A hydrophilic macromolecular silicone monomer with good mechanical properties and a preparation method and application thereof

Abstract

The application discloses a preparation method of a hydrophilic macromolecular organosilicon monomer with good mechanical properties, and steps are as follows: (1) carrying out a silicon hydrogen addition reaction on double-end hydrogen-containing polydimethylsiloxane and allyl polyether to obtain an intermediate 1; (2) carrying out a silicon hydrogen addition reaction on single-end hydrogen-containing polydimethylsiloxane and allyl polyether to obtain an intermediate 2; (3) carrying out addition on the intermediate 1 and isocyanylethyl methacrylate / acrylic acid 2-isocyanylethyl ester to obtain an intermediate reaction system 1; (4) carrying out addition on the intermediate 2 and a fatty diisocyanate base to obtain an intermediate reaction system 2; and (5) carrying out mixed reaction on the intermediate reaction system 1 and the intermediate reaction system 2 to obtain a target compound. The preparation method is simple, raw materials are easy to obtain, and reaction conditions are mild, and thus the method is suitable for large-scale production. The hydrophilic macromolecular organosilicon monomer can be applied to a silicon hydrogel contact lens, and the contact lens has high water content, good mechanical properties and air permeability.

Description

Technical Field

[0001] This invention relates to the field of organosilicon materials, and in particular to a hydrophilic macromolecular organosilicon monomer with good mechanical properties, its preparation method, and its application. Background Technology

[0002] Organosilicon materials possess excellent temperature resistance, weather resistance, electrical insulation, good flexibility and elasticity, and stable chemical properties. They also exhibit good biocompatibility and high breathability, leading to their widespread application in various fields. For example, silicone hydrogel lenses are a novel material created by combining traditional hydrogel materials with organosilicon materials. They possess both the high oxygen permeability of organosilicon and the softness and hydrophilicity of hydrogel materials. These contact lenses have a dual-channel material structure consisting of silicone channels and water channels, allowing oxygen from the air to easily penetrate the lens and reach the cornea, effectively improving the lens's oxygen permeability and significantly enhancing wearing comfort.

[0003] However, due to the helical structure of silicone molecules, their side groups are mostly hydrophobic, with the most common being the nonpolar methyl group (-CH3). Materials with these side groups have extremely low surface energy, far lower than that of water, making silicone inherently hydrophobic. This characteristic often leads to poor compatibility when silicone is used in conjunction with hydrophilic monomers due to the significant difference in their surface energies. This limits the application range and effectiveness of silicone materials. For example, high molecular weight silicone monomers, due to their strong hydrophobicity, have poor compatibility with hydrophilic monomers, resulting in strict limitations on their addition in formulations, thus restricting further improvements in the oxygen permeability of lens materials.

[0004] In addition, silicon-containing monomers are inherently rigid and have high hardness. Even if the silicon hydrogels prepared using them can solve the problem of unsatisfactory mechanical strength, the prepared silicon hydrogels have poor resilience and are difficult to return to their original shape after stretching, which affects the lifespan of the lenses and the wearing experience.

[0005] Therefore, there is an urgent need to develop a hydrophilic macromolecular organosilicon monomer with good mechanical properties, as well as its preparation method and application, in order to overcome the shortcomings of existing technologies. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the primary objective is to provide a hydrophilic macromolecular organosilicon monomer with good mechanical properties.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] A hydrophilic macromolecular organosilicon monomer with good mechanical properties has the following structural formula:

[0009]

[0010] Where R1 and R5 are polydimethylsiloxane groups with a molecular weight of less than 10,000, R2, R4, and R6 are polyethylene glycol segments with a molecular weight of less than 3,000, R3 is an alkyl or alkyl ester segment with a carbon number greater than or equal to 4, and R7 is... or .

[0011] To address the shortcomings of existing technologies, the second objective is to provide a method for preparing hydrophilic macromolecular organosilicon monomers with good mechanical properties. This method involves simple steps, readily available raw materials, mild reaction conditions, and easy product purification, making it suitable for large-scale production.

