A polymer, its preparation and use

Abstract

The application discloses a kind of polymer and its preparation method and application, belong to the field of chemical synthesis.The application is carried out by hydrogen-containing silane and cyclopolycyclomultihydrogenated with the action of catalyst one under the action of silane hydrogenation reaction, the product after reaction is completed without purification, hydrolysis reaction is carried out again with catalyst two, after separation, washing, drying to obtain the polymer of phenolic, the amount of catalyst is less in the reaction process, but can make the conversion rate of reactant increase, the yield of product is improved, and after one-step reaction, no need to handle, by-product is green gas alkane, can directly carry out next step hydrolysis reaction, all reaction processes are room temperature, and green and environmental protection.

Description

Technical Field

[0001] This invention relates to the field of chemical synthesis, specifically to a polymer, its preparation method, and its applications. Background Technology

[0002] Cyclic polycatechins are a class of cyclic polyphenolic compounds formed by covalently linked catechin units as their basic structure. Cyclic tricatechins and cyclic tetracatechins are typical examples, exhibiting irreplaceable application value in multiple fields due to their unique cyclic structure and abundant phenolic hydroxyl active sites. Their core advantages lie in the strong chelating ability, antioxidant properties, and biocompatibility of the phenolic hydroxyl groups, making them widely applicable in fields such as biomedicine, materials science, and environmental remediation.

[0003] Cyclic polycatechols are often prepared by dealkylation of cyclic polyarsenic trioxides. However, the dealkylation process of cyclic polyarsenic trioxides is subject to harsh conditions. It usually needs to be carried out in Lewis acids such as titanium tetrachloride, aluminum trichloride, tin tetrachloride, boron trifluoride, and boron tribromide. Only boron tribromide can achieve complete demethylation. In addition, the excess of boron tribromide should be about 16 times. Only when the above conditions are met can cyclic polycatechols be prepared within 24-48 hours.

[0004] For example, John A. Hyatt in 1978 The Journal of Organic Chemistry The article "Octopus molecules in the cyclotriveratrylene series" (doi:10.1021 / jo00403a041) discloses a method for preparing hexahydroxy compounds by reacting cyclotriveratrylene with 200g of boron tribromide. The yield of the hexahydroxy compounds obtained was only 73.2%.

[0005] Ananya Chakrabarti et al. in 2005 Tetrahedron The article "Convenient synthesis of selectively substituted tribenzo [a,d,g]cyclononatrienes" (doi:10.1016 / j.tet.2005.09.101), published in Volume 61, pp. 12323-12329, discloses that the reaction of cyclotribenzoatrienes with boron tribromide produces different products under different solvent, amount of boron tribromide, temperature and reaction time conditions. Excess boron tribromide can demethylate as many methoxy groups as possible in cyclotribenzoatrienes.

[0006] However, boron tribromide is highly toxic, and the reaction process easily generates large amounts of mist that can damage the respiratory tract or corrode the skin. Furthermore, the post-processing of excess boron tribromide is complex, requiring slow addition of water at low temperatures down to -78°C or dropwise addition of pre-cooled methanol to prevent acid gas explosions. Therefore, existing methods for the dealkylation of cyclopolyhexane to prepare cyclopolycatechols are not suitable for large-scale production.

[0007] Furthermore, existing technologies rarely mention the structures of tetracyclic or polycyclic catechols, with only Joseph B et al. mentioning them in 1940. Journal of the American Chemical Society The article "Aldehyde-Resorcinol Condensations" (DOI: 10.1021 / ja01866a067) discloses the preparation of cyclic octyl-hydroxy structures by dehydration condensation between resorcinol and hydrate.

[0008] In summary, there are few existing methods for preparing cyclic polycatechols, and all of them require boron tribromide, which is highly toxic, as a catalyst. Furthermore, the amount of boron tribromide added must be 16 times in excess, making the preparation conditions for cyclic polycatechols even more demanding. The yield of cyclic polycatechols prepared in this way has not reached the ideal level, and these are all problems that urgently need to be solved. Summary of the Invention

[0009] To address the above problems, this invention provides a polymer, its preparation method, and its application. The polymer reacts with a hydrogen-containing silane and a cyclic polyhexane. The reaction requires a small amount of catalyst, yet it can increase the conversion rate of the reactants and the yield of the product. Furthermore, no further processing is required after the first step of the reaction, and the next step of hydrolysis can be carried out directly. The entire reaction process is green and environmentally friendly.

