Contact lens compound, contact lens material composition, and contact lens

Abstract

The application relates to the technical field of high polymer materials and ophthalmic medical devices, and provides a compound for contact lenses, a contact lens material composition and a contact lens, the compound for contact lenses has the following structural formula: wherein R1 is a methylpropionyl group, an acryl group or a siloxane alkyl group; R2 is at least one of a dimethylsilyl group and a silylalkyl group, and is absent; R3 is a methylpropionyl group, an acryl group or a siloxane alkyl group; the N is a natural number between 1 and 20, and the M is a natural number between 1 and 20. The fluorosilicone chain segment and the polyethylene glycol chain segment are chemically bonded through molecular design, the problem of poor compatibility is solved, excellent hydrophilicity and uniformity are realized while the high oxygen permeability is ensured.

Description

Technical Field

[0001] This invention relates to the fields of polymer materials and ophthalmic medical devices, and more specifically to a compound for contact lenses, a contact lens material composition, and contact lenses. Background Technology

[0002] In the field of soft contact lens materials, silicone hydrogels have become the mainstream choice due to their high oxygen permeability. However, silicone components are inherently highly hydrophobic, while hydrophilic components must be introduced into the lenses to maintain wearing comfort. In existing technologies, although fluorinated siloxane monomers can provide excellent oxygen permeability, their compatibility with conventional hydrophilic monomers (such as N-vinylpyrrolidone, hydroxyethyl methacrylate, etc.) is poor, and microphase separation easily occurs during polymerization, leading to decreased lens transparency, uneven mechanical properties, or poor surface wettability.

[0003] For example, CN106256842B (BenQ Materials) discloses a contact lens material that uses a specific first siloxane polymer (Formula I, containing a terminal methacryloyloxy group) and a second siloxane polymer (Formula II, containing a polyurethane structure) combined with a hydrophilic monomer, aiming to reduce the modulus and increase the water content and oxygen permeability, but still relies on a specific siloxane structure design to balance the performance.

[0004] CN119638919A (Jiangsu Liwen Optics et al.) discloses a high oxygen permeability silicone hydrogel contact lens, which uses macromolecular siloxane I (introducing quaternary ammonium salt functional groups) and macromolecular siloxane II with narrow molecular weight distribution, combined with small molecule siloxanes, hydrophilic monomers, etc., and improves the uniformity in PP mold by optimizing the preparation process, so as to obtain a good hydrophilic surface without surface treatment. However, the preparation process involves multiple intermediate synthesis and post-processing, which requires high process control.

[0005] CN102686630A (Aokutek) relates to thermoplastic polyurethane contact lens materials based on polyethylene glycol, diisocyanate and specific diols. The polyurethane dry gel is prepared by reaction under essentially anhydrous conditions, followed by injection molding and hydration. It focuses on solving the balance between comfort and oxygen permeability of traditional materials. However, it belongs to the polyurethane system, which has a different approach to solving the compatibility and phase separation problems compared to siloxane-alkyl silicone hydrogels.

[0006] Traditional solutions often require the addition of large amounts of internal wetting agents or the use of complex surface treatment processes, which may lead to a significant decrease in oxygen permeability or complicate the manufacturing process. Therefore, how to develop a novel functional monomer that can maintain high oxygen permeability while being well miscible with hydrophilic components without delamination, in order to achieve a balance between oxygen permeability and comfort in contact lenses, is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0007] To address the shortcomings of existing technologies and solve the aforementioned problems, a compound for contact lenses, a composition of contact lens materials, and a contact lens are proposed, along with the following technical solutions:

[0008] A compound for use in contact lenses has the following structural formula:

[0009]

[0010] Wherein, R1 is methylpropionyl, acryloyl, or siloxane alkyl;

[0011] R2 is absent or is at least one of dimethylsilyl and silylalkyl;

[0012] R3 is methylpropionyl, acryloyl, or siloxane alkyl;

[0013] N is a natural number between 1 and 20, and M is a natural number between 1 and 20.

[0014] Furthermore, the structural formula is , , or

[0015] .

[0016] Furthermore, the structural formula is: or .

[0017] The present invention also provides a contact lens material composition, the raw materials of which include: the contact lens compound as described above, a hydrophilic monomer, a silica hydrophobic monomer, and a crosslinking agent.

[0018] Furthermore, the hydrophilic monomer is selected from N-vinylpyrrolidone, N,N-dimethylacetamide, hydroxyethyl methacrylate, or combinations thereof; the silicon-containing hydrophobic monomer is selected from methacryloyloxypropyltris(trimethylsiloxane)silane, methacrylate compounds containing siloxane segments, fluorosiloxane acrylate monomers, or combinations thereof.

[0019] Furthermore, the crosslinking agent is selected from dual-terminated methacrylate compounds containing siloxane segments, dual-terminated monomers of fluorosiloxane acrylates, or combinations thereof.

[0020] Furthermore, based on the total weight of the composition, the amount of the contact lens compound added is 0.1%-70%.

[0021] Furthermore, the composition also contains a photoinitiator.

[0022] A contact lens is prepared by ultraviolet light polymerization, extraction, equilibration and sterilization of the above-mentioned contact lens material composition.

[0023] Furthermore, the method for preparing the contact lens includes the following steps: (1) Weigh and mix the raw materials according to the formula;

[0024] (2) Inject the mixture into the female mold made of PP material and align the male and female molds;

[0025] (3) Irradiation under ultraviolet light source;

[0026] (4) Open the mold and take out the lens, wash with ethanol, and then wash with purified water;

[0027] (5) Place the lens in a standard phosphate solution for 1 hour to equilibrate;

[0028] (6) Pour into a PP cup, add phosphate preservation solution, seal and steam sterilize.

[0029] Due to the adoption of the above technical solutions, the beneficial technical effects of the present invention are as follows:

[0030] 1. The contact lens compound provided in this application chemically bonds fluorosiloxane segments and polyethylene glycol segments through molecular design. The high free volume of the fluorosilicone component ensures unobstructed oxygen transport channels, while the hydrophilicity and flexibility of the PEG segments improve the hydration state of the material surface. The two are covalently linked, fundamentally solving the phase separation problem caused by physical blending and achieving a simultaneous improvement in oxygen permeability and hydrophilicity.

[0031] 2. This polymer plays a dual role as both a reactive monomer and an endogenous compatibilizer in the composition, eliminating the need for additional non-reactive surfactants. This avoids the risk of eye irritation caused by the precipitation of small molecule additives, and also avoids the decrease in oxygen permeability caused by excessive hydrophilic modification. As a result, the manufactured contact lenses maintain a high Dk / t value while possessing excellent wetting angle and wearing comfort.

[0032] 3. The contact lenses prepared based on this material composition exhibit a uniform nanoscale phase domain distribution in their microstructure, resulting in minimal light scattering and high optical transparency. Furthermore, due to the introduction of flexible siloxane-PEG blocks into the crosslinking network, the material has a moderate elastic modulus and enhanced tensile strength, effectively reducing the breakage rate of the lenses during insertion and removal, and improving the durability and safety of the product. Detailed Implementation

[0033] To enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Based on the embodiments in this application, other similar embodiments obtained by those skilled in the art without creative effort should all fall within the scope of protection of this application.

[0034] A compound for use in contact lenses has the following structural formula:

[0035]

[0036] Wherein, R1 is methylpropionyl, acryloyl, or siloxane alkyl;

[0037] R2 is absent or is at least one of dimethylsilyl and silylalkyl;

[0038] R3 is methylpropionyl, acryloyl, or siloxane alkyl;

[0039] N is a natural number between 1 and 20, and M is a natural number between 1 and 20.

[0040] Unlike traditional technologies that rely on physical blending to add surfactants, this polymer forcibly binds the hydrophobic fluorosilicone segments and the hydrophilic PEG segments within the same molecule via covalent bonds. In the polymerization system, this unique block or graft structure allows it to function as both a reactive monomer and an endogenous compatibilizer. Specifically, the fluorosilicone portion tends to aggregate with the hydrophobic monomers in the system, while the PEG portion is compatible with the hydrophilic monomers. The two are linked by chemical bonds, effectively reducing the interfacial tension between the fluorosilicone component and the hydrophilic monomers, suppressing macroscopic or microscopic phase separation. This results in excellent optical transparency and wearing comfort while maintaining high oxygen permeability.

[0041] Specifically, there are several compounds used in contact lenses, as shown in Table 1.

[0042] Table 1. Relevant Indicators of Compounds Used in Contact Lenses

[0043] The specific structures represent preferred variants of general formula I with varying siloxane chain lengths, PEG polymerization degrees, and linkage methods. Compounds designated 1, 21, 22, 23, 24, 25, 26, and 3, 41, 42, 43, 44, 45, 46 are all linear or comb-shaped macromonomers with polymerizable groups at one end. During free radical polymerization, they are primarily suspended on the main crosslinking network of the contact lens as grafted side chains.