[0012] To achieve the above objectives, the present invention adopts the following technical solution:

[0013] A method for preparing a hydrophilic macromolecular organosilicon monomer with good mechanical properties includes the following steps:

[0014] Step 1: Weigh out the hydrogen-containing polydimethylsiloxane, add allyl polyether, add catalyst 1, heat to 60-120℃, and carry out the addition reaction for 1-24 hours to obtain intermediate 1. Intermediate 1 is a macromolecular organosilicon monomer with R4, R5 and R6 introduced.

[0015] Step 2: Weigh out single-end hydrogen-containing polydimethylsiloxane, add allyl polyether, add catalyst 2, heat to 60-120℃, react for 1-24h to obtain intermediate 2, intermediate 2 is a macromolecular organosilicon monomer introduced with R2 and R1.

[0016] Step 3: Dissolve intermediate 1 in the first solvent, add isocyanate monomer and catalyst 3, and react at 10-120℃ for 1-24 h to obtain intermediate reaction system 1. The isocyanate monomer is isocyanoethyl methacrylate and / or 2-isocyanoethyl acrylate. The intermediate reaction system 1 obtained by reacting the isocyanate monomer with intermediate 1 is further introduced with R7.

[0017] Step 4: Weigh intermediate 2 and dissolve it in the second solvent, add fatty diisocyanate, add catalyst 4, control the reaction temperature at 10-120℃, and react for 1-24 hours to obtain intermediate reaction system 2 with R3.

[0018] Step 5: Mix intermediate reaction system 1 and intermediate reaction system 2, control the reaction temperature at 10-120℃, and continue the reaction for 1-24 hours. Then, perform activated carbon adsorption filtration and rotary evaporation to obtain the target product.

[0019] As a preferred technical solution, in step one, the molar ratio of hydrogen-terminated polydimethylsiloxane to allyl polyether is 1:1.6~2.4, for example, it can be 1:1.6, 1:1.8, 1:2.0, 1:2.3 or 1:2.4, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable. This ratio range ensures that the hydrogen groups at both ends of the hydrogen-terminated polydimethylsiloxane react fully, while avoiding the waste of raw materials and increased difficulty in subsequent purification caused by excessive allyl polyether, and also preventing the problem of incomplete reaction caused by insufficient allyl polyether.

[0020] The catalyst 1 is at least one or more of chloroplatinic acid, Karstedt catalyst, and Wilkinson catalyst. The concentration of the catalyst 1 in the reaction solution is 2 to 100 ppm, for example, it can be 2 ppm, 5 ppm, 8 ppm, 10 ppm, 20 ppm, 30 ppm, 40 ppm, 60 ppm, 80 ppm or 100 ppm, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0021] Specifically, the reaction temperature in step one is 60℃~120℃, which can be 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, or 120℃. The reaction time is 1~24h, for example, it can be 1h, 4h, 8h, 12h, 16h, 18h, 20h, 22h, or 24h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0022] As a preferred technical solution, in step two, the molar ratio of single-ended hydrogen-containing polydimethylsiloxane to allyl polyether is 1:0.8~1.2, for example, it can be 1:0.8, 1:1.0, 1:1.1, 1:1.15 or 1:1.2, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable. The single-ended hydrogen group of the polydimethylsiloxane can react with the allyl polyether in an addition reaction.

[0023] Specifically, the reaction temperature in step two is 60℃~120℃, for example, it can be 60℃, 70℃, 80℃, 90℃, 100℃, 110℃ or 120℃, and the reaction time is 1~24h, for example, it can be 1h, 4h, 8h, 12h, 16h, 18h, 20h, 22h or 24h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0024] As a preferred technical solution, catalyst 2 is at least one of chloroplatinic acid, Karstedt catalyst, and Wilkinson catalyst; the concentration of catalyst 2 in the reaction solution is 2~100 ppm, for example, it can be 2 ppm, 5 ppm, 8 ppm, 10 ppm, 20 ppm, 30 ppm, 40 ppm, 60 ppm, 80 ppm or 100 ppm, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable. Catalysts 1 and 2 have highly efficient catalytic activity for addition reactions, which can significantly accelerate the reaction rate, shorten the reaction time, complete the reaction in less than 24 hours, and reduce the activation energy required for the reaction. The reaction temperature setting is mild, eliminating the need for demanding high-temperature equipment, thus reducing production energy consumption and equipment investment. At the same time, the use of low-concentration catalysts can reduce production costs and will not cause catalyst residue to affect the purity of intermediate 1, thereby ensuring the smooth progress of subsequent reactions.