[0010] This invention provides a polymer, wherein the cyclic structure comprises n benzene rings ( ), where n is an integer ≥ 3;

[0011] Each pair of adjacent benzene rings is connected by a methylene group (-CH2-), and each benzene ring is connected to two hydroxyl groups; The two hydroxyl groups (-OH) on each benzene ring are in the ortho, meta, or para positions.

[0012] Furthermore, n is 3 or 4.

[0013] Furthermore, the hydroxyl groups in the polymer are located on the carbon atoms at positions 1 and 2 of the benzene ring.

[0014] Furthermore, the carbon atoms at positions 4 and 5 of the benzene ring in the polymer are connected by the methylene group.

[0015] Furthermore, the structural formula of the polymer is: (trimer) or (Tetramer).

[0016] The present invention also provides a method for preparing the polymer, wherein the polymer is prepared by hydrosilylation of a hydrogen-containing silane and a cyclohexane in the presence of a catalyst one. The product after the reaction is completed does not need to be purified. It is then subjected to hydrolysis again using a catalyst two. After separation, the polymer is washed and dried to obtain the polymer.

[0017] Furthermore, the yield of the polymer is ≥95%.

[0018] Furthermore, the method for preparing the polymer includes the following steps: Hydrogen-containing silanes were added to the solvent, and catalyst one was added while stirring. Cyclopolyhexane was added at room temperature, and the reaction was continued while stirring. After the reaction was completed, catalyst two was added while stirring again. The solvent was then distilled off under reduced pressure and allowed to stand. After standing, the solution separated into layers. The lower layer was taken and a precipitant was added. A light gray powder precipitated in the system. The light gray powder was filtered, washed, and dried to obtain the polymer.

[0019] Furthermore, the mass-to-volume ratio of the hydrogen-containing silane to the solvent is (5-10g):(20-80mL).

[0020] Furthermore, the structure of the hydrogen-containing silane is as follows: R1, R2, and R3 are alkyl, vinyl, phenyl, benzyl, alkylsilyl ether, and substituted phenyl and benzyl groups.

[0021] Furthermore, R1, R2, and R3 may be the same or different.

[0022] Furthermore, the structure of the hydrogen-containing silane includes at least the following: (trimethylsilane) (triethylsilane) (tert-butyldimethylsilane) (Phenylacetyldimethylsilane) (Benzyldimethylsilane) One or more of (pentamethyldisilane), where Xn is a phenyl or benzyl substituent, which can be one of H, C1-C6 alkyl, alkyl ether, cyano, nitro, or halogen, and n is one of 1-5.

[0023] Furthermore, the solvent includes polar solvents and non-polar solvents.

[0024] Furthermore, the polar solvent includes one or both of tetrahydrofuran and acetonitrile.

[0025] Furthermore, the nonpolar solvent includes one or more of aliphatic alkanes, aromatic hydrocarbons, and haloalkanes.

[0026] Furthermore, the aliphatic alkanes include one or more of petroleum ether, hexane, cyclohexane, and octane.

[0027] Furthermore, the aromatic hydrocarbon includes one or more of toluene, ethylbenzene, and chlorobenzene.

[0028] Furthermore, the haloalkane includes one or more of dichloromethane, chloroform, and dichloroethane.

[0029] Furthermore, when the solvent is a non-polar solvent, after the cyclopolyarsenic is added to the reaction, it is first distilled under reduced pressure, then methanol is added, and then catalyst two is added. The pressure of the reduced pressure distillation is 0.1-0.8 MPa, the temperature is 30-70℃, and the volume ratio of methanol to solvent is (20-80):(20-80).

[0030] Furthermore, the catalyst accounts for 0.1%-0.5% of the mass of the hydrogen-containing silane.

[0031] Furthermore, the catalyst is tris(pentafluorophenyl)borane.

[0032] Furthermore, the stirring speed after the catalyst is added is 300-500 rpm, and the stirring time is 10-30 min.

[0033] Furthermore, the molar ratio of the cyclopolyhexane to the hydrogen-containing silane is (1:6) to (1:20).

[0034] Furthermore, the cyclohexane is slowly added into the system over 30-60 minutes.

[0035] Furthermore, the general structural formula of the cyclic polyarsenic is as follows: , where R is a C1-C10 saturated alkyl group and n is a positive integer greater than 1.

