Multifunctional polymer for synthesizing artificial lens material as well as preparation method and application of multifunctional polymer

Abstract

The invention relates to the field of high-molecular polymerization, in particular to a multifunctional polymer for synthesizing an artificial lens material as well as a preparation method and application of the multifunctional polymer. The multifunctional polymer for synthesizing the artificial lens material, provided by the invention, is used as a polymer type multifunctional cross-linking agent for preparing an artificial lens, so that the artificial lens with low flash density can be obtained, and the multifunctional polymer has high refractive index, low glass transition temperature and good biocompatibility; if a combination of a specific copolymerization unit and a copolymerization unit derived from glycidyl (meth) acrylate or a derivative thereof is adopted, the synthesized intraocular lens material has better performance, and the sparkling density can be reduced to dozens of even 0 / mm < 2 >. The polymer is prepared in a controllable polymerization mode, the multifunctional cross-linking agent with a rich structure is easy to obtain, and the synthesis method is free of small molecule byproducts, simpler, more convenient, atom-economical and environment-friendly.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high molecular polymerization, and particularly relates to a multifunctional polymer for synthesizing an intraocular lens material and a preparation method and application thereof. BACKGROUND

[0002] Cataract is the primary cause of blindness and low vision in China and even the whole world. Cataract extraction combined with intraocular lens implantation is the most effective treatment method. At present, whether the phenomenon of glint occurs has become an important indicator for evaluating the optical performance of intraocular lenses. Glint phenomenon refers to the appearance of fine and dense microbubble-like changes in the optical zone when the intraocular lens is placed in a water environment. Due to the difference in refractive index, light diffuses, resulting in the microbubble glinting. This phenomenon usually occurs in hydrophobic acrylate intraocular lenses. Different types of hydrophobic acrylate intraocular lenses have different degrees of glint phenomenon, and their optical performance will further deteriorate with the increase of glint density, affecting the visual quality of patients. At present, the performance adjustment and optimization of intraocular lenses are mainly achieved by changing monomers, while the significant influence of crosslinking agent structure on the performance of crosslinked network system is ignored.

[0003] Intraocular lenses are crosslinked network structures obtained by a series of polymerization reactions of different monomers and crosslinking agents. Although the content of crosslinking agent in the polymer is small, it has a significant influence on the performance of the crosslinked network system. Even a slight structural change can cause a major change in the performance of the polymer, producing a "four ounces move a thousand catties" effect. In different elastic systems (such as dielectric elastomers), the network structure of the crosslinked polymer can be optimized by adjusting the chemical structure or average molecular weight of the crosslinking agent, so that it has high toughness, high transparency and other characteristics (Sci Adv. 2018; 4(10): eaat7629; Nat Commun. 2021; 12(1): 4517).

[0004] However, the types of commercial cross-linking agents in the existing artificial lenses are relatively single, among which the bifunctional (methyl) acrylate is more commonly used, and the improvement of the properties of the artificial lenses is limited. The commercial cross-linking agents applied to the artificial lens materials are generally polymerized by using the "di- or polyol esterification method", the operability and reaction efficiency of which are limited by the solubility of the polyol, the structural richness and adjustability of the obtained cross-linking agent are limited by the structure of the small molecule di- or polyol, and the by-product is based on the condensation reaction of hydroxyl and acyl chloride, the reaction process generally needs to be kept at low temperature, and the acid binding agent and solvent are needed. The selective ring-opening polymerization of commercial glycidyl methacrylate (GMA) and its derivatives can directly retain the methacrylic functional group quantitatively in the side group of the polymer, endow the polymer with multiple chemical properties, and provide ideas for the structural design and precise synthesis of new polymer-type multifunctional cross-linking agents. In summary, the key to the successful implementation of the present application is to develop a multi(methyl) acrylate multifunctional polymer based on the "controlled polymerization method", which makes up for the shortcomings of the existing commercial cross-linking agents, and then obtains an artificial lens material with high optical performance. SUMMARY

[0005] Therefore, the technical problem to be solved by the present application is a multifunctional polymer for synthesizing an artificial lens material and a preparation method and application thereof. The multifunctional polymer for synthesizing an artificial lens material provided by the present application is a multi(methyl) acrylate multifunctional polymer prepared based on the "controlled polymerization method", which can be used as a cross-linking agent for preparing an artificial lens material, meets the basic performance required in the clinical application of the artificial lens, and can improve the internal structural stability of the artificial lens, optimize the network structure of the cross-linked polymer, improve the performance of the artificial lens material, and thus greatly reduce or completely eliminate the occurrence of artificial lens flash.