[0025] As a preferred technical solution, the first solvent in step three is at least one of toluene, ethyl acetate, acetone, tetrahydrofuran, dichloromethane, tetrachloromethane, diethyl ether, dimethylformamide, or dimethyl sulfoxide. The above solvents are miscible with intermediate 1 and the isocyanate monomer to form a homogeneous reaction system and avoid side reactions caused by excessively high local concentrations.

[0026] The unsaturated bond of the isocyanate monomer undergoes an addition reaction with the hydroxyl group at the end of intermediate 1. The molar ratio of the total isocyanate monomers of ethyl methacrylate and 2-isocyanate acrylate to intermediate 1 is 0.5~1.2:1, for example, it can be 1:0.5, 1:0.7, 1:0.9, 1:1.1 or 1:1.2, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable. The above ratio ensures that the isocyanate monomer reacts fully with intermediate 1, while avoiding residues caused by excess isocyanate monomer, reducing the pressure of subsequent purification.

[0027] The catalyst 3 is at least one of dibutyltin dilaurate and bismuth neodecanoate, which has a highly efficient catalytic effect on the reaction of isocyanate and intermediate 1. The mass of the catalyst 3 is 0.1% to 5% of the total amount of intermediate 1 and isocyanate monomer, for example, it can be 0.1%, 0.5%, 1%, 3%, 4% or 5%. The reaction time in step three is 1 to 24 hours, for example, it can be 1 hour, 4 hours, 8 hours, 12 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours. The reaction temperature can be 10°C, 30°C, 50°C, 70°C, 90°C, 110°C or 120°C, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0028] As a preferred technical solution, the second solvent in step four is at least one selected from toluene, ethyl acetate, acetone, tetrahydrofuran, dichloromethane, tetrachloromethane, diethyl ether, dimethylformamide, and dimethyl sulfoxide. This allows intermediate 2 to fully dissolve with the aliphatic diisocyanate, ensuring a uniform reaction. Furthermore, the second solvent can be the same substance as the first solvent, facilitating subsequent mixing with the intermediate reaction system 1 and avoiding phase separation problems caused by solvent differences.

[0029] The unsaturated bond at one end of the aliphatic diisocyanate undergoes an addition reaction with intermediate 2, while the unsaturated bond at the other end of the aliphatic diisocyanate must be retained for subsequent addition reaction with intermediate reaction system 1. The molar ratio of intermediate 2 to aliphatic diisocyanate is 1:0.5~1.2; for example, it can be 1:0.5, 1:0.7, 1:0.9, 1:1.1 or 1:1.2, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0030] This ensures that the unsaturated bond at the other end of the fatty diisocyanate is retained, and that it needs to undergo an addition reaction with intermediate reaction system 1.

[0031] The fatty diisocyanate is at least one selected from 1,12-diisocyanododecane, L-lysine diisocyanate, 1,4-butyl diisocyanate, isophorone diisocyanate, 1,6-hexane diisocyanate, cyclohexane-1,4-diisocyanate, 2-heptyl-3,4-di(9-nonyl isocyanate)-1-pentyl-cyclohexane, trimethylhexamethylene diisocyanate, and 1,3-bis(methyl isocyanate)cyclohexane. All of the above fatty diisocyanates have long alkane chain structures, which can further enhance the overall flexibility of the molecule.