[0036] Furthermore, the cyclic polyarsenic includes cyclic triarsenic ( ) or cyclotetrahydropalmatine ( ), where R is a C1-C10 saturated alkyl group.

[0037] Furthermore, the ether in the cyclotriazine includes one or more of methyl ether, diethyl ether, and butyl ether.

[0038] Furthermore, the ether in the cyclotetrahydropalmatine includes one or more of methyl ether, diethyl ether, and butyl ether.

[0039] Furthermore, the stirring speed after the addition of the cyclopolyarsenic is 300-500 rpm, and the stirring time is 1-3 h.

[0040] Furthermore, the volume ratio of the second catalyst to the solvent is (1-2):(20-80).

[0041] Furthermore, the catalyst 2 has a mass fraction of 20-50% and includes inorganic or organic acids. The inorganic acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and the organic acid is one or more of formic acid, acetic acid, butyric acid, trifluoroacetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, ethanesulfonic acid, butyric acid, and p-toluenesulfonic acid.

[0042] Furthermore, the stirring time after adding the second catalyst is 1-24 hours.

[0043] Furthermore, the pressure of the vacuum distillation is 0.1-0.5 MPa, and the temperature of the vacuum distillation is 20-60°C.

[0044] Furthermore, the settling time is 0.5-24 hours.

[0045] Further, the volume ratio of the precipitant to the solvent is (20-50):(20-80).

[0046] Furthermore, the precipitant is one or more of hexane, octane, and ethyl acetate.

[0047] Furthermore, the washing method involves washing twice with 20 mL of precipitant.

[0048] Furthermore, the drying temperature is room temperature, and the drying time is 24-48 hours.

[0049] The present invention also provides an antioxidant, wherein the raw material in the antioxidant is the polymer.

[0050] The present invention also provides a krypton fluoride photoresist, wherein the krypton fluoride photoresist is the polymer or includes the polymer.

[0051] The present invention also provides an EUV photoresist, wherein the EUV photoresist is the polymer or includes the polymer.

[0052] The beneficial effects of this invention are: This invention provides a simple, safe, and efficient method for synthesizing cyclic polycatechols. Although it involves a two-step reaction, the intermediate product does not require purification and can be directly used in the second step. It requires a small amount of catalyst, can be performed at room temperature, has a short reaction time, facilitates product separation, achieves 100% conversion of the intermediate product, and all solvents used can be recycled and reused. The byproduct of the first step is a gas that easily escapes from the reaction system. The byproduct of the second step is separated from the product phase, with most of the byproduct discarded. The product is obtained by vacuum distillation or alkane extraction. The second-step byproduct, disilane, is safe and non-toxic, and is a high-value-added chemical. The production process of this invention has low energy consumption, requires no waste treatment, and is suitable for the industrial production of cyclic polycatechols. Attached Figure Description

[0053] Figure 1 The 1H NMR spectrum of the methyl ether-based cyclotriazine described in Example 4; Figure 2 The hydrogen nuclear magnetic resonance spectrum of the liquid described in Example 4 is shown below. Figure 3 The hydrogen nuclear magnetic resonance spectrum of the trimer described in Example 4; Figure 4 This is the infrared spectrum of the reactants in Example 4. Detailed Implementation

[0054] The invention will be described in detail below with reference to the embodiments: This invention provides a polymer, its preparation method, and its application. The polymer is prepared by reacting a hydrogen-containing silane with a cyclic polyhexane. The reaction process requires a small amount of catalyst, but can improve the conversion rate of the reactants and the yield of the product. Furthermore, no further processing is required after the first step of the reaction, and the next step of the catalytic reaction can be carried out directly. The entire reaction process is green and environmentally friendly.

[0055] Example 1 This embodiment provides a polymer, specifically a trimer, the structural formula of which is: .

[0056] This embodiment also provides a method for preparing the trimer, including the following steps: 7.75 g of triethylsilane was added to 50 mL of tetrahydrofuran, followed by the addition of 10 mg of tris(pentafluorophenyl)borane. The mixture was stirred at 300 rpm for 10 min, and then 5 g of methyl ether-based cyclotriazine was slowly added at room temperature over 30 min. The mixture was stirred at 300 rpm for 1 h to allow the reaction to proceed. After the reaction was complete, 1 mL of 37% (w / w) concentrated hydrochloric acid was added and stirred for another 1 h. The solvent was then distilled off under reduced pressure at 0.1 MPa and 60 °C and allowed to stand for 30 min. After standing, the solution separated into two layers: a transparent liquid on top and a slightly yellow transparent viscous liquid on the bottom. The upper layer was poured off, and 30 mL of hexane was added to the lower viscous liquid. A light gray powder precipitated in the system. The light gray powder was filtered and washed twice with 20 mL of hexane. The mixture was then dried at room temperature for 24 h to obtain 3.9 g of trimer, with a yield of 97.5%.