[0006] The present application provides a multifunctional polymer for synthesizing an artificial lens material, which has the structure of formula I.

[0007]

[0008] wherein x is an integer of 2-8; y is an integer of 1-4;

[0009] R1 is H, C1-C5 alkyl, C6-C 10 aryl or C2-C8 alkanoyl;

[0010] R2 is H or methyl;

[0011] A is a group having the structure of formula I-1, formula I-2 or formula I-3;

[0012]

[0013] wherein n is an integer from 0 to 10;

[0014] M1 is substituted or unsubstituted C1-C5 alkyl;

[0015] M2 is substituted or unsubstituted C3-C 10 alkenyl, substituted or unsubstituted C6-C 12 aryl, or substituted or unsubstituted C3-C 10 cycloalkenyl.

[0016] The multifunctional polymer provided by the present application is obtained by copolymerization of (meth)acrylic acid glycidyl ester or its derivative and specific comonomer as comonomer raw material and active hydrogen compound. The x is an integer from 2 to 8, indicating that there are 2 to 8 comonomer units derived from (meth)acrylic acid glycidyl ester or its derivative in the polymer structure of the present application, and the (meth)acrylic acid glycidyl ester includes one of methacrylic acid glycidyl ester and acrylic acid glycidyl ester, so the R2 is H or methyl.

[0017] The y in the present application is an integer from 1 to 4, indicating that there are 1 to 4 integers of initiation sites on the active hydrogen compound to polymerize with the comonomer raw material. The R1 is a residue derived from the active hydrogen compound, which is H, C1-C5 alkyl, C6-C 10 aryl, or C2-C8 alkanoyl; when the R1 is H, it indicates that the active hydrogen compound derived therefrom is water, and y is 1; when the R1 is C2 alkanediyl, i.e. -CH2-CH2-, it indicates that the active hydrogen compound derived therefrom is ethylene glycol, and y is 2; when the R1 is C5 alkanetetrayl, i.e. C(CH2)4-, it indicates that the active hydrogen compound derived therefrom is pentaerythritol, and y is 4; when the R1 is C6 aryl, i.e. phenyl, it indicates that the active hydrogen compound derived therefrom is phenol, and y is 1; when the R1 is C2 alkanoyl, i.e. CH3-CH2-CO-, it indicates that the active hydrogen compound derived therefrom is acetic acid, and y is 1; other cases are similar and will not be repeated.

[0018] The A in the present application is derived from specific comonomer. The present inventors have creatively found that the polymer provided by the present application, as a polymer type multifunctional crosslinking agent, can be used in the preparation of intraocular lenses to obtain intraocular lenses with low flash density, high refractive index, low glass transition temperature and good biocompatibility; if specific comonomer units and comonomer units derived from (meth)acrylic acid glycidyl ester or its derivative are combined, the effect is better, and the flash density is as low as dozens or even 0 / mm 2 .

[0019] A is a group having the structure of Formula I-1, Formula I-2 or Formula I-3; wherein M1 in Formula I-1 is a substituted or unsubstituted C1-C5 alkyl; M2 in Formula I-2 is a substituted or unsubstituted C3-C 10 alkyl, a substituted or unsubstituted C6-C 12 aryl or a substituted or unsubstituted C3-C 10 cycloalkenyl; n in Formula I-1 to Formula I-3 is an integer from 0 to 10. Preferably, the group having the structure of Formula I-1 is selected from M2 in the group having the structure of Formula I-2 is a group having the structure of Formula I-2-a: Formula I-2-a, R4 and R5 are independently H, methyl, ethyl or phenyl; or M2 is a substituted or unsubstituted phenyl; or M2 is a substituted or unsubstituted C7-C 10 cycloalkenyl. More preferably, the group having the structure of Formula I-2 is selected from

[0020]

[0021] In some embodiments of the present application, the polymer provided by the present application has one of the structures of Formula a to Formula g:

[0022] In Formula f and Formula g, m = (n+x) / 2, and n = x; the wavy line refers to the same group in the formula that is connected to the oxygen atom in the active hydrogen compound.