[0032] The catalyst 4 is at least one of dibutyltin dilaurate and bismuth neodecanoate; the mass of the catalyst 4 is 0.1% to 5% of the total amount of intermediate 2 and fatty diisocyanate, for example, it can be 0.5%, 1%, 3%, 4% or 5%; the reaction time of step four is 1 to 24 hours, for example, it can be 1 hour, 4 hours, 8 hours, 12 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours; the reaction temperature can be 10°C, 30°C, 50°C, 70°C, 90°C, 110°C or 120°C, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0033] As a preferred technical solution, the reaction temperature in step five can be 10℃, 30℃, 50℃, 70℃, 90℃, 110℃, or 120℃, and the mass of activated carbon is 0.5% to 10% of the total of intermediate reaction system 1 and intermediate reaction system 2, for example, 0.5%, 1%, 3%, 4%, 5%, 6%, 8%, or 10%; the adsorption time of activated carbon is 1 to 12 hours, for example, 1 hour, 2 hours, 3 hours, 5 hours, 6 hours, 8 hours, 9 hours, 10 hours, or 12 hours, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0034] To address the shortcomings of existing technologies, the third objective is to provide an application for a hydrophilic macromolecular organosilicon monomer with good mechanical properties.

[0035] Application of a hydrophilic macromolecular organosilicon monomer with good mechanical properties: The hydrophilic macromolecular organosilicon monomer with good mechanical properties is used as a raw material for hydrogel contact lenses, wherein the mass fraction of the hydrophilic macromolecular organosilicon monomer with good mechanical properties in the silicone hydrogel contact lenses is 10%~70%.

[0036] Compared with the prior art, the beneficial effects of the present invention are:

[0037] 1. The macromolecular organosilicon monomer of the present invention has polyethylene glycol segments, namely R2, R4, and R6, and introduces a polyether structure into the molecule, which greatly increases the compatibility of organosilicon molecules with hydrophilic monomers.

[0038] Simultaneously, the introduction of aliphatic diisocyanate groups into the molecular structure imbues the molecule with polyurethane soft segments. These soft segments possess excellent flexibility and toughness, enhancing the molecule's flexibility and mechanical strength. This effectively addresses the shortcomings of existing silicon-containing macromolecules, which are characterized by high rigidity and hardness, resulting in poor resilience and difficulty in restoring the original shape after stretching, thus affecting lens lifespan and wearing experience. The nitrogen-containing groups on the polyurethane soft segments have highly electronegative nitrogen atoms with lone pairs of electrons, enabling them to form hydrogen bonds with water molecules, further enhancing the hydrophilicity of the macromolecular organosilicon monomer. Furthermore, the aliphatic diisocyanate groups are chemically stable, remaining stable in the tear environment for extended periods without degradation, ensuring stable performance throughout the lens's lifespan. Unlike aromatic materials, it does not yellow, can withstand UV disinfection and gamma ray sterilization, and leaves very little residual monomer after complete reaction. Moreover, the aliphatic structure itself exhibits superior biocompatibility.

[0039] 2. The macromolecular organosilicon monomer of the present invention has polydimethylsiloxane segments, namely R1 and R5, which continue the excellent breathability of organosilicon materials. The special structure of its molecular chain can provide a basic channel for oxygen conduction, which is one of the core supports for ensuring the oxygen permeability of silicone hydrogel contact lenses. Detailed Implementation

[0040] The following examples further illustrate the features of the present invention and other related features in detail, so as to facilitate understanding by those skilled in the art.

[0041] Example 1

[0042] Example 1 provides a hydrophilic macromolecular organosilicon monomer with good mechanical properties, the structural formula of which is as follows:

[0043]

[0044] The preparation method of hydrophilic macromolecular organosilicon monomers is as follows:

[0045] Step 1: Weigh 35.0g of hydrogen-terminated polydimethylsiloxane with a molecular weight of 3600, add 9.7g of allyl polyether with a molecular weight of 500, add 5ppm of Karstedt catalyst, heat to 90℃, and react for 10h to obtain intermediate 1.

[0046] Step 2: Weigh 10.0g of single-ended hydrogen-containing polydimethylsiloxane with a molecular weight of 500, add 9.0g of allyl polyether with a molecular weight of 500, add 5ppm of Karstedt catalyst, heat to 90℃, and react for 10h to obtain intermediate 2.

[0047] Step 3: Weigh 44.0g of intermediate 1 obtained in step 1 and dissolve it in toluene. Add 1.5g of isocyanate methacrylate and 0.08g of bismuth neodecanoate. Control the reaction temperature at 30℃ and react for 6h to obtain intermediate reaction system 1.