[0057] Example 2 This embodiment provides a trimer identical to that in Example 1.

[0058] This embodiment also provides a method for preparing the trimer, including the following steps: 7.75 g of triethylsilane was added to 50 mL of tetrahydrofuran, followed by the addition of 10 mg of tris(pentafluorophenyl)borane. The mixture was stirred at 300 rpm for 10 min, and then 5.9 g of diethyl ether-based cyclotriazine was slowly added at room temperature over 30 min. The mixture was stirred at 300 rpm for 1 h to carry out the reaction. After the reaction was completed, 1 mL of 37% hydrochloric acid was added while stirring. After 5 min, the emulsion became a transparent solution. The mixture was stirred for another 1 h, and then the solvent was distilled off under reduced pressure at 0.1 MPa and 60 °C. The mixture was allowed to stand for 30 min. After standing, the solution separated into two layers: a transparent liquid on top and a slightly yellow transparent viscous liquid on the bottom. The upper liquid was poured off, and 30 mL of hexane was added to the lower viscous liquid. A light gray powder precipitated in the system. The light gray powder was filtered and washed twice with 20 mL of hexane. The mixture was then dried at room temperature for 24 h to obtain 3.8 g of trimer, with a yield of 95%.

[0059] Example 3 This embodiment provides a polymer, specifically a tetramer, the structural formula of which is: .

[0060] This embodiment also provides a method for preparing the tetramer, including the following steps: 7.75 g of triethylsilane was added to 50 mL of tetrahydrofuran, followed by the addition of 10 mg of tris(pentafluorophenyl)borane. The mixture was stirred at 300 rpm for 10 min, and then 5 g of methyl ether-based cyclotetrarhein was slowly added at room temperature over 30 min. The mixture was stirred at 300 rpm for 1 h to carry out the reaction. After the reaction was completed, 1 mL of 37% hydrochloric acid was added while stirring. After 5 min, the emulsion became a transparent solution. The mixture was stirred for another 1 h, and then the solvent was distilled off under reduced pressure at 0.1 MPa and 60 °C. The mixture was allowed to stand for 30 min. After standing, the solution separated into two layers: a transparent liquid on top and a slightly yellow transparent viscous liquid on the bottom. The upper liquid was poured off, and 30 mL of hexane was added to the lower viscous liquid. A light gray powder precipitated in the system. The light gray powder was filtered and washed twice with 20 mL of hexane. The mixture was then dried at room temperature for 24 h to obtain 3.9 g of tetramer, with a yield of 95%.

[0061] Example 4 This embodiment provides a trimer identical to that in Example 1, and the synthesis process is as follows: .

[0062] This embodiment also provides a method for preparing the trimer, including the following steps: 7.75 g of triethylsilane was added to 30 mL of dichloromethane, followed by the addition of 10 mg of tris(pentafluorophenyl)borane. The mixture was stirred at 300 rpm for 10 min, and then 5 g of methyl ether-based cyclotrusene was slowly added over 30 min at room temperature. The reaction was continued with stirring at 300 rpm for 1 h. After the reaction was complete, the solvent was distilled off under reduced pressure at 0.1 MPa and 60 °C to obtain a colorless, viscous liquid (cyclotrusene triethylsilane). 50 mL of methanol was then added to the liquid, and the mixture was stirred at 300 rpm for 10 min until an emulsion was formed. The mixture was then stirred further with the addition of... 1 mL of 37% hydrochloric acid was added. After 5 minutes, the emulsion became a transparent solution. After stirring for another hour, the solvent was distilled off under reduced pressure at 0.1 MPa and 60 °C and allowed to stand for 30 minutes. After standing, the solution separated into two layers: a transparent liquid on top and a slightly yellow transparent viscous liquid on the bottom. The upper liquid was poured off, and 30 mL of hexane was added to the lower viscous liquid. A light gray powder precipitated in the system. The light gray powder was filtered and washed twice with 20 mL of hexane. Then, it was dried at room temperature for 24 hours to obtain 3.8 g of trimer. The yield of the trimer (cyclotricatechin) was 95%.