[0023] The present application provides a preparation method of the multifunctional polymer for synthesizing the intraocular lens material, comprising the following steps:

[0024] under the action of a catalyst, the active hydrogen compound, the first comonomer and the optional second comonomer are subjected to a polymerization reaction to obtain the polymer described above;

[0025] The active hydrogen compound is selected from water, a C1-C5 alkyl y-alcohol, a C6-C 10 aryl y-phenol, a C2-C8 alkyl y-carboxylic acid;

[0026] The first comonomer is

[0027] The second comonomer is selected from or one or more of CO2.

[0028] The structure of the first comonomer is R2 is the same as described above and will not be repeated here; it is derived from glycidyl methacrylate or its derivatives, and the meaning of glycidyl methacrylate is the same as described above and will not be repeated here.

[0029] The second comonomer of the present invention is selected from Alternatively, one or more of CO2. M1 and M2 are the same as described above and will not be repeated. The second comonomer may or may not be added. If added, it must be selected from a specific second comonomer to ensure that the resulting polymer has specific comonomer units that synergistically achieve excellent crosslinking agent effects with the comonomer units formed by the first comonomer. Preferably, the second comonomer is selected from one or more of ethylene oxide, propylene oxide, phthalic anhydride, or bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride.

[0030] The active hydrogen compound of this invention is selected from water, C1-C5 alkyl y alcohols, C6-C4 alkyl y alcohols, and C6-C4 alkyl y alcohols. 10 The aryl γ-phenol or C2-C8 alkyl γ-carboxylic acid is preferably selected from ethylene glycol or pentaerythritol; the γ- is the same as described above and will not be repeated. The catalyst of the present invention is selected from an organic base or a combination with an organoboron; the organic base is selected from at least one of phosphazene base, triaminophosphine, tertiary amine, amidine, and guanidine; the organoboron is selected from at least one of trimethylborane, triethylborane, and diethylmethoxyborane.

[0031] The polymerization reaction temperature of the present invention is 0–100°C; the polymerization reaction time is 0.5–300 h. In one technical solution of the present invention, in an inert gas atmosphere, an active hydrogen compound and a catalyst are mixed, and a second comonomer is added at 0°C for a pre-reaction of 0.5–1 h, followed by the addition of a first comonomer and a heating process to obtain the polymer of the present invention. In another technical solution of the present invention, in an inert gas atmosphere, an active hydrogen compound, a first comonomer, and a second comonomer are mixed and polymerized to obtain the polymer of the present invention.

[0032] This invention provides a method for preparing multifunctional polymers for synthesizing intraocular lens (IOL) materials. The method utilizes a controlled polymerization process to prepare a series of poly(meth)acrylate multifunctional polymers. By designing and changing the proportions and feeding methods, the relative reaction rates of the two monomers are adjusted, thereby controlling the sequence structure of the copolymer, i.e., the content and distribution of (meth)acrylate groups. This allows for the synthesis of multifunctional polymers with different side groups and main chain structures, which are then used as crosslinking agents in the preparation of IOL materials. When applied to the synthesis of IOL materials, by controlling the functionality, topology, and type and length of the linking groups of the multifunctional crosslinking agent, the brilliance of the IOL can be improved, thereby obtaining IOL materials with high optical performance.

[0033] The present application provides an application of the multifunctional polymer of any of the above technical solutions as a crosslinking agent for preparing an intraocular lens material. The present application also provides an intraocular lens material, which is polymerized from a multifunctional polymer for synthesizing an intraocular lens material, at least two main monomers and an optional ultraviolet absorber; the main monomers are selected from at least two of (meth) acrylate containing aromatic ring and optional hydrophilic (meth) acrylate.

[0034] The present application can prepare an intraocular lens material with high optical performance by using the multifunctional polymer for synthesizing an intraocular lens material as a crosslinking agent, which meets the basic performance of intraocular lens in clinical application, can improve the internal stability of the intraocular lens material, optimize the network structure of the crosslinked polymer, and further improve the performance of the intraocular lens, greatly reduce or completely eliminate the occurrence of intraocular lens flash; endow the material with good mechanical properties, and at the same time improve the memory performance of the material. The polymer of the present application can be used alone or in combination of two or more. After the intraocular lens material is prepared, the structure unit formed is a high molecular repeat unit containing unsaturated double bond. When all monomer components contained in the main monomer are set to 100 mol%, the content of the crosslinking agent structure unit can be set to 0.1 mol% to 5 mol%, preferably 0.5 mol% to 4 mol%, and more preferably 1 mol% to 3 mol%.

[0035] Specifically, in the at least two main monomers of the present application, all can be selected from (meth) acrylate containing aromatic ring, or can be selected from a combination of (meth) acrylate containing aromatic ring and hydrophilic (meth) acrylate, and cannot all be selected from hydrophilic (meth) acrylate.

[0036] The (meth) acrylate containing aromatic ring of the present application includes one of acrylate containing aromatic ring and methacrylate containing aromatic ring, which can improve the refractive index and flexibility of the intraocular lens material, and is specifically selected from at least one of 2-phenylethyl acrylate, 2-methylphenylethyl acrylate, 3-phenylpropyl acrylate, 3-phenylpropyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate or 3-phenoxypropyl methacrylate, which are numbered as ① to ⑦ in turn, and the specific structural formula is as follows:

[0037]

[0038] When all monomer components contained in the main monomer are set to 100 mol%, the content of the (meth) acrylate containing aromatic ring is 30 mol% to 70 mol%, preferably 35 mol% to 65 mol%, and more preferably 40 mol% to 60 mol%.

[0039] The hydrophilic (meth)acrylate in the present application includes one of hydrophilic acrylate and hydrophilic methacrylate, and is specifically at least one of (2-hydroxy)ethyl acrylate, (2-hydroxy)ethyl methacrylate, (2-hydroxy)propyl methacrylate, (3-hydroxy)propyl acrylate, (3-hydroxy)propyl methacrylate, (3-hydroxy)butyl acrylate, (3-hydroxy)butyl methacrylate, (2-hydroxy)butyl acrylate or (2-hydroxy)butyl methacrylate, which are numbered as ①-⑨ in sequence, and the specific structural formula is as follows:

[0040]

[0041] When all monomer components contained in the main monomer are set as 100 mol%, the content of the hydrophilic (meth)acrylate monomer is 0 mol%-45 mol%, preferably 10 mol%-40 mol%, and more preferably 15 mol%-40 mol%.

[0042] The ultraviolet absorber in the present application can be selectively added or not added. Preferably, the ultraviolet absorber is 2-hydroxy-4-octyloxybenzophenone. The content of this structural unit can be appropriately set within a range that does not impair the effect of the present application.

[0043] The artificial lens material provided by the present application has high optical performance, and the flash density is preferably less than 100 / mm 2 , more preferably less than 25 / mm 2 . The refractive index reaches 1.50 or more, preferably 1.55, and more preferably 1.60. At the same time, it has excellent mechanical properties, with an elongation at break of more than 150%, preferably more than 200%, and more preferably more than 300%; and a tensile strength of more than 2 MPa, preferably 2.5 MPa-11 MPa, and more preferably 3 MPa-10.5 MPa.

[0044] Specifically, the preparation method of the artificial lens material includes: under the action of a free radical polymerization initiator, a polymer, at least two main monomers and an optional ultraviolet absorber are subjected to thermal polymerization reaction to obtain. The content of each of the raw materials and the structural unit thereof is the same as described above, and will not be repeated here. The free radical polymerization initiator in the present application includes azobisisobutyronitrile or benzoyl peroxide, and the content of the free radical polymerization initiator structural unit can be appropriately set within a range that does not impair the effect of the present application.

[0045] The preparation method is a segmented heating free radical polymerization method, and specifically comprises the following steps: stirring a polymer, at least two main monomers and an optional ultraviolet absorber at room temperature until all the components are dissolved; then adding a free radical polymerization initiator to the mixture and stirring for at least 5 min until the initiator is dissolved; bubbling the reaction components with nitrogen for 15-30 min, and injecting the reaction components into a polytetrafluoroethylene mold for thermal polymerization; the thermal polymerization comprises a first stage and a second stage, the first stage is thermal polymerization at 60-80 DEG C for 2-3 h, and the second stage is post-curing at 100