[0048] Step 4: Weigh 10.0g of intermediate 2 obtained in step 2 and dissolve it in toluene. Add 2.0g of isophorone diisocyanate and 0.03g of bismuth neodecanoate. Control the reaction temperature at 30℃ and react for 6h to obtain intermediate reaction system 2.

[0049] Step 5: Mix intermediate reaction system 1 and intermediate reaction system 2, control the reaction temperature at 30°C, and continue the reaction for 6 hours. Then, add 3% of the total mass of the mixture of intermediate reaction system 1 and intermediate reaction system 2 with activated carbon for adsorption for 3 hours. After filtration and rotary evaporation, the hydrophilic macromolecular organosilicon monomer of Example 1 is obtained.

[0050] Example 2

[0051] Example 2 provides a hydrophilic macromolecular organosilicon monomer with good mechanical properties, the structural formula of which is as follows:

[0052]

[0053] The preparation method of hydrophilic macromolecular organosilicon monomers is as follows:

[0054] Step 1: Weigh 35.0g of hydrogen-terminated polydimethylsiloxane with a molecular weight of 3600, add 9.7g of allyl polyether with a molecular weight of 500, add 5ppm of Karstedt catalyst, heat to 90℃, and react for 10h to obtain intermediate 1.

[0055] Step 2: Weigh 10.0g of single-ended hydrogen-containing polydimethylsiloxane with a molecular weight of 500, add 9.0g of allyl polyether with a molecular weight of 500, add 5ppm of Karstedt catalyst, heat to 90℃, and react for 10h to obtain intermediate 2.

[0056] Step 3: Weigh 44.0g of intermediate 1 obtained in step 1 and dissolve it in toluene. Add 1.4g of 2-isocyanoethyl acrylate and 0.08g of bismuth neodecanoate. Control the reaction temperature at 30℃ and react for 6h to obtain intermediate reaction system 3.

[0057] Step 4: Weigh 10.0g of intermediate 2 obtained in step 2 and dissolve it in toluene. Add 2.0g of L-lysine diisocyanate and 0.03g of bismuth neodecanoate. Control the reaction temperature at 30℃ and react for 6h to obtain intermediate reaction system 4.

[0058] Step 5: Mix intermediate reaction system 3 and intermediate reaction system 4, control the reaction temperature at 30°C, and continue the reaction for 6 hours. Then, add 3% of the total mass of the mixture of intermediate reaction system 3 and intermediate reaction system 4 with activated carbon for adsorption for 3 hours. After filtration and rotary evaporation, the hydrophilic macromolecular organosilicon monomer of Example 2 is obtained.

[0059] Example 3

[0060] Example 3 provides a hydrophilic macromolecular organosilicon monomer with good mechanical properties, the structural formula of which is as follows:

[0061]

[0062] The preparation method of hydrophilic macromolecular organosilicon monomers is as follows:

[0063] Step 1: Weigh 35.0g of hydrogen-terminated polydimethylsiloxane with a molecular weight of 3600, add 9.7g of allyl polyether with a molecular weight of 500, add 5ppm of Karstedt catalyst, heat to 90℃, and react for 10h to obtain intermediate 1.

[0064] Step 2: Weigh 10.0g of single-ended hydrogen-containing polydimethylsiloxane with a molecular weight of 500, add 9.0g of allyl polyether with a molecular weight of 500, add 5ppm of Karstedt catalyst, heat to 90℃, and react for 10h to obtain intermediate 2.

[0065] Step 3: Weigh 44.0g of intermediate 1 obtained in step 1 and dissolve it in toluene. Add 1.5g of isocyanate methacrylate and 0.08g of bismuth neodecanoate. Control the reaction temperature at 30℃ and react for 6h to obtain intermediate reaction system 4.

[0066] Step 4: Weigh 10.0g of intermediate 2 obtained in step 2 and dissolve it in toluene. Add 2.0g of trimethylhexamethylene diisocyanate and 0.03g of bismuth neodecanoate. Control the reaction temperature at 30℃ and react for 6h to obtain intermediate reaction system 5.