[0044] Compounds designated 5, 61, 62, 63, 64, 65, and 66 have both ends capable of participating in UV-induced polymerization reactions, chemically bonded and embedded within a three-dimensional network. The contained fluorosilicone components directly constitute the supporting structure of the oxygen permeability channels, ensuring that even at high crosslinking densities, the material's oxygen permeability does not experience a precipitous drop. Therefore, by combining these dual-end polymerization structures with the aforementioned single-end polymerization structures, synergistic regulation of the microstructure, mechanical modulus, and oxygen permeability of contact lenses can be achieved, meeting the comprehensive clinical needs for high-performance silicone hydrogel lenses.

[0045] We designed and synthesized a series of compounds to introduce fluorosilicone components to ensure high oxygen permeability, while simultaneously introducing PEG functional groups to guarantee a certain level of hydrophilicity. This allows us to maximize the hydrophilic component while maintaining the lens's oxygen permeability, ultimately resulting in lenses that offer both wearing comfort and high oxygen permeability. This effect is achieved because our compounds are miscible with both hydrophilic and hydrophobic components. In summary, we synthesized a series of compounds that allow for maximum miscibility between the hydrophilic component and the organosilicon component without delamination, while minimizing the decrease in oxygen permeability.

[0046] A contact lens material composition comprising the following raw materials: the contact lens compound as described above, a hydrophilic monomer, a silica hydrophobic monomer, and a crosslinking agent.

[0047] Specifically, contact lenses with the above-mentioned codes were prepared using compounds. The formulations of each embodiment are shown in Table 2 and Table 3 below.

[0048] Table 2 Formulation table for Examples 1-11

[0049] Table 3 Formulation table for Examples 12-18

[0050] The formulations for each comparative example are shown in Tables 4 and 5 below.

[0051] Table 4 Formulations for Comparative Examples 1-4

[0052] Table 5 Formulation table for Comparative Examples 5-9

[0053] Lens preparation steps for formulation examples and formulation comparison examples: Weigh and mix each component according to the respective formulation table; inject the mixture into a PP negative mold and quickly align the male and female molds; quickly place the mold under a 405nm UVLED light source for 30 minutes, then open the mold and remove the lens; wash the lens with ethanol for 4 hours to remove residual monomers, then wash with purified water for 4 hours to remove organic solvents, place the obtained lens in a standard phosphate solution for equilibration for 1 hour, then place the lens in a PP cup, add freshly prepared phosphate preservation solution, seal, and steam sterilize.

[0054] Oxygen permeability was measured using a CREATECH 201T oxygen permeability meter at 35°C. The unit of oxygen permeability is 10⁻⁹ (cm / s) [mLO² / (ml*hPa)]. When measured according to the principles of GB 11417, an error within ±10% is acceptable.

[0055] Code name explanation:

[0056] The structural formula of the PDMSMA compound is as follows:

[0057]

[0058] The structural formula of the PDMSFMA compound is as follows:

[0059]

[0060] The structural formula of the PDMSDIDA compound is as follows:

[0061]

[0062] The structural formula of the PDMSFDIMA compound is as follows:

[0063]

[0064] NVP: N-vinylpyrrolidone

[0065] DMA: N,N-dimethylacetamide

[0066] HEMA: Hydroxyethyl methacrylate

[0067] TRISS: Methacryloxypropyltris(trimethylsiloxane)silane

[0068] Darocur-1173: 2-Hydroxy-2-methylphenylacetone photoinitiator

[0069] The following provides the synthetic route for the compound used in contact lenses according to this application.

[0070] 1. Synthesis process of compound 1:

[0071] Synthetic route

[0072]

[0073]

[0074]

[0075] Synthesis process:

[0076] Intermediate 1-1 (4-hydroxy-3,6,9,12-tetraoxatetradecyl methacrylate): Add 50.0 g pentaethylene glycol, 200 ml DCM, and 26.6 g TEA to a reaction flask. Under N2 protection, cool to 0℃, maintain temperature at 0±5℃, and slowly add 50 ml of a DCM solution containing 22.8 g methacryloyl chloride (dropwise over 10 min). After addition, stir at 25±5℃ for 15 h. Under nitrogen protection, cool the system to 0℃, quench the reaction with 100 ml water, stir, and separate the layers. Wash with water (2*100 ml), wash with saturated sodium chloride (1*100 ml), and concentrate to dryness at 35℃ to obtain a pale yellow oil. Elute by column chromatography (hexane:EA=5:1) to obtain 21.6 g of a colorless oil. Yield: 34%. H-NMR (400MHz, CDCl3) δ 6.14 (dq, 1H, CH3C=CH2),5.60(dt,1H,CH3C= CH2),4.32(m,2H,CH3CH2=C-COOCH2),3.72

[0077] (m,4H,CH3CH2=C-COOCH2CH2OCH2CH2OCH2CH2OCH2CH2OCH2CH2OH),3.68(d,12H,CH3CH2=C-COOCH2CH2OCH2CH2OCH2CH2OCH2CH2OCH2CH2OH),3.63(m,2H,CH3CH2COOCH2CH2OCH2CH2OC LCMS: M / Z calc .for:C14H26O7:306, 329(M+23).

[0078] Intermediate 1-2 (1-chloro-1,1,3,5,7-pentamethyl-3,5,7-tris(3,3,3-trifluoropropyl)tetrasiloxane):

[0079] Add 50g of trifluoropropylmethylcyclotrisiloxane, 10.5g of dimethylchlorosilane, and TFA (1.2g, 0.1mmol) to the reaction flask. Stir at 25-30℃ for 24h. Purify by distillation (5pa, 40℃). A total of 45.8g of product was collected, with Y=76.3%.

[0080] Intermediate 1-3 (1,1,3,5,7-pentamethyl-3,5,7-tris(3,3,3-trifluoropropyl)tetrasiloxane-1-ol):

[0081] Add 45g of intermediate 1-2 and 135ml of n-hexane to the reaction flask. Under nitrogen protection, cool to 5℃, then control the temperature to 5-10℃. Add 60ml of 6.7g of NaHCO3 aqueous solution dropwise. After the addition is complete, continue stirring at 5-10℃ for 30min. Remove the ice bath and stir at 25℃ for 2h. Cool the system to 5℃ and quench with 90ml of saturated ammonium chloride solution. Wash with water (2*90ml) and saturated sodium chloride solution (1*90ml). Concentrate to dryness at 35℃. Purify by distillation (5pa, 60℃). Collect a total of 38.3g of product. Y=88%. H-NMR (400MHz, CDCl3) δ 4.70 (p, 1H, H-Si), 2.19 [t, 1H,H-(Si(CH3)-CH2-CH2-CF3)3-Si(CH3)2-OH],2.11[m,6H,H-(Si(CH3)-CH2-CH2-CF3)3-Si(CH3)2-OH],0.66[m,6H,H-(Si(CH3)-

[0082] for C14H29F9O4Si4: 545; found 568([M+23]).

[0083] Intermediate 1-4 (1-Butyl-1,1,3,5,7,9-heptamethyl-5,7,9-tris(3,3,3-trifluoropropyl)pentasiloxane): Add 15.0 g of intermediate 1-3 and 30 ml of toluene to a reaction flask. Under nitrogen protection, cool to 0°C, control the temperature to 0-5°C, and add 2.4 g of pyridine dropwise. After the addition is complete, continue to control the temperature to 0-5°C, and add 15 ml of a toluene solution containing 4.4 g of n-butyldimethylchlorosilane dropwise. After the addition is complete, remove the ice bath, stir at 25°C for 3 hours, cool the system to 5°C, quench with 78 ml of saturated sodium bicarbonate solution, wash with water (2*78 ml), wash with saturated sodium chloride solution (1*78 ml), concentrate to dryness at 60°C, and purify by distillation (5.0 Pa, 87°C). A total of 11.7 g of product was collected, Y = 64%. H-NMR(400MHz, CDCl3)δ4.7(tq,1H,H-Si),1.96 [m,6H,H-(Si-CH3-CH2-CH2-CF3-O)3-],1.34[m,4H,-O-(CH3)2Si-CH2CH2CH2CH3],0.8[t,

[0084] 3H,-O-(CH3)2Si-CH2CH2CH2CH3],0.57[m,6H,H-(Si-CH3-CH2-CH2-CF3-O)3-],0.46[m,2H,-O-(CH3)2Si-CH2CH2CH2CH3],0.1[s,6H,-Si(CH3)2- O-Si(CH3)2-CH2CH2CH2CH3],0.04[s,9H,H-(Si-CH3-CH2-CH2-CF3-O)3-],-0.08[s,6H,-Si(CH3)2-O-Si(CH3)2-CH2CH2CH2CH3]ppm,MALDI-TOF: m / z Cal

[0085] c. ForC20H43F9O4Si5: 659; found 698([M+39]).

[0086] Intermediate 1-5 [1-Butyl-9-chloro-1,1,3,3,5,7,9-heptamethyl-5,7,9-tris(3,3,3-trifluoropropyl)pentasiloxane]: Add 30 ml of dichloromethane and 100 mg of PdCl to the reaction flask. Under nitrogen protection, cool to 0 °C and add 10.0 g of intermediate 1-4 dropwise. After the addition is complete, stir at 20-25 °C for 2 h under nitrogen protection and proceed directly to the next step.