[0063] like Figure 1The above is the 1H NMR spectrum of the methyl ether-based cyclotriazine described in Example 4, with deuterated chloroform as the solvent. In the figure, the singlet at δ6.86 corresponds to 2 H atoms in the benzene ring, the doublet at δ4.8 corresponds to 1 H atom in the nine-membered ring hydrogen 1, the singlet at δ3.86 corresponds to 6 H atoms in the methyl ether hydrogen, and the singlet at δ3.6 corresponds to 1 H atom in the nine-membered ring hydrogen 2.

[0064] like Figure 2 The image shows the hydrogen nuclear magnetic resonance spectrum of the liquid described in Example 4, where the solvent is deuterated chloroform, and the liquid is cyclopentaenoic acid triethyl silyl ether. The singlet at δ 6.73 corresponds to two H atoms in the benzene ring, the doublet at δ 4.6 corresponds to one H atom in the nine-membered ring hydrogen atom 1, the doublet at δ 3.4 corresponds to one H atom in the nine-membered ring hydrogen atom 2, the triplet at δ 0.9 corresponds to 54 H atoms in the methyl group, and the multiplet at δ 0.7 corresponds to 36 H atoms in the methylene group. Figure 1 The comparison shows that the peak of the hydrogen in the methyl ether group at δ3.86 of the cyclotriazine completely disappears, while the methyl and methylene groups in the silyl ether are located at δ0.9 and 0.7, respectively. The hydrogen peaks of the benzene ring and the nine-membered ring also show shifts, indicating that the position of hydrogen changes with different substituents.

[0065] like Figure 3 The image shows the proton nuclear magnetic resonance (NMR) spectrum of the trimer described in Example 4, with deuterated acetone as the solvent. The trimer in the image is cyclotricatechin. The singlet at δ7.5 corresponds to one H atom in the phenolic hydroxyl group, the singlet at δ6.79 corresponds to two H atoms in the benzene ring, the doublet at δ4.64 corresponds to one H atom in the nine-membered ring hydrogen atom 1, the doublet at δ3.36 corresponds to one H atom in the nine-membered ring hydrogen atom 2, and δ2.08 and δ2.9 correspond to the acetone peak and the peak of water impurity in acetone, respectively, proving that cyclotricatechin was successfully synthesized.

[0066] like Figure 4 The image shows the infrared spectra of the reactants in Example 4, including cyclohexane, triethylsilane, and the intermediate product (liquid). It can be seen that the intermediate product has an infrared spectrum at 2100 cm⁻¹. -1 The Si-H absorption peak disappears at 801 cm⁻¹, and the Si-C vibrational peak changes from 801 cm⁻¹. -1 The displacement reached 719cm -1 At 1260 cm, the methoxy ether in cycloastragalus was found at 1260 cm. -1 The absorption peak completely disappeared at 1500. -1 and 1600cm -1 The absorption peaks are fully preserved, and new Si-OC appears at 1310 cm⁻¹. -1 The corresponding hydrogen nuclear magnetic resonance spectrum illustrates the reaction process.

[0067] Example 5 This embodiment provides a trimer identical to that in Example 1.

[0068] This embodiment also provides a method for preparing the trimer, including the following steps: 7.75 g of tert-butyldimethylsilane was added to 30 mL of dichloromethane, followed by the addition of 20 mg of tris(pentafluorophenyl)borane. The mixture was stirred at 300 rpm for 10 min, and then 5 g of methyl ether-based cyclotrusene was slowly added over 30 min at room temperature. The reaction was continued with stirring at 300 rpm for 1 h. After the reaction was complete, the solvent was distilled off under reduced pressure at 0.1 MPa and 60 °C to obtain a colorless, viscous liquid (cyclotrusene-tert-butyldimethylsilane). 50 mL of methanol was then added to the liquid, and the mixture was stirred at 300 rpm for 10 min to form an emulsion. Continue stirring and add 1 mL of concentrated hydrochloric acid (37% by mass). After 5 minutes, the emulsion becomes a transparent solution. Stir for another hour, then distill off the solvent under reduced pressure at 0.1 MPa and 60°C and let stand for 30 minutes. After standing, the solution separates into layers: the upper layer is a transparent liquid, and the lower layer is a slightly yellow transparent viscous liquid. Pour off the upper liquid and add 30 mL of hexane to the lower viscous liquid. A light gray powder precipitates in the system. Filter the light gray powder and wash it twice with 20 mL of hexane. Then dry it at room temperature for 24 hours to obtain 3.9 g of trimer. The yield of the trimer is 97.5%.