[0067] Step 5: Mix intermediate reaction system 1 and intermediate reaction system 5, control the reaction temperature at 30°C, and continue the reaction for 6 hours. Then, add 3% of the total mass of the mixture of intermediate reaction system 1 and intermediate reaction system 5 with activated carbon for adsorption for 3 hours. After filtration and rotary evaporation, the hydrophilic macromolecular organosilicon monomer of Example 3 is obtained.

[0068] Example 4

[0069] Example 4 provides a hydrophilic macromolecular organosilicon monomer with good mechanical properties, the structural formula of which is as follows:

[0070]

[0071] The preparation method of hydrophilic macromolecular organosilicon monomers is as follows:

[0072] Step 1: Weigh 35.0g of hydrogen-terminated polydimethylsiloxane with a molecular weight of 3600, add 9.7g of allyl polyether with a molecular weight of 500, add 5ppm of Karstedt catalyst, heat to 90℃, and react for 10h to obtain intermediate 1.

[0073] Step 2: Weigh 10.0g of single-ended hydrogen-containing polydimethylsiloxane with a molecular weight of 500, add 9.0g of allyl polyether with a molecular weight of 500, add 5ppm of Karstedt catalyst, heat to 90℃, and react for 10h to obtain intermediate 2.

[0074] Step 3: Weigh 28.4g of intermediate 3 obtained in step 1 and dissolve it in toluene. Add 0.7g of isocyanate methacrylate and 0.06g of bismuth neodecanoate. Control the reaction temperature at 50℃ and react for 5h to obtain intermediate reaction system 6.

[0075] Step 4: Weigh 11.0g of intermediate 4 obtained in step 2 and dissolve it in toluene. Add 0.9g of isophorone diisocyanate and 0.06g of bismuth neodecanoate. Control the reaction temperature at 50℃ and react for 5h to obtain intermediate reaction system 7.

[0076] Step 5: Mix intermediate reaction system 6 and intermediate reaction system 7, control the reaction temperature at 50°C, and continue the reaction for 5 hours. Then, add 7% of the total mass of the mixture of intermediate reaction system 6 and intermediate reaction system 7 with activated carbon for 1 hour of adsorption. After filtration and rotary evaporation, the hydrophilic macromolecular organosilicon monomer of Example 4 is obtained.

[0077] Comparative Example 1

[0078] Comparative Example 1 provides an organosilicon monomer (PDMS-IEM) obtained by reacting isocyanate methacrylate and hydroxypropyl silicone oil.

[0079] This invention also provides contact lenses 1-5, which are mixed according to the mass ratio of each component listed in Table 1. The mixture is injected into a plastic mold using a liquid injection molding machine, and the mold is closed under a certain injection pressure and speed. The completed mold is then cured under appropriate light source irradiation. After curing, the lens is removed using a mold separation and lens removal machine. The resulting lens is washed with an appropriate proportion of alcohol / water solution, and then rinsed several times with pure water to finally obtain a silicone hydrogel contact lens.

[0080] The abbreviations used in Table 1 are as follows: TRIS: Methacryloxypropyltris(trimethylsiloxane), DMA: N,N-dimethylacrylamide, NVP: N-vinylpyrrolidone, D-1173: 2-hydroxy-2-methylphenylacetone, EGDMA: ethylene glycol dimethacrylate.

[0081] Table 1 lists the components of contact lenses 1-6.

[0082]

[0083] Performance tests were conducted on contact lenses 1-6, and the results are shown in Table 2. The testing standards and methods are as follows:

[0084] 1. Moisture content test: Weigh the slide Q1, place the contact lens on the slide, weigh the lens and slide together Q2, dry in an oven at 50℃ until constant weight, and then weigh the gross weight G3. Moisture content = (Q2-G3) / (Q2-Q1).

[0085] 2. Elongation at break test: The elongation at break of the silicone hydrogel materials prepared in the above examples and comparative examples was determined according to the tensile test method in GB / T 1040. The test speed was 20 mm / min.

[0086] Table 2 shows the test results for contact lenses 1-6.

[0087]

[0088] As can be seen from Table 2, the hydrophilic macromolecular organosilicon monomer with good mechanical properties provided by the present invention can increase the water content and improve the mechanical properties.