[0087] Compound 1: [2-(9-butoxy-1,3,5,7,7,9,9-heptamethyl-1,3,5-tris(3,3,3-trifluoropropyl)pentasiloxane)-3,6,9,12-tetraoxytetradecyl methacrylate]: Add 4.6 g of intermediate 1-1, 50 ml of dichloromethane, and 1.44 g of pyridine to a reaction flask. Under nitrogen protection, cool to 0°C, maintain the temperature at 0-5°C, and add intermediate 1 dropwise. After the reaction solution of -5°C was added dropwise, the mixture was stirred at 25±5°C for 2.5 hours. The system was then cooled to 0°C, and 50 ml of water was added dropwise at 0-5°C to quench the reaction. The mixture was stirred, allowed to stand, and separated. The solution was washed with water (2*50 ml) and saturated with sodium chloride (1*50 ml). The solution was concentrated to dryness at 35°C and eluted by column chromatography (200-300 mesh silica gel, hexane:EA=90:1) to obtain 5.1 g of colorless oil, with a yield of 35%.

[0088] 2. Synthesis process of compound 3:

[0089] Synthetic route

[0090]

[0091]

[0092]

[0093] Synthesis process:

[0094] Intermediate 3-1 (16,16-dimethyl-3,6,9,12,15-pentoxo-16-silicoeicosan-1-ol):

[0095] Add 25g pentaethylene glycol, 125ml dichloromethane, and 11.8g triethylamine to the reaction flask. Under nitrogen protection, cool to 0℃ and maintain the temperature between 0-5℃. Add 16.6g n-butyldimethylchlorosilane dropwise. After the addition is complete, stir at 25±5℃ for 3 hours. Cool the system to 0-5℃ and quench with 100ml water. Stir, allow to stand, separate, wash with water (2*100ml), wash with saturated sodium chloride (1*100ml), concentrate to dryness at 35℃, and elute by column chromatography (hexane:EA=8:1). Collect 9.1g of colorless oily substance. Y=24.6%. ¹H-NMR (400MHz, CDCl₃) δ 3.71[m,20H,H(OCH2CH2)5OSi(CH3)2CH2CH2CH2CH3],2.71[t,1H,H(OCH2CH2)5OSi(CH3)2CH2CH 2CH2CH3],1.67[m,2H,H(OCH2CH2)5OSi(CH3)2CH2CH2CH2CH3],1.35[m,2H,H(OCH2CH2)5OSi(CH 3)2CH2CH2CH2CH3],0.8[t,3H,H(OCH2CH2)5OSi(CH3)2CH2CH2CH2CH3],0.64[t,2H,H(OCH2CH2) 5OSi(CH3)2CH2CH2CH2CH3],0.11[s,6H,H(OCH2CH2)5OSi(CH3)2CH2CH2CH2CH3]ppm,MALDI-TOF: m / z calc.for:C16H36O6Si:353; Found: 376([M+23]).

[0096] Intermediate 3-2 [(2-(1,3-dimethyl-1,3-bis(3,3,3-trifluoropropyl)disiloxyl)oxy)-1,1,3-trimethyl-3-(3,3,3-trifluoropropyl)-2,3,3,3-tetrasiloxyl methacrylate]:

[0097] Add 20.0 g of intermediate 1-3, 100 ml of dichloromethane, and 3.2 g of pyridine to the reaction flask. Under nitrogen protection, cool to 0°C and maintain the temperature at 0-5°C. Add 4.0 g of methacrylamide chloride dropwise. After the addition is complete, stir at 25±5°C for 3 h. Cool the system to 0-5°C and quench with 50 ml of water. Stir, allow to stand, separate, wash with water (2*50 ml), wash with saturated sodium chloride (1*50 ml), concentrate to dryness at 35°C, and elute by column chromatography (hexane:EA=90:1). Collect 14.2 g of colorless oil. Y=63%. H-NMR (400MHz, CDCl3) δ 6.1 (dq,

[0098] 1H,CH3CH2=CC=O),5.8(tq,1H,CH3CH2=CC=O),4.7[tq,1H,-(OSiCH3CH2CH2CF3)3-H],2.4[t,6H,C H3CH2=C-COO(CH3)2Si(OCH3SiCH2CH2CF3)3-H],1.9[m,3H,CH3CH2=C-COO(CH3)2Si(OCH3SiCH2CH 2CF3)3-H],0.7[tdq,6H,CH3CH2=C-COO(CH3)2Si(OCH3SiCH2CH2CF3)3-H],0.17[s,9H,CH3CH2=C- COO(CH3)2Si(OCH3SiCH2CH2CF3)3-H],0.07[d,6H,CH3CH2=C-COO(CH3)2Si(OCH3SiCH2CH2CF3)3- H]ppm,MALDI-TOF: m / zcalc.for:C18H33F9O5Si4:613; found: 636([M+23]).

[0099] Intermediate 3-3 [2-((3-chloro-1,3-dimethyl-1,3-bis(3,3,3-trifluoropropyl)disiloxyl)oxy)-1,1,3-trimethyl-3-(3,3,3-trifluoropropyl)-2,3,3-trisiloxyl methacrylate]:

[0100] Add 42 ml of dichloromethane and 140 mg of Pdcl to the reaction flask. Under nitrogen protection, cool to 0 °C and control the temperature at 0-5 °C. Add 14.0 g of intermediate 3-2 dropwise. After the addition is complete, stir at 25 ± 5 °C for 2 h. Monitor with GC and proceed directly to the next step.

[0101] Compound 3 [2,5,7,24,24-pentamethyl-3-(methyl(3,3,3-trifluoropropyl)-13-silyl)-5,7-bis(3,3,3-3-trifluoropropyl)-313,4,6,8,11,14,17,20,23-nonoxy-2,5,7,24-tetrasilicostacadec-2-ylmethacrylate]:

[0102] Add 4.1 g of intermediate 3-1, 35 ml of dichloromethane, and 1.0 g of pyridine to the reaction flask. Under nitrogen protection, cool to 0°C and maintain the temperature at 0-5°C. Add half of the reaction solution of intermediate 3-3 dropwise. After the addition is complete, stir at 25±5°C for 2 hours. Quench the solution with 30 ml of water. Stir, let stand, separate the contents, wash with water (2*30 ml), wash with saturated sodium chloride (1*30 ml), concentrate to dryness at 35°C, concentrate to dryness at 35°C, and elute by column chromatography (hexane:EA=100:1). Collect 4.4 g of colorless oily substance. Y=39%. ¹H NMR (400MHz, CDCl₃) δ 6.1 (dq, 1H,

[0103] CH3CH2=C),5.6(dt,1H,CH3CH2=C),3.6[m,20H,-(O-CH2-CH2)5-O-],2.03[qt,6H,-(OCH3SiCH2-CH2-CF3)3-],1 .9(m,3H,CH3CH2=C),1.55[m,2H,-(CH3)2Si-CH2-CH2-H2-CH3)],1.35[m,2H-(CH3)2Si-CH2-CH2-CH2-CH3)],0. 89(t,3H,-(CH3)2Si-CH2-CH2-CH2-CH3)],0.67[m,6H,-(OCH3SiCH2-CH2-CF3)3-],0.5[m,2H,-(CH3)2Si-CH2-C H2-CH2-CH3)],0.15[s,21H,-(CH3)2Si-(OCH3SiCH2-CH2-CF3)3-(CH3)2Si-CH2-CH2-CH2-CH3)]ppm,MALDI-TOF: m / z calc.for:C34H67F9O 11Si5:693; found: 716([M+23]).

[0104] 3. Synthesis process of compound 5

[0105] Synthetic route

[0106]

[0107] Synthesis process

[0108] Compound 5 [2,4,6,8-tetramethyl-4,6,8-tris(3,3,3-trifluoropropyl)-3,5,7,9,12,15,18,21-octaoxa-2,4,6,8-trisilylation-2,23-dimethylbis(2-methacrylate)]:

[0109] Add 3.5g of intermediate 1-1, 21ml of dichloromethane, and 1.1g of pyridine to the reaction flask. Under nitrogen protection, cool to 0℃ and maintain the temperature at 0-5℃. Add half of the reaction solution of intermediate 3-3 dropwise. After the addition is complete, stir at 25±5℃ for 2 hours. Quench with 30ml of water. Stir, let stand, separate, wash with water (2*30ml), wash with saturated sodium chloride (1*30ml), concentrate to dryness at 35℃, concentrate to dryness at 35℃, and elute by column chromatography (hexane:EA=100:1). Collect a total of 5.6g of colorless oily substance. Y=53.4%. H-NMR (400MHz, CDCl3) δ6.1 (dp, 2H, C

[0110] H3CH2=C),5.8(m,2H,CH3CH2=C),3.6[m,20H,-(O-CH2-CH2)5-O-],2.03[qt,6H,-O(CH3SiOCH2-CH2-CF3)3-],1.9(m,6H,CH3CH2=C)2,0.67[m,6H,-O(C H3SiOCH2-CH2-CF3)3-],0.17[s,9H,-O(CH3SiOCH2-CH2-CF3)3-(CH3)2Si-O-],0.11[s,6H,-O(CH3SiOCH2-CH2-CF3)3-(CH3)2Si-O-]ppm,MALDI-TOF: m / zcalc.for:C32H57F9O12Si4:917 Found: 940 ([M+23])

[0111] 4. Synthesis process of compounds 21, 22, and 23

[0112] Synthetic route

[0113]

[0114] Synthesis process

[0115] Intermediate (21, 22, 23)-1:

[0116] Add 100g of trifluoropropylmethylcyclotrisiloxane, 200ml of n-hexane, and 10.0g of tetramethylammonium hydroxide to a reaction flask. Under nitrogen protection, cool to 0℃ and maintain the temperature at 0-5℃. Add 40.4g of 1-butyl-1,1,3,3-tetramethyldisiloxane dropwise. After the addition is complete, stir at 25-30℃ for 3.5h. Cool the system to 0℃ and quench with 100ml of water. Stir, allow to stand, separate the contents, wash with water (2 x 100ml), wash with saturated sodium chloride (1 x 100ml), dry with anhydrous sodium sulfate for 1h, filter, and concentrate to dryness at 30℃. A total of 134g of colorless oily substance was obtained, with Y=97%.

