentration can further reduce the shrinkage rate (e.g., Figure 2 The concentration of PEG can be reduced from 60% to 33.5%, and it is superior to PEG in the concentration range of 20%-60%.

[0034] Experimental Example 2

[0035] The bulkhead of the South China Sea No. 1's spruce-filled compartment (made of Masson pine wood, with an absolute moisture content of 596.8% and a basic density of 0.152 g / cm³) 3 Using this as the subject of the experiment, the same wooden block was cut into several sample pieces for comparative testing. Polyethylene glycol (PEG2000) and 3-aminopropyltriethoxysilane (APTES) were dissolved in water to prepare solutions with a total mass percentage concentration of 10%-30%, wherein the ratio of polyethylene glycol to water-soluble aminosiloxane was 4:1. 1% by mass of 4-trifluoromethylphenylboronic acid (p-TFMPBA) was added under rapid stirring conditions; the actual content of the phenylboronic acid derivative in this formulation was ≤1% and controlled by its solubility. In addition, 20%, 40%, and 60% polyethylene glycol 2000 solutions were prepared as comparative examples. The water-saturated wooden artifact samples were immersed in the solutions under the above different conditions for 7 days and then dried at 25±3℃ and 65±5% RH.

[0036] The comparison of the effects of the examples is as follows: as the concentration of the ternary formulation increases (10%-30%), the volume shrinkage rate of the cultural relic samples gradually decreases from 55% in the unreinforced form to 1.75%, demonstrating excellent dehydration and shaping effects, far superior to the reinforcement effects of PEG solutions at various concentrations. The hygroscopicity comparison of this experimental example is as follows: Figure 4 As shown, the ternary formulation treatment resulted in a lower equilibrium moisture content under high humidity conditions. For example, at 95% RH, the equilibrium moisture content of the artifact sample treated with 20% ternary formulation was 46.4%, significantly lower than that of the sample treated with PEG alone (62.4%). The appearance effect of this experimental example is compared to... Figure 5As shown, both the unreinforced, naturally dried samples and the polyethylene glycol-reinforced, naturally dried samples exhibited reduced light scattering due to shrinkage and pore collapse, resulting in a significantly darker color compared to the freeze-dried samples. The samples reinforced with the ternary formulation had a similar color to the freeze-dried samples, displaying a more natural pine wood hue, and showed better results than the PEG-reinforced, naturally dried samples.

[0037] The embodiments described above are merely illustrative of implementation methods of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A polyethylene glycol composite solution for reinforcing waterlogged bamboo and wood artifacts, characterized in that, It is composed of polyethylene glycol, water-soluble aminosiloxane, phenylboronic acid derivative and solvent; the total mass percentage concentration of polyethylene glycol and water-soluble aminosiloxane is 10%-60%, and the mass percentage concentration of phenylboronic acid derivative is 0.01-1%; wherein the mass ratio of polyethylene glycol to water-soluble aminosiloxane is 1:1 to 8:

1.

2. The polyethylene glycol composite liquid according to claim 1, characterized in that, The molecular weight of the polyethylene glycol is 200-4000.

3. The polyethylene glycol composite liquid according to claim 1, characterized in that, The water-soluble aminosiloxanes include 3-aminopropyltriethoxysilane (APTES), 3-aminopropyltrimethoxysilane (APTMS), and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (AAPTMS).

4. The polyethylene glycol composite liquid according to claim 1, characterized in that, The phenylboronic acid derivatives include phenylboronic acid (PBA), 4-trifluoromethylphenylboronic acid (p-TFMPBA), 3-trifluoromethylphenylboronic acid (m-TFMPBA), and 4-nitrophenylboronic acid (p-NPBA).

5. The polyethylene glycol composite liquid according to claim 1, characterized in that, The solvent is water.

6. The polyethylene glycol composite liquid according to claim 1, characterized in that, The total mass percentage concentration of polyethylene glycol and water-soluble aminosiloxane is 20%-40%, and the mass percentage concentration of phenylboronic acid derivative is 0.5%-1%.

7. The polyethylene glycol composite liquid according to claim 1, characterized in that, The ratio of polyethylene glycol to water-soluble aminosiloxane is 2-4:1, preferably 4:

1.

8. A method for preparing the polyethylene glycol composite liquid according to any one of claims 1-7, characterized in that, The preparation method of the polyethylene glycol composite liquid includes the following steps: (1) Dissolve polyethylene glycol and water-soluble aminosiloxane in solvents respectively to prepare a solution with a total mass percentage concentration of 10%-60%, wherein the ratio of polyethylene glycol to water-soluble aminosiloxane is 1:1 to 8:1; (2) Add the phenylboronic acid derivative in proportion under rapid stirring and stir until uniform to obtain the product.

9. A method for reinforcing waterlogged bamboo and wood artifacts using the polyethylene glycol composite liquid according to any one of claims 1-7, characterized in that, Includes the following steps: (1) Immerse the water-saturated bamboo and wood artifacts in the prepared polyethylene glycol composite liquid, or keep the artifacts in the polyethylene glycol composite liquid environment at all times through a circulating spraying method, and the treatment time is 7 days or more. (2) Place the treated cultural relics in a room temperature environment with constant temperature and humidity to dry naturally.

10. The method according to claim 9, characterized in that, In step (1), the volume of the solution is more than 5 times the volume of the artifact; in step (2), natural drying is carried out at a temperature of 5-25℃ and a humidity of 60-95%RH.

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