[0089] Compared to contact lens 6, which was prepared from organosilicon monomers in Comparative Example 1, the water content of contact lenses 1-5 increased by more than 4.70%. This is because polyethylene glycol segments (R2, R4, R6) were introduced into the monomer molecules of this invention. Their ether bonds can form stable hydrogen bonds with water molecules, giving the monomers intrinsic hydrophilicity. At the same time, in the polyurethane soft segments formed by aliphatic diisocyanate groups, the nitrogen atoms of the nitrogen-containing groups have lone pairs of electrons, which can form additional hydrogen bonds with water molecules, further enhancing the hydrophilicity. In addition, the polyethylene glycol segments and polyurethane soft segments synergistically regulate the surface energy of organosilicon molecules, significantly improving their compatibility with hydrophilic comonomers such as NVP and DMA, avoiding hydrophobic phase aggregation, and allowing water molecules to fully penetrate into the material network, ultimately achieving a water content increase of more than 4.70% compared to the comparative example.

[0090] This invention fundamentally improves upon the inherent rigidity of traditional silicon-containing monomers by introducing multiple flexible structures and optimizing phase structure uniformity. Firstly, the polyethylene glycol segments and the long alkane chains of the aliphatic diisocyanate groups are flexible segments, while the polyurethane soft segments themselves possess excellent flexibility and toughness. These three elements synergistically increase the rotatability of the molecular chains, reducing segment rigidity. Secondly, the polydimethylsiloxane segments (R1, R5) are precisely controlled in molecular weight to achieve alternating grafting with the flexible segments, forming a molecular structure that balances rigidity and flexibility, taking into account both breathability and tensile stability. Thirdly, improved molecular compatibility ensures uniform dispersion of the organosilicon, hydrophilic, and polyurethane phases, eliminating stress concentration at the phase interface. During stretching, stress can be uniformly transmitted within the molecular network, preventing material fracture. Ultimately, the elongation at break is increased by more than 135.27% compared to the comparative example, with all elongations at break exceeding 150%. The contact lenses of this invention exhibit excellent flexibility, ductility, and resistance to tensile deformation.

[0091] In Example 1 of this invention, isophorone diisocyanate was used; in Example 2, L-lysine diisocyanate was used; and in Example 3, trimethylhexamethylene diisocyanate was used. Different types of aliphatic diisocyanates have different alkane chain lengths and degrees of branching, resulting in slight differences in the flexibility and hydrophilicity of the polyurethane soft segments, thus affecting performance. In Example 4, the reaction temperature was increased to 50°C and the activated carbon adsorption amount was increased to 7%. Although the molecular structure was not changed, the purity and crosslinking uniformity of the product changed slightly, resulting in a slightly lower water content and elongation at break compared to Examples 1-3.

[0092] Obviously, the above embodiments of the present invention are merely examples to clearly illustrate the technical solutions of the present invention, and are not intended to limit the specific implementation of the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the claims of the present invention should be included within the protection scope of the claims of the present invention.

Claims

1. A hydrophilic macromolecular organosilicon monomer with good mechanical properties, characterized in that, The structural formula is as follows:

2. Wherein R1 and R5 are polydimethylsiloxane segments with a molecular weight of less than 10,000, R2, R4, and R6 are polyethylene glycol segments with a molecular weight of less than 3,000, R3 is an alkyl or alkyl ester segment with 4 or more carbon atoms, and R7 is... or .

3. A method for preparing a hydrophilic macromolecular organosilicon monomer with good mechanical properties as described in claim 1, characterized in that, Includes the following steps: Step 1: Weigh out hydrogen-terminated polydimethylsiloxane, add allyl polyether, add catalyst 1, heat to 60-120℃, react for 1-24 hours to obtain intermediate 1; Step 2: Weigh out single-ended hydrogen-containing polydimethylsiloxane, add allyl polyether, add catalyst 2, heat to 60-120℃, react for 1-24 hours to obtain intermediate 2; Step 3: Dissolve intermediate 1 in the first solvent, add isocyanate monomer and catalyst 3, and react at 10-120℃ for 1-24h to obtain intermediate reaction system 1; the isocyanate monomer is ethyl isocyanate methacrylate and / or ethyl isocyanate acrylate. Step 4: Weigh intermediate 2 and dissolve it in the second solvent, add fatty diisocyanate, add catalyst 4, control the reaction temperature at 10-120℃, and react for 1-24 hours to obtain intermediate reaction system 2. Step 5: Mix intermediate reaction system 1 and intermediate reaction system 2, control the reaction temperature at 10-120℃, and continue the reaction for 1-24 hours. Then, perform activated carbon adsorption filtration and rotary evaporation to obtain hydrophilic macromolecular organosilicon monomers.