[0117] Three-stage distillation: The fractions were collected in three stages. The first stage: 21-1 (n≈1-5, 5.0 Pa, 55℃), a total of 56 g of fraction was collected. The second stage: 22-1 (n≈4-10, 5.0 Pa, 135℃), a total of 40.8 g of fraction was collected. The third stage: 23-1 (n≈9-15), which was the remaining substrate, a total of 35.4 g of fraction was collected.

[0118] 21-2 (n≈1-5): Add 240mg Pdcl and 72ml dichloromethane to the reaction flask. Under nitrogen protection, cool to 5℃ and control the temperature at 5-10℃. Add 24.0g of intermediate 21-1 dropwise. After the addition is complete, stir at 25±5℃ for 2h and concentrate to dryness at 40℃ to obtain 24.1g of oily product, which can be directly added to the next step.

[0119] 22-2 (n≈4-10): Add 240mg Pdcl and 72ml dichloromethane to the reaction flask. Under nitrogen protection, cool to 5℃ and control the temperature at 5-10℃. Add 24.0g of intermediate 22-1 dropwise. After the addition is complete, stir at 25±5℃ for 2h and concentrate to dryness at 40℃ to obtain 24.06g of oily product, which can be directly added to the next step.

[0120] 23-2 (n≈9-15): Add 240mg Pdcl and 72ml dichloromethane to the reaction flask. Under nitrogen protection, cool to 5℃ and control the temperature at 5-10℃. Add 24.0g of intermediate 23-1 dropwise. After the addition is complete, stir at 25±5℃ for 2h and concentrate to dryness at 40℃ to obtain 24.28g of oily product, which can be directly added to the next step.

[0121] Compounds 21, 22, and 23:

[0122] Compound 21 (n≈1-5, m≈7): Add 12.0 g of intermediate 21-2, 45 ml of dichloromethane, and 1.7 g of pyridine to a reaction flask. Under nitrogen protection, cool to 0°C and maintain the temperature at 0-5°C. Add 15 ml of dichloromethane containing 6.9 g of poly(ethylene glycol) methacrylate (Mn:400). After the addition is complete, stir at 25±5°C for 2.5 h. Cool the system to 0°C and add 50 ml of water to quench the reaction. Stir, let stand, separate the contents, wash with water (2*50 ml), wash with saturated brine (1*50 ml), concentrate to dryness at 35°C, and elute and purify by column chromatography (hexane:EA=80:1) to obtain 6.9 g of colorless transparent oily product, Y=37.0%.

[0123] Compound 22 (n≈4-10, m≈7): 12.0 g of intermediate 22-2, 45 ml of dichloromethane, and 0.9 g of pyridine were added to a reaction flask. Under nitrogen protection, the mixture was cooled to 0°C and maintained at 0-5°C. 15 ml of dichloromethane containing 3.6 g of poly(ethylene glycol) methacrylate (Mn:400) was added dropwise. After the addition was complete, the mixture was stirred at 25±5°C for 2.5 h. The system was then cooled to 0°C, and 50 ml of water was added dropwise to quench the reaction. The mixture was stirred, allowed to stand, separated, and washed with water (2*50 ml), then washed with saturated brine (1*50 ml). The mixture was concentrated to dryness at 35°C, and purified by column chromatography (hexane:EA=80:1) to obtain 6.47 g of a colorless, transparent oily product, Y=41%.

[0124] Compound 23 (n≈9-15, m≈7): 12.0 g of intermediate 23-2, 45 ml of dichloromethane, and 0.54 g of pyridine were added to a reaction flask. Under nitrogen protection, the mixture was cooled to 0°C and maintained at 0-5°C. 15.0 ml of dichloromethane containing 2.3 g of poly(ethylene glycol) methacrylate (Mn:400) was added dropwise. After the addition was complete, the mixture was stirred at 25±5°C for 2.5 h. The system was then cooled to 0°C, and 50 ml of water was added dropwise to quench the reaction. The mixture was stirred, allowed to stand, separated, and washed with water (2*50 ml), then with saturated brine (1*50 ml). The solution was concentrated to dryness at 35°C, and purified by column chromatography (hexane:EA=80:1) to obtain 5.12 g of a colorless, transparent oily product, Y=35.8%.

[0125] 5. Synthesis process of compounds 24, 25, and 26

[0126] Synthetic route

[0127]

[0128] Synthesis process

[0129] Compounds 24, 25, and 26:

[0130] Compound 24 (n≈1-5, m≈20): 12g of intermediate 21-2, 45ml of dichloromethane, and 1.7g of pyridine were added to a reaction flask. Under nitrogen protection, the mixture was cooled to 0℃ and maintained at 0-5℃. 15ml of dichloromethane containing 16g of poly(ethylene glycol) methacrylate (Mn:950) was added dropwise. After the addition was complete, the mixture was stirred at 25±5℃ for 2.5h. The system was then cooled to 0℃, and 50ml of water was added dropwise to quench the reaction. The mixture was stirred, allowed to stand, separated, and washed with water (2*50ml), then washed with saturated saline (1*50ml). The mixture was concentrated to dryness at 35℃, and purified by column chromatography (hexane:EA=80:1) to obtain 10.6g of a colorless, transparent oily product with Y==37.8%.

[0131] Compound 25 (n≈4-10, m≈20): 12.0 g of intermediate 22-2, 45 ml of dichloromethane, and 0.9 g of pyridine were added to a reaction flask. Under nitrogen protection, the mixture was cooled to 0°C and maintained at 0-5°C. 15.0 ml of dichloromethane containing 8.6 g of poly(ethylene glycol) methacrylate (Mn:950) was added dropwise. After the addition was complete, the mixture was stirred at 25±5°C for 2.5 h. The system was then cooled to 0°C, and 50 ml of water was added dropwise to quench the reaction. The mixture was stirred, allowed to stand, separated, and washed with water (2*50 ml), then with saturated brine (1*50 ml). The solution was concentrated to dryness at 35°C, and purified by column chromatography (hexane:EA=80:1) to obtain 7.37 g of a colorless, transparent oily product, Y=35.8%.

[0132] Compound 26 (n≈9-15, m≈20): 12.0 g of intermediate 23-2, 45 ml of dichloromethane, and 0.54 g of pyridine were added to a reaction flask. Under nitrogen protection, the mixture was cooled to 0°C and maintained at 0-5°C. 5.4 g of poly(ethylene glycol) methacrylate (Mn:950) in 15.0 ml of dichloromethane was added dropwise. After the addition was complete, the mixture was stirred at 25±5°C for 2.5 h. The system was then cooled to 0°C, and 50 ml of water was added dropwise to quench the reaction. The mixture was stirred, allowed to stand, separated, and washed with water (2*50 ml), then with saturated saline (1*50 ml). The mixture was concentrated to dryness at 35°C, and purified by column chromatography (hexane:EA=80:1) to obtain 6.05 g of a colorless, transparent oily product, Y=34.8%.

[0133] 6. Synthesis process of compounds 41, 42, and 43

[0134] Synthetic route

[0135]

[0136]

[0137] Synthesis process

[0138] Intermediate S1:

[0139] Add 50.0g PEG-300 (m≈7), 200ml dichloromethane, and 17.2g triethylamine to the reaction flask. Under nitrogen protection, cool to 0℃ and maintain the temperature at 0-5℃. Add 50ml of a dichloromethane solution containing 24.1g n-butyldimethylchlorosilane. After the addition is complete, stir at 20-25℃ for 3 hours. Quench the solution with 150ml of water. Stir, let stand, separate the contents, wash with water (2*150ml), wash with saturated sodium chloride (1*150ml), concentrate to dryness at 35℃, concentrate to dryness at 35℃, and elute by column chromatography (hexane:EA=8:1). A total of 25.6g of colorless oily substance was collected, Y=37.8%.