[0069] Example 6 This embodiment provides a trimer identical to that in Example 1.

[0070] This embodiment also provides a method for preparing the trimer, including the following steps: 9.1 g of phenyldimethylsilane was added to 30 mL of dichloromethane, followed by the addition of 15 mg of tris(pentafluorophenyl)borane. The mixture was stirred at 300 rpm for 10 min, and then 5 g of methyl ether-based cyclotristalane was slowly added over 30 min at room temperature. The reaction was continued with stirring at 300 rpm for 1 h. After the reaction was complete, the solvent was distilled off under reduced pressure at 0.1 MPa and 60 °C to obtain a colorless, viscous liquid (cyclotristalane phenyldimethylsilane). 50 mL of methanol was then added to the liquid, and the mixture was stirred at 300 rpm for 10 min until an emulsion was formed. 1 mL of methanol was then added while stirring. 37% concentrated hydrochloric acid was added, and after 5 minutes the emulsion became a transparent solution. After stirring for another hour, the solvent was distilled off under reduced pressure at 0.1 MPa and 60°C, and the mixture was allowed to stand for 30 minutes. After standing, the solution separated into two layers: a transparent liquid on top and a slightly yellow transparent viscous liquid on the bottom. The upper liquid was poured off, and 30 mL of hexane was added to the lower viscous liquid. A light gray powder precipitated in the system. The light gray powder was filtered, washed twice with 20 mL of hexane, and then dried at room temperature for 24 hours to obtain 3.82 g of trimer, with a yield of 95.5%.

[0071] Example 7 This embodiment provides a trimer identical to that in Example 1.

[0072] This embodiment also provides a method for preparing the trimer, including the following steps: 11.1 g of 4-methoxyphenyldimethylsilane was added to 30 mL of dichloromethane, followed by the addition of 15 mg of tris(pentafluorophenyl)borane. The mixture was stirred at 300 rpm for 10 min, and then 5 g of methyl ether-based cyclotrusene was slowly added over 30 min at room temperature. The reaction was continued with stirring at 300 rpm for 1 h. After the reaction was complete, the solvent was distilled off under reduced pressure at 0.1 MPa and 60 °C to obtain a colorless, viscous liquid (cyclotrusene 4-methoxyphenyldimethylsilane). 50 mL of methanol was then added to the liquid, and the mixture was stirred at 300 rpm for 10 min until an emulsion was formed. 1 mL of methanol was then added while stirring. After 5 minutes of stirring with 37% concentrated hydrochloric acid, the emulsion became a transparent solution. After stirring for another hour, the solvent was distilled off under reduced pressure at 0.1 MPa and 60°C and allowed to stand for 30 minutes. After standing, the solution separated into two layers: a transparent liquid on top and a slightly yellow transparent viscous liquid on the bottom. The upper layer was poured off, and 30 mL of hexane was added to the lower viscous liquid. A light gray powder precipitated in the system. The light gray powder was filtered and washed twice with 20 mL of hexane. Then, it was dried at room temperature for 24 hours to obtain 3.9 g of trimer, with a yield of 97.5%.

[0073] Example 8 This embodiment provides a trimer identical to that in Example 1.

[0074] This embodiment also provides a method for preparing the trimer, including the following steps: 7.75 g of triethylsilane was added to 30 mL of dichloromethane, followed by the addition of 15 mg of tris(pentafluorophenyl)borane. The mixture was stirred at 300 rpm for 10 min, and then 5.9 g of diethyl ether-based cyclotrusene was slowly added over 30 min at room temperature. The reaction was continued with stirring at 300 rpm for 1 h. After the reaction was complete, the solvent was distilled off under reduced pressure at 0.1 MPa and 60 °C to obtain a colorless, viscous liquid (cyclotrusene triethylsilane). 50 mL of methanol was then added to the liquid, and the mixture was stirred at 300 rpm for 10 min until an emulsion was formed. 1 mL of methanol was then added while stirring. After 5 minutes of stirring with 37% concentrated hydrochloric acid, the emulsion became a transparent solution. After stirring for another hour, the solvent was distilled off under reduced pressure at 0.1 MPa and 60°C and allowed to stand for 30 minutes. After standing, the solution separated into two layers: a transparent liquid on top and a slightly yellow transparent viscous liquid on the bottom. The upper layer was poured off, and 30 mL of hexane was added to the lower viscous liquid. A light gray powder precipitated in the system. The light gray powder was filtered and washed twice with 20 mL of hexane. Then, it was dried at room temperature for 24 hours to obtain 3.8 g of trimer, with a yield of 95%.