4. The method for preparing a hydrophilic macromolecular organosilicon monomer with good mechanical properties according to claim 2, characterized in that, In step one, the molar ratio of hydrogen-terminated polydimethylsiloxane to allyl polyether is 1:1.6~2.4; the catalyst 1 is at least one or more of chloroplatinic acid, Karstedt catalyst, and Wilkinson catalyst; the concentration of the catalyst 1 in the reaction solution is 2~100 ppm.

5. The method for preparing a hydrophilic macromolecular organosilicon monomer with good mechanical properties according to claim 2, characterized in that, In step two, the molar ratio of single-ended hydrogen-containing polydimethylsiloxane to allyl polyether is 1:0.8~1.2; the catalyst 2 is at least one of chloroplatinic acid, Karstedt catalyst, and Wilkinson catalyst; the concentration of the catalyst 2 in the reaction solution is 2~100 ppm.

6. The method for preparing a hydrophilic macromolecular organosilicon monomer with good mechanical properties according to claim 2, characterized in that, In step three, the first solvent is at least one of toluene, ethyl acetate, acetone, tetrahydrofuran, dichloromethane, tetrachloromethane, diethyl ether, dimethylformamide, or dimethyl sulfoxide; the molar ratio of the total isocyanate monomers of ethyl isocyanate methacrylate and 2-isocyanate acrylate to intermediate 1 is 0.5~1.2:1; the catalyst 3 is at least one of dibutyltin dilaurate and bismuth neodecanoate; the mass of the catalyst 3 is 0.1%~5% of the total amount of intermediate 1 and isocyanate monomers.

7. The method for preparing a hydrophilic macromolecular organosilicon monomer with good mechanical properties according to claim 2, characterized in that, In step four, the second solvent is at least one of toluene, ethyl acetate, acetone, tetrahydrofuran, dichloromethane, tetrachloromethane, diethyl ether, dimethylformamide, and dimethyl sulfoxide; the molar ratio of intermediate 2 to aliphatic diisocyanate is 1:0.5~1.2; the aliphatic diisocyanate is at least one of 1,12-diisocyanododecane, L-lysine diisocyanate, 1,4-butyl diisocyanate, isophorone diisocyanate, 1,6-hexanediisocyanate, cyclohexane-1,4-diisocyanate, 2-heptyl-3,4-di(9-nonyl isocyanate)-1-pentyl-cyclohexane, trimethylhexamethylene diisocyanate, and 1,3-bis(methyl isocyanate)cyclohexane; the catalyst 4 is at least one of dibutyltin dilaurate and bismuth neodecanoate; the mass of the catalyst 4 is 0.1%~5% of the total mass of intermediate 2 and aliphatic diisocyanate.

8. The method for preparing a hydrophilic macromolecular organosilicon monomer with good mechanical properties according to claim 2, characterized in that, In step five, the mass of activated carbon is 0.5% to 10% of the total mass of intermediate reaction system 1 and intermediate reaction system 2; the adsorption time of activated carbon is 1 to 12 hours.

9. The application of a hydrophilic macromolecular organosilicon monomer with good mechanical properties as described in claim 1, or a hydrophilic macromolecular organosilicon monomer with good mechanical properties prepared by any one of claims 2 to 7, characterized in that, The hydrophilic macromolecular organosilicon monomer with good mechanical properties is used as the raw material for hydrogel contact lenses, and the mass fraction of the hydrophilic macromolecular organosilicon monomer in the hydrogel contact lenses is 10%~70%.

Images