[0140] Intermediates 41-1, 42-1, and 43-1:

[0141] Add 240g of trifluoropropylmethylcyclotrisiloxane and 15.36g of trifluoromethanesulfonic acid to the reaction flask. Under nitrogen protection, lower the temperature to 0℃ and control the temperature at 0-5℃. Add 52.8g of dimethylchlorosilane dropwise. After the addition is complete, stir at 25-30℃ for 3.5h. Collect a total of 292g of product. Distill in three stages: Stage 1: 41-1 (n≈1-6, 5.0pa, 50℃), collect 107.8g of fraction; Stage 2: 42-1 (n≈5-12, 5.0pa, 135℃), collect 92.1g of fraction; Stage 3: 43-1 (n≈9-17, remaining fraction), collect 86.4g of fraction.

[0142] 41-2 (m≈7, n≈1-6): Add 12.3g of intermediate S1, 60ml of toluene, and 2.4g of pyridine to the reaction flask. Under nitrogen protection, cool to 0℃ and maintain the temperature at 0-5℃. Add 20.0g of intermediate 41-1 dropwise. After the addition is complete, stir at 20-25℃ for 3 hours. Cool the system to 0℃ and quench with 60ml of water. Stir, let stand, separate, wash with water (2*60ml), wash with saturated sodium chloride (1*60ml), concentrate to dryness at 60℃, and elute by column chromatography (hexane:EA=80:1). Collect a total of 14.7g of colorless oily substance, Y=45.5%.

[0143] 42-2 (m≈7, n≈5-12): Add 6.6g of intermediate S1, 60ml of toluene, and 1.29g of pyridine to the reaction flask. Under nitrogen protection, cool to 0℃ and maintain the temperature at 0-5℃. Add 20.0g of intermediate 42-1 dropwise. After the addition is complete, stir at 20-25℃ for 3 hours. Cool the system to 0℃ and quench with 60ml of water. Stir, let stand, separate, wash with water (2*60ml), wash with saturated sodium chloride (1*60ml), concentrate to dryness at 60℃, and elute by column chromatography (hexane:EA=80:1). A total of 11.4g of colorless oily substance was collected, Y=42.8%.

[0144] 43-2 (m≈7, n≈9-17): Add 4.2g of intermediate S1, 60ml of toluene, and 0.8g of pyridine to the reaction flask. Under nitrogen protection, cool to 0℃ and maintain the temperature at 0-5℃. Add 20g of intermediate 43-1 dropwise. After the addition is complete, stir at 20-25℃ for 3 hours. Cool the system to 0℃ and quench with 60ml of water. Stir, let stand, separate, wash with water (2*60ml), wash with saturated sodium chloride (1*60ml), concentrate to dryness at 60℃, and elute by column chromatography (hexane:EA=80:1). Collect a total of 10.8g of colorless oily substance, Y=45%.

[0145] 41-3 (m≈7, n≈1-6): Add 30ml of 1,4-dioxane, 11ml of H2O, and 170mg of pd / c to the reaction flask. Under nitrogen protection, cool to 5℃, control the temperature to 5-10℃, and add 10.0g of intermediate 41-2 dropwise. After the addition is complete, continue stirring at 5-10℃ for 3 hours. Remove the ice bath, stir at 25±5℃ for 1 hour, add 30ml of toluene to the reaction flask, add 25g of diatomaceous earth for filtration, rinse with 10ml of toluene, rinse with 50ml of water, stir, let stand, separate the liquid, wash with water (2*50ml), wash with saturated sodium chloride (1*50ml), concentrate to dryness at 60℃, and elute by column chromatography (hexane:EA=50:1). A total of 8.25g of colorless oily substance was collected, Y=82.5%.

[0146] 42-3 (m≈7, n≈5-12): Add 30ml of 1,4-dioxane, 11ml of H2O, and 170mgpd / c to the reaction flask. Under nitrogen protection, cool to 5℃, control the temperature to 5-10℃, and add 10.0g of intermediate 42-2 dropwise. After the addition is complete, continue stirring at 5-10℃ for 3 hours. Remove the ice bath, stir at 25±5℃ for 1 hour, add 30ml of toluene to the reaction flask, add 25g of diatomaceous earth for filtration, rinse with 10ml of toluene, rinse with 50ml of water, stir, let stand, separate the liquid, wash with water (2*50ml), wash with saturated sodium chloride (1*50ml), concentrate to dryness at 60℃, and elute by column chromatography (hexane:EA=50:1). A total of 7.8g of colorless oily substance was collected, Y=78.0%.

[0147] 43-3 (m≈7, n≈9-17): Add 30ml of 1,4-dioxane, 11ml of H2O, and 170mgpd / c to the reaction flask. Under nitrogen protection, cool to 5℃, control the temperature to 5-10℃, and add 10.0g of intermediate 43-2 dropwise. After the addition is complete, continue stirring at 5-10℃ for 3 hours. Remove the ice bath, stir at 25±5℃ for 1 hour, add 30ml of toluene to the reaction flask, filter with 25g of diatomaceous earth, rinse with 10ml of toluene, rinse with 50ml of water, stir, let stand, separate the liquid, wash with water (2*50ml), wash with saturated sodium chloride (1*50ml), concentrate to dryness at 60℃, and elute by column chromatography (hexane:EA=50:1). A total of 8.7g of colorless oily substance was collected, Y=87.0%.

[0148] Compounds 41, 42, and 43:

[0149] Compound 41 (m≈7, n≈1-6): Add 7.5g of intermediate 41-3, 22.5ml of dimethylchlorosilane, and 545mg of pyridine to a reaction flask. Under nitrogen protection, cool to 5℃, control the temperature to 5-10℃, and add 725mg of methacryloyl chloride dropwise. After the addition is complete, stir at 25±5℃ for 2.5h. Cool the system to 0℃, add 30ml of water to quench the reaction mixture, stir, let stand, separate the layers, wash with water (2*30ml), wash with saturated sodium chloride (1*30ml), concentrate to dryness at 35℃, and elute by column chromatography (hexane:EA=90:1). A total of 3.72g of colorless oily substance was collected, Y=45%.

[0150] Compound 42 (m≈7, n≈5-12): 7.5 g of intermediate 42-3, 22.5 ml of dimethylchlorosilane, and 352 mg of pyridine were added to the reaction flask. Under nitrogen protection, the mixture was cooled to 5 °C, and then controlled at 5-10 °C. 469 mg of methacryloyl chloride was added dropwise. After the addition was complete, the mixture was stirred at 25±5 °C for 2.5 h. The system was then cooled to 0 °C, and 30 ml of water was added to quench the reaction mixture. The mixture was stirred, allowed to stand, and separated. The mixture was washed with water (2*30 ml) and saturated sodium chloride (1*30 ml). The mixture was concentrated to dryness at 35 °C. Column chromatography was performed (hexane:EA=90:1), and a total of 2.99 g of colorless oily substance was collected. Y=37.5%.

[0151] Compound 43 (m≈7, n≈9-17) was reacted by adding 7.5 g of intermediate 42-3, 22.5 ml of dimethylchlorosilane, and 244 mg of pyridine to a reaction flask. Under nitrogen protection, the mixture was cooled to 5 °C and then controlled at 5-10 °C. 325 mg of methacryloyl chloride was added dropwise. After the addition was complete, the mixture was stirred at 25±5 °C for 2.5 h. The mixture was then cooled to 0 °C and quenched with 30 ml of water. The mixture was stirred, allowed to stand, and separated. It was washed with water (2*30 ml) and saturated sodium chloride (1*30 ml). The mixture was concentrated to dryness at 35 °C and eluted by column chromatography (hexane:EA=100:1). A total of 3.17 g of colorless oily substance was collected, with a Y=40.5%.

[0152] 7. Synthesis process of compounds 44, 45, and 46

[0153] Synthetic route

[0154]

[0155]

[0156] Synthesis process

[0157] Intermediate S2:

[0158] Add 75.0g PEG-900 (m≈20), 300ml dichloromethane, and 9.3g triethylamine to the reaction flask. Under nitrogen protection, cool to 0℃ and control the temperature at 0-5℃. Add 75ml of a dichloromethane solution containing 13.1g n-butyldimethylchlorosilane. After the addition is complete, stir at 20-25℃ for 3h. Cool the system to 0℃ and quench with 150ml of water. Stir, let stand, separate, wash with water (2*150ml), wash with saturated sodium chloride (1*150ml), concentrate to dryness at 35℃, concentrate to dryness at 35℃, and elute by column chromatography (hexane:EA=8:1). A total of 30.2g of colorless oily substance was collected, Y=35.7%.

[0159] Intermediates 44-1, 45-1, 46-1:

[0160] 44-1 (m≈20, n≈1-6): Add 14.1g of intermediate S2, 30ml of toluene, and 1.2g of pyridine to the reaction flask. Under nitrogen protection, cool to 0℃ and control the temperature at 0-5℃. Add 10.0g of intermediate 41-1 dropwise. After the addition is complete, stir at 20-25℃ for 3h. Cool the system to 0℃ and quench with 30ml of water. Stir, let stand, separate, wash with water (2*30ml), wash with saturated sodium chloride (1*30ml), concentrate to dryness at 60℃, and elute by column chromatography (hexane:EA=80:1). A total of 11.6g of colorless oily substance was collected, Y=49.2%.

[0161] 45-1 (m≈20, n≈5-12): Add 7.5g of intermediate S2, 30ml of toluene, and 0.65g of pyridine to the reaction flask. Under nitrogen protection, cool to 0℃ and control the temperature at 0-5℃. Add 10.0g of intermediate 42-1 dropwise. After the addition is complete, stir at 20-25℃ for 3h. Cool the system to 0℃ and quench with 30ml of water. Stir, let stand, separate, wash with water (2*30ml), wash with saturated sodium chloride (1*30ml), concentrate to dryness at 60℃, and elute by column chromatography (hexane:EA=80:1). A total of 8.2g of colorless oily substance was collected, Y=47.5%.

[0162] 46-1 (m≈20, n≈9-17): Add 4.8g of intermediate S2, 30ml of toluene, and 0.4g of pyridine to the reaction flask. Under nitrogen protection, cool to 0℃ and control the temperature at 0-5℃. Add 10.0g of intermediate 43-1 dropwise. After the addition is complete, stir at 20-25℃ for 3h. Cool the system to 0℃ and quench with 30ml of water. Stir, let stand, separate, wash with water (2*30ml), wash with saturated sodium chloride (1*30ml), concentrate to dryness at 60℃, and elute by column chromatography (hexane:EA=80:1). A total of 5.5g of colorless oily substance was collected, Y=37.6%.

[0163] Intermediates 44-2, 45-2, 46-2:

[0164] 44-2 (m≈20, n≈1-6): Add 15ml of 1,4-dioxane, 5.5ml of H2O, and 85mgpd / c to the reaction flask. Under nitrogen protection, cool to 5℃, control the temperature to 5-10℃, and add 5.0g of intermediate 44-1 dropwise. After the addition is complete, continue stirring at 5-10℃ for 3 hours. Remove the ice bath, stir at 25±5℃ for 1 hour, add 12ml of toluene to the reaction flask, add 12.5g of diatomaceous earth and filter. Rinse with 5ml of toluene and 20ml of water. Stir, let stand, separate the contents, wash with water (2*20ml), wash with saturated sodium chloride (1*20ml), concentrate to dryness at 60℃, and elute by column chromatography (hexane:EA=50:1). A total of 3.9g of colorless oily substance was collected, Y=77.4%.

[0165] 45-2 (m≈20, n≈5-12): Add 15ml of 1,4-dioxane, 5.5ml of H2O, and 85mgpd / c to the reaction flask. Under nitrogen protection, cool to 5℃, control the temperature to 5-10℃, and add 5.0g of intermediate 45-1 dropwise. After the addition is complete, continue stirring at 5-10℃ for 3 hours. Remove the ice bath, stir at 25±5℃ for 1 hour, add 12ml of toluene to the reaction flask, add 12.5g of diatomaceous earth and filter. Rinse with 5ml of toluene and 20ml of water. Stir, let stand, separate the contents, wash with water (2*20ml), wash with saturated sodium chloride (1*20ml), concentrate to dryness at 60℃, and elute by column chromatography (hexane:EA=50:1). A total of 3.3g of colorless oily substance was collected, Y=66.0%.

[0166] 46-2 (m≈20, n≈9-17): Add 15ml of 1,4-dioxane, 5.5ml of H2O, and 85mgpd / c to the reaction flask. Under nitrogen protection, cool to 5℃, control the temperature to 5-10℃, and add 5.0g of intermediate 46-1 dropwise. After the addition is complete, continue stirring at 5-10℃ for 3 hours. Remove the ice bath, stir at 25±5℃ for 1 hour, add 15ml of toluene to the reaction flask, add 12.5g of diatomaceous earth and filter. Rinse with 5ml of toluene and 20ml of water. Stir, let stand, separate the contents, wash with water (2*20ml), wash with saturated sodium chloride (1*20ml), concentrate to dryness at 60℃, and elute by column chromatography (hexane:EA=50:1). A total of 3.1g of colorless oily substance was collected, Y=62.0%.

[0167] Compounds 44, 45, and 46:

[0168] Compound 44 (m≈20, n≈1-6): Add 2.5g of intermediate 44-2, 7.5ml of dimethylchlorosilane, and 121mg of pyridine to the reaction flask. Under nitrogen protection, cool to 5℃, control the temperature to 5-10℃, and add 153mg of methacryloyl chloride dropwise. After the addition is complete, stir at 25±5℃ for 2.5h. Cool the system to 0℃, add 20ml of water to quench the reaction mixture, stir, let stand, separate the contents, wash with water (2*20ml), wash with saturated sodium chloride (1*20ml), concentrate to dryness at 35℃, and elute by column chromatography (hexane:EA=90:1). A total of 1.9g of colorless oily substance was collected, Y=71.6%.

[0169] Compound 45 (m≈20, n≈5-12): Add 2.5g of intermediate 45-2, 7.5ml of dimethylchlorosilane, and 89mg of pyridine to a reaction flask. Under nitrogen protection, cool to 5℃, control the temperature to 5-10℃, and add 112mg of methacrylamide chloride dropwise. After the addition is complete, stir at 25±5℃ for 2.5h. Cool the system to 0℃, quench with 20ml of water, stir, let stand, separate the contents, wash with water (2*20ml), wash with saturated sodium chloride (1*20ml), concentrate to dryness at 35℃, and elute by column chromatography (hexane:EA=90:1). A total of 1.71g of colorless oily substance was collected, Y=65.5%.

[0170] Compound 46 (m≈20, n≈9-17): Add 2.5 g of intermediate 46-2, 7.5 ml of dimethylchlorosilane, and 67 mg of pyridine to a reaction flask. Under nitrogen protection, cool to 5°C, maintain the temperature at 5-10°C, and add 84 mg of methacrylamide chloride dropwise. After the addition is complete, stir at 25±5°C for 2.5 h. Cool the system to 0°C, quench with 20 ml of water, stir, allow to stand, separate the contents, wash with water (2*20 ml), wash with saturated sodium chloride (1*20 ml), concentrate to dryness at 35°C, and elute by column chromatography (hexane:EA=100:1). A total of 1.83 g of colorless oily substance was collected, Y=70.8%.

[0171] 8. Synthesis process of compounds 61, 62, and 63

[0172] Synthetic route

[0173]

[0174]

[0175] Synthesis process

[0176] Intermediates 61-1, 62-1, 63-1

[0177] 61-1 (n≈1-6): Add 3.5g NaHCO3 and 45ml water to the reaction flask. Under nitrogen protection, cool to 5℃, control the temperature to 5-10℃, and add 90ml of n-hexane solution of 30g intermediate 41-1 dropwise. After the addition is complete, continue stirring at 5-10℃ for 30min. Remove the ice bath and stir at 25℃ for 1.5h. Cool the system to 5℃ and quench with 60ml of saturated ammonium chloride solution. Wash with water (2*60ml) and saturated sodium chloride solution (1*60ml). Concentrate to dryness at 35℃. Collect a total of 27.1g of product, Y=92.8%.

[0178] 62-1 (n≈5-12): Add 1.88g NaHCO3 and 45ml water to the reaction flask. Under nitrogen protection, cool to 5℃, control the temperature to 5-10℃, and add 90ml of n-hexane solution of 30g intermediate 42-1 dropwise. After the addition is complete, continue stirring at 5-10℃ for 30min. Remove the ice bath and stir at 25℃ for 1.5h. Cool the system to 5℃ and quench with 60ml of saturated ammonium chloride solution. Wash with water (2*60ml) and saturated sodium chloride solution (1*60ml). Concentrate to dryness at 35℃. A total of 27.4g of product was collected, Y=92.6%.

[0179] 63-1 (n≈9-17): Add 1.2g NaHCO3 and 45ml water to the reaction flask. Under nitrogen protection, cool to 5℃, control the temperature to 5-10℃, and add 90ml of n-hexane solution containing 30g of intermediate 43-1 dropwise. After the addition is complete, continue stirring at 5-10℃ for 30min. Remove the ice bath, stir at 25℃ for 1.5h, cool the system to 5℃, quench with 60ml of saturated ammonium chloride solution, wash with water (2*60ml), wash with saturated sodium chloride solution (1*60ml), concentrate to dryness at 35℃, and collect a total of 26.9g of product. Y=90.6%. H-NMR (400MHz, CDCl3) δ 4.70 (tq, 1H, H-Si, HSICH = 2.8 Hz), 2.3 [t, 1H, HO-Si(CH3)2-(O-Si-CH2-CH2-CF3-CH3)nH], 2.1 [qt, 26H, HO-Si(CH3)2-(O-SiCH3-CH2-CH2-CF3)nH], 0.67 [m, 26H, HO-Si(CH3)2-(O-SiCH3-CH2-CH2-CF3)nH],0.17(s,6H,HO-Si(CH3)2-(O-Si-CH2-CH2-CF3-CH3)nH],0.11[s, 39H, HO-Si(CH3)2-

[0180] (O-SiCH3-CH2-CH2-CF3)nH]ppm,MALDI-TOF: m / z calc. for C(4n+2)H(7n+8)F3nO(n+1)Si(n+1);found [(M+23)].

[0181] Intermediates 61-2, 62-2, 63-2

[0182] 61-2 (n≈1-6): Add 3.9g of methacryloyl chloride, 100ml of dichloromethane, and 4.0g of triethylamine to the reaction flask. Under nitrogen protection, cool to 0℃ and maintain the temperature at 0-5℃. Add 25ml of a dichloromethane solution containing 25g of intermediate 61-1 dropwise. After the addition is complete, stir at 20-25℃ for 3 hours. Cool the system to 0℃ and quench with 80ml of water. Stir, allow to stand, separate, wash with water (2*80ml), wash with saturated sodium chloride (1*80ml), concentrate to dryness at 35℃, and elute by column chromatography (hexane:EA=100:1). Collect a total of 24.3g of colorless oily substance. Y=88.7%. ¹H-NMR (400MHz, CDCl₃) δ 6.1(dq,1H,CH3C=CH2),5.8(dt,1H,CH3C=CH2),4.7[tq,1H,H-(CH3SiCH2CH2CF3)n-],2.1[tq,8H,H-(CH3SiCH2CH2C

[0183] F3)n-],1.9(m,3H,CH3C=CH2),0.67[tdq,8H,H-(CH3SiCH2CH2CF3)n-],0.2[s,6H,H-(CH3SiCH2CH 2CF3)n-(CH3)2-Si-OO=C-(CH3)C=CH2],0.14[d,12H,H-(CH3SiCH2CH2CF3)n-]ppm, MALDI-TOF:m / z calc.for:C(4n+6)H(7n+12)F3nO(n+2)Si(n+1); found:([M+23]).

[0184] 62-2 (n≈5-12): Add 2.1g of methacryloyl chloride, 100ml of dichloromethane, and 2.11g of triethylamine to a reaction flask. Under nitrogen protection, cool to 0℃ and maintain the temperature at 0-5℃. Add 25ml of a dichloromethane solution containing 25g of intermediate 62-1 dropwise. After the addition is complete, stir at 20-25℃ for 3 hours. Cool the system to 0℃ and quench with 80ml of water. Stir, allow to stand, separate, wash with water (2*80ml), wash with saturated sodium chloride (1*80ml), concentrate to dryness at 35℃, and elute by column chromatography (hexane:EA=100:1). Collect a total of 20.7g of colorless oily substance. Y=79%. ¹H-NMR (400MHz, CDCl₃) δ 6.1(dq,1H,CH3C=CH2),5.8(dt,1H,CH3C=CH2),4.7[tq,1H,H-(CH3SiCH2CH2CF3)n-],2.1[tq,16H,H-(CH3SiCH2CH2C

[0185] F3)n-],1.9(m,3H,CH3C=CH2),0.67[tdq,16H,H-(CH3SiCH2CH2CF3)n-],0.2[s,6H,H-(CH3SiCH2 CH2CF3)n-(CH3)2-Si-OO=C-(CH3)C=CH2],0.14[d,24H,H-(CH3SiCH2CH2CF3)n-]ppm,MALDI-TOF: m / z calc.for:C(4n+6)H(7n+12)F3nO(n+2)Si(n+1); found:([M+23]).

[0186] 63-2 (n≈9-17): Add 1.3g of methacryloyl chloride, 100ml of dichloromethane, and 1.3g of triethylamine to the reaction flask. Under nitrogen protection, cool to 0℃ and maintain the temperature at 0-5℃. Add 25ml of a dichloromethane solution containing 25g of intermediate 63-1 dropwise. After the addition is complete, stir at 20-25℃ for 3 hours. Cool the system to 0℃ and quench with 60ml of water. Stir, let stand, separate, wash with water (2*60ml), wash with saturated sodium chloride (1*60ml), concentrate to dryness at 35℃, and elute by column chromatography (hexane:EA=100:1). Collect a total of 21.9g of colorless oily substance. Y=84.9%. ¹H-NMR (400MHz, CDCl₃) δ 6.1(dq,1H,CH3C=CH2),5.8(dt,1H,CH3C=CH2),4.7[tq,1H,H-(CH3SiCH2CH2CF3)n-],2.1[tq,26H,H-(CH3SiCH2CH2C

[0187] F3)n-],1.9(m,3H,CH3C=CH2),0.67[tdq,26H,H-(CH3SiCH2CH2CF3)n-],0.2[s,6H,H-(CH3SiCH2 CH2CF3)n-(CH3)2-Si-OO=C-(CH3)C=CH2],0.14[d,39H,H-(CH3SiCH2CH2CF3)n-]ppm,MALDI-TOF: m / z calc.for:C(4n+6)H(7n+12)F3nO(n+2)Si(n+1); found:([M+23].

[0188] Intermediates 61-3, 62-3, 63-3

[0189] 61-3 (n≈1-6): Add 60 ml of dichloromethane and 200 mg of Pdcl to the reaction flask. Under nitrogen protection, cool to 0 °C and control the temperature at 0-5 °C. Add 20.0 g of intermediate 61-2 dropwise. After the addition is complete, stir at 25 ± 5 °C for 2 h and proceed directly to the next step.

[0190] 62-3 (n≈5-12): Add 60 ml of dichloromethane and 200 mg of Pdcl to the reaction flask. Under nitrogen protection, cool to 0 °C and control the temperature at 0-5 °C. Add 20.0 g of intermediate 62-2 dropwise. After the addition is complete, stir at 25 ± 5 °C for 2 h and proceed directly to the next step.

[0191] 63-3 (n≈9-17): Add 60 ml of dichloromethane and 200 mg of Pdcl to the reaction flask. Under nitrogen protection, cool to 0 °C and control the temperature at 0-5 °C. Add 20.0 g of intermediate 63-2 dropwise. After the addition is complete, stir at 25 ± 5 °C for 2 h and proceed directly to the next step.

[0192] Compounds 61, 62, and 63

[0193] Compound 61 (m≈7, n≈1-6): 5.2 g of poly(ethylene glycol) methacrylate (Mn:400), 50 ml of dichloromethane, and 1.1 g of pyridine were added to a reaction flask. Under nitrogen protection, the mixture was cooled to 0°C and maintained at 0-5°C. Half of the reaction solution of intermediate 61-3 was added dropwise. After the addition was complete, the mixture was stirred at 25±5°C for 2.5 h. The system was then cooled to 0°C, and 60 ml of water was added dropwise to quench the reaction. The mixture was stirred, allowed to stand, separated, and washed with water (2*60 ml), then washed with saturated sodium chloride (1*60 ml). The solution was concentrated to dryness at 35°C. Column chromatography (hexane:EA=100:1) was performed, and 7.2 g of a colorless oily substance was collected. Y=47.7%. ¹H-NMR (400MHz, CDCl₃) δ 6.1(dq,2H,CH3CH2=C),5.8(dt,2H,(CH3CH2=C),3.6[m,28H,-(O-CH2-CH2)mO

[0194] -],2.1[qt,8H,-O(CH3SiOCH2-CH2-CF3)n-],1.9[m,6H,(CH3CH2=C)2],0.67[m,8H,-O(CH3SiOCH2-CH2-CF3)n,0.17[s ,6H,-O(CH3SiOCH2-CH2-CF3)n-(CH3)2Si-O-],0.11[s,12H,-O(CH3SiOCH2-CH2-CF3)n-(CH3)2Si-O-]ppm, MALDI-TOF: m / z calc.for:C(2m+4n+10)H(4m+7n+16)F3nO(m+n+4)Si(n+1); found: ([M+23]).

[0195] Compound 62 (m≈7, n≈5-12): 2.9 g of poly(ethylene glycol) methacrylate (Mn:400), 50 ml of dichloromethane, and 623 mg of pyridine were added to a reaction flask. Under nitrogen protection, the mixture was cooled to 0°C and maintained at 0-5°C. Half of the intermediate 62-3 reaction solution was added dropwise. After the addition was complete, the mixture was stirred at 25±5°C for 2.5 h. The system was then cooled to 0°C, and 60 ml of water was added dropwise to quench the reaction. The mixture was stirred, allowed to stand, separated, and washed with water (2*60 ml), then washed with saturated sodium chloride (1*60 ml). The solution was concentrated to dryness at 35°C. Column chromatography (hexane:EA=100:1) was performed, and a total of 5.85 g of colorless oily residue was collected. Y=45.7%. ¹H-NMR (400MHz, CDCl₃) δ 6.1(dq,2H,CH3CH2=C),5.8(dt,2H,(CH3CH2=C),3.6[m,28H,-(O-CH2-CH2)m-

[0196] ],2.1[qt,16H,-O(CH3SiOCH2-CH2-CF3)n-],1.9[m,6H,(CH3CH2=C)2],0.67[m,16H,-O(CH3SiOCH2-CH2-CF3)n,0.17[s ,6H,-O(CH3SiOCH2-CH2-CF3)n-(CH3)2Si-O-],0.11[s,24H,-O(CH3SiOCH2-CH2-CF3)n-(CH3)2Si-O-]ppm, MALDI-TOF: m / z calc.for:C(2m+4n+10)H(4m+7n+16)F3nO(m+n+4)Si(n+1); found: ([M+23])

[0197] Compound 63 (m≈7, n≈9-17): 1.8 g of poly(ethylene glycol) methacrylate (Mn:400), 50 ml of dichloromethane, and 400 mg of pyridine were added to a reaction flask. Under nitrogen protection, the mixture was cooled to 0°C and maintained at 0-5°C. Half of the intermediate 63-3 reaction solution was added dropwise. After the addition was complete, the mixture was stirred at 25±5°C for 2.5 h. The system was then cooled to 0°C, and 60 ml of water was added dropwise to quench the reaction. The mixture was stirred, allowed to stand, separated, and washed with water (2*60 ml), then washed with saturated sodium chloride (1*60 ml). The solution was concentrated to dryness at 35°C. Column chromatography (hexane:EA=100:1) was performed, and a total of 5.31 g of colorless oily residue was collected. Y=45%. ¹H-NMR (400MHz, CDCl₃) δ 6.1(dq,2H,CH3CH2=C),5.8(dt,2H,(CH3CH2=C),3.6[m,28H,-(O-CH2-CH2)mO

[0198] -],2.1[qt,26H,-O(CH3SiOCH2-CH2-CF3)n-],1.9[m,6H,(CH3CH2=C)2],0.67[m,26H,-O(CH3SiOCH2-CH2-CF3)n,0.17[ s,6H,-O(CH3SiOCH2-CH2-CF3)n-(CH3)2Si-O-],0.11[s,39H,-O(CH3SiOCH2-CH2-CF3)n-(CH3)2Si-O-]ppm, MALDI-TOF: m / z calc.for:C(2m+4n+10)H(4m+7n+16)F3nO(m+n+4)Si(n+1);

[0199] found: ([M+23])

[0200] 9. Synthesis process of compounds 64, 65, and 66

[0201] Synthetic route

[0202]

[0203] Synthesis process

[0204] Compounds 64, 65, and 66

[0205] Compound 64 (m≈20, n≈1-6): 12.3 g of poly(ethylene glycol) methacrylate (Mn:950), 50 ml of dichloromethane, and 1.1 g of pyridine were added to a reaction flask. Under nitrogen protection, the mixture was cooled to 0°C and maintained at 0-5°C. Half of the reaction solution of intermediate 61-3 was added dropwise. After the addition was complete, the mixture was stirred at 25±5°C for 2.5 h. The system was then cooled to 0°C, and 60 ml of water was added dropwise to quench the reaction. The mixture was stirred, allowed to stand, separated, and washed with water (2*60 ml), then with saturated sodium chloride (1*60 ml). The solution was concentrated to dryness at 35°C. Column chromatography (hexane:EA=100:1) was performed, and a total of 9.9 g of colorless oily residue was collected. Y=44%. H-NMR (400MHz, CDCl3) δ 6.1 (dq,2H,CH3CH2=C),5.8(dt,2H,(CH3CH2=C),3.6[m,80H,-(O-CH2-CH2)mO-],

[0206] 2.1[qt,8H,-O(CH3SiOCH2-CH2-CF3)n-],1.9[m,6H,(CH3CH2=C)2],0.67[m,8H,-O(CH3SiOCH2-CH2-CF3)n,0.17[s,6 H,-O(CH3SiOCH2-CH2-CF3)n-(CH3)2Si-O-],0.11[s,12H,-O(CH3SiOCH2-CH2-CF3)n-(CH3)2Si-O-]ppm, MALDI-TOF: m / z calc.for:C(2m+4n+10)H(4m+7n+16)F3nO(m+n+4)Si(n+1); found: ([M+23])

[0207] Compound 65 (m≈20, n≈5-12): 6.8 g of poly(ethylene glycol) methacrylate (Mn:950), 50 ml of dichloromethane, and 623 mg of pyridine were added to a reaction flask. Under nitrogen protection, the mixture was cooled to 0°C and maintained at 0-5°C. Half of the intermediate 62-3 reaction solution was added dropwise. After the addition was complete, the mixture was stirred at 25±5°C for 2.5 h. The system was then cooled to 0°C, and 60 ml of water was added dropwise to quench the reaction. The mixture was stirred, allowed to stand, separated, and washed with water (2*60 ml), followed by washing with saturated sodium chloride (1*60 ml). The solution was concentrated to dryness at 35°C. Column chromatography (hexane:EA=100:1) was performed, and 8.1 g of a colorless oily substance was collected. Y=48%. ¹H NMR (400 MHz, CDCl₃) δ 6.1(dq,2H,CH3CH2=C),5.8(dt,2H,(CH3CH2=C),3.6[m,80H,-(O-CH2-CH2)mO-],

[0208] 2.1[qt,16H,-O(CH3SiOCH2-CH2-CF3)n-],1.9[m,6H-,(CH3CH2=C)2],0.67[m,16H,-O(CH3SiOCH2-CH2-CF3)n,0.17[s ,6H,-O(CH3SiOCH2-CH2-CF3)n-(CH3)2Si-O-],0.11[s,24H,-O(CH3SiOCH2-CH2-CF3)n-(CH3)2Si-O-]ppm,MALDI-TOF: m / z calc.for:C(2m+4n+10)H(4m+7n+16)F3nO(m+n+4)Si(n+1); Found: ([M+23])

[0209] Compound 66 (m≈20, n≈9-17): 4.4 g of poly(ethylene glycol) methacrylate (Mn:950), 50 ml of dichloromethane, and 400 mg of pyridine were added to a reaction flask. Under nitrogen protection, the mixture was cooled to 0°C and maintained at 0-5°C. Half of the intermediate 63-3 reaction solution was added dropwise. After the addition was complete, the mixture was stirred at 25±5°C for 2.5 h. The system was then cooled to 0°C, and 60 ml of water was added dropwise to quench the reaction. The mixture was stirred, allowed to stand, separated, and washed with water (2*60 ml), then with saturated sodium chloride (1*60 ml). The solution was concentrated to dryness at 35°C. The mixture was then eluted by column chromatography (hexane:EA=100:1), and a total of 7.23 g of colorless oily residue was collected. Y=50.2%, H-NMR (400MHz, CDCl3) δ 6.1(dq,2H,CH3CH2=C),5.8(dt,2H,(CH3CH2=C),3.6[m,80H,-(O-CH2-CH2)m

[0210] -O-],2.1[qt,26H,-O(CH3SiOCH2-CH2-CF3)n-],1.9[m,6H,(CH3CH2=C)2],0.67[m,26H,-O(CH3SiOCH2-CH2-CF3)n,0.17 [s,6H,-O(CH3SiOCH2-CH2-CF3)n-(CH3)2Si-O-],0.11[s,39H,-O(CH3SiOCH2-CH2-CF3)n-(CH3)2Si-O-]ppm,MALDI-TOF: m / z calc.for:C(2m+4n+10)H(4m+7n+16)F3nO(m+n+4)Si(n+1);

[0211] found: ([M+23]).

[0212] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A compound for contact lenses, characterized in that, Its structural formula is shown below: Wherein, R1 is methylpropionyl, acryloyl, or siloxane alkyl; R2 is absent or is at least one of dimethylsilyl and silylalkyl; R3 is methylpropionyl, acryloyl, or siloxane alkyl; N is a natural number between 1 and 20, and M is a natural number between 1 and 20.

2. The compound for contact lenses according to claim 1, characterized in that, The structural formula is , , or 。 3. The compound for contact lenses according to claim 1, characterized in that, The structural formula is: or .

4. A contact lens material composition, characterized in that, Its raw materials include: the contact lens compound as described in any one of claims 1-3, a hydrophilic monomer, a silica hydrophobic monomer, and a crosslinking agent.

5. The contact lens material composition according to claim 4, characterized in that, The hydrophilic monomer is selected from N-vinylpyrrolidone, N,N-dimethylacetamide, hydroxyethyl methacrylate, or combinations thereof; the silicon-containing hydrophobic monomer is selected from methacryloyloxypropyltris(trimethylsiloxane), methacrylate compounds containing siloxane segments, fluorosiloxane acrylate monomers, or combinations thereof.

6. The contact lens material composition according to claim 4, characterized in that, The crosslinking agent is selected from dual-terminated methacrylate compounds containing siloxane segments, dual-terminated monomers of fluorosiloxane acrylates, or combinations thereof.

7. The contact lens material composition according to claim 4, characterized in that, Based on the total weight of the composition, the amount of the compound added for contact lenses is 0.1%-70%.

8. The contact lens material composition according to claim 4, characterized in that, The composition also contains a photoinitiator.

9. A contact lens, characterized in that, The contact lens material composition according to any one of claims 4 to 8 is prepared by ultraviolet light polymerization, extraction, equilibration and sterilization.

10. The contact lens according to claim 9, characterized in that, The method for preparing the contact lens includes the following steps: (1) Weigh and mix the raw materials according to the formula; (2) Inject the mixture into the female mold made of PP material and align the male and female molds; (3) Irradiate under ultraviolet light; (4) Open the mold and take out the lens, wash with ethanol, and then wash with purified water; (5) Place the lens in a standard phosphate solution for 1 hour to equilibrate; (6) Pour into a PP cup, add phosphate preservation solution, seal and steam sterilize.

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