[0075] Example 9 This embodiment provides a trimer identical to that in Example 1.

[0076] This embodiment also provides a method for preparing the trimer, including the following steps: 7.75 g of triethylsilane was added to 30 mL of dichloromethane, followed by the addition of 10 mg of tris(pentafluorophenyl)borane. The mixture was stirred at 300 rpm for 10 min, and then 7.8 g of butylated cyclopentaenoic acid was slowly added over 30 min at room temperature. The mixture was stirred at 300 rpm for 1 h to allow the reaction to proceed. After the reaction was complete, the solvent was distilled off under reduced pressure at 0.1 MPa and 60 °C to obtain a colorless, viscous liquid (cyclopentaenoic acid triethylsilane). 50 mL of methanol was then added to the liquid, and the mixture was stirred at 300 rpm for 10 min until an emulsion was formed. 1 mL of methanol was then added while stirring. After 5 minutes of stirring with 37% concentrated hydrochloric acid, the emulsion became a transparent solution. After stirring for another hour, the solvent was distilled off under reduced pressure at 0.1 MPa and 60°C and allowed to stand for 30 minutes. After standing, the solution separated into two layers: a transparent liquid on top and a slightly yellow transparent viscous liquid on the bottom. The upper liquid was poured off, and 30 mL of hexane was added to the lower viscous liquid. A light gray powder precipitated in the system. The light gray powder was filtered and washed twice with 20 mL of hexane, and then dried at room temperature for 24 hours to obtain 3.92 g of trimer, with a yield of 98%.

[0077] Example 10 This embodiment provides a tetramer identical to that in Example 3, and the synthesis process is as follows: .

[0078] This embodiment also provides a method for preparing the tetramer, including the following steps: 7.75 g of triethylsilane (HSiEt3) was added to 30 mL of dichloromethane, followed by the addition of 10 mg of tris(pentafluorophenyl)borane. The mixture was stirred at 300 rpm for 10 min, and then 5 g of methyl ether-based cyclotetrarhane was slowly added over 30 min at room temperature. The reaction was continued with stirring at 300 rpm for 1 h. After the reaction was complete, the solvent was distilled off under reduced pressure at 0.1 MPa and 60 °C to obtain a colorless, viscous liquid. 50 mL of methanol was then added to the liquid, and the mixture was stirred at 300 rpm for 10 min until an emulsion was formed. 1 mL of methanol was then added while stirring. After 5 minutes of stirring with 37% concentrated hydrochloric acid, the emulsion became a transparent solution. After stirring for another hour, the solvent was distilled off under reduced pressure at 0.1 MPa and 60°C and allowed to stand for 30 minutes. After standing, the solution separated into two layers: a transparent liquid on top and a slightly yellow transparent viscous liquid on the bottom. The upper liquid was poured off, and 30 mL of hexane was added to the lower viscous liquid. A light gray powder precipitated in the system. The light gray powder was filtered and washed twice with 20 mL of hexane. Then, it was dried at room temperature for 24 hours to obtain 3.9 g of tetramer, with a yield of 95% for the tetramer (cyclotetracatechin).

[0079] Comparative Example 1 This comparative example provides a trimer identical to that in Example 1.

[0080] This comparative example also provides a method for preparing the trimer, comprising the following steps: 7.75 g of triethylsilane was added to 50 mL of tetrahydrofuran, followed by the addition of 10 mg of tris(pentafluorophenyl)borane. The mixture was stirred at 300 rpm for 10 min, and then 5.9 g of diethyl ether-based cyclotriazine was slowly added at room temperature over 30 min. The mixture was stirred at 300 rpm for 1 h to allow the reaction to proceed. After the reaction was complete, 1 mL of 10% hydrochloric acid was added while stirring. After 60 min, the emulsion became a transparent solution. The mixture was stirred for another h, and then the solvent was distilled off under reduced pressure at 0.1 MPa and 60 °C. The mixture was allowed to stand for 30 min. After standing, the solution separated into two layers: a transparent liquid on top and a slightly yellow transparent viscous liquid on the bottom. The upper liquid was poured off, and 30 mL of hexane was added to the lower viscous liquid. A light gray powder precipitated in the system. The light gray powder was filtered and washed twice with 20 mL of hexane. The mixture was then dried at room temperature for 24 h to obtain 3.8 g of trimer, with a yield of 58%.

[0081] Comparative Example 2 This comparative example provides a polymer as in Example 3, specifically a tetramer.

[0082] This comparative example also provides a method for preparing the tetramer, comprising the following steps: 5 g of triethylsilane was added to 50 mL of tetrahydrofuran, followed by the addition of 10 mg of tris(pentafluorophenyl)borane. The mixture was stirred at 300 rpm for 10 min, and then 5 g of methyl ether-based cyclotetrarhane was added at room temperature for 30 min. The mixture was stirred at 300 rpm for 1 h to carry out the reaction. After the reaction was completed, 1 mL of 37% (w / w) concentrated hydrochloric acid was added and stirred for another 1 h. The solvent was then distilled off under reduced pressure at 0.1 MPa and 60 °C and allowed to stand for 30 min. After standing, the solution separated into two layers: a transparent liquid on top and a slightly yellow transparent viscous liquid on the bottom. The upper liquid was poured off, and 30 mL of hexane was added to the lower viscous liquid. A light gray powder precipitated in the system. The light gray powder was filtered and washed twice with 20 mL of hexane. The mixture was then dried at room temperature for 24 h to obtain 3.9 g of tetramer, with a yield of 61%.

[0083] As can be seen from the comparison of this embodiment and the comparative example, this application can prepare high-yield polymers, including trimers and tetramers, through a simple process. No purification is required during the reaction process. High-yield polymers can be prepared through one-step reaction and two-step catalysis, with a purity of 99.9-100%. However, when the ratio of catalyst and reactants is reduced, the catalytic efficiency during the reaction process decreases, and the polymer yield decreases significantly.

[0084] As can be seen from the above, the polymer described in this invention has a wide range of applications, low cost, and a very high market prospect.

[0085] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any other way. Any modifications or equivalent changes made based on the technical essence of the present invention shall still fall within the scope of protection claimed by the present invention.

Claims

1. A polymer, characterized in that, The polymer has a cyclic structure, which includes n benzene rings, where n is an integer ≥ 3; Each pair of adjacent benzene rings is connected by a methylene group, and each benzene ring is connected to two hydroxyl groups; The two hydroxyl groups on each benzene ring are in the ortho, meta, or para positions.

2. The polymer according to claim 1, characterized in that, The value of n is 3 or 4.

3. The polymer according to claim 2, characterized in that, The hydroxyl groups in the polymer are located on the carbon atoms at positions 1 and 2 of the benzene ring.

4. The polymer according to claim 3, characterized in that, In the polymer, the carbon atoms at positions 4 and 5 of the benzene ring are connected by the methylene group.

5. A method for preparing the polymer according to any one of claims 1-4, characterized in that, The polymer is produced by hydrosilylation of hydrogen-containing silanes and cyclohexanes under the action of catalyst one. The product after the reaction is completed does not need to be purified. It is then hydrolyzed again using catalyst two. After separation, washing and drying, the polymer is obtained.

6. The preparation method according to claim 5, characterized in that, The yield of the polymer is ≥95%.

7. The preparation method according to claim 5, characterized in that, The method for preparing the polymer includes the following steps: Hydrogen-containing silanes were added to the solvent, and catalyst one was added while stirring. Cyclopolyhexane was added at room temperature, and the reaction was continued while stirring. After the reaction was completed, catalyst two was added while stirring again. The solvent was then distilled off under reduced pressure and allowed to stand. After standing, the solution separated into layers. The lower layer was taken and a precipitant was added. A light gray powder precipitated in the system. The light gray powder was filtered, washed, and dried to obtain the polymer.

8. An antioxidant, characterized in that, The raw material in the antioxidant is the polymer described in any one of claims 1-4.

9. A krypton fluoride photoresist, characterized in that, The krypton fluoride photoresist is the polymer described in any one of claims 1-4 or includes the polymer described in any one of claims 1-4.

10. An EUV photoresist, characterized in that, The EUV photoresist is the polymer described in any one of claims 1-4 or includes the polymer described in any one of claims 1-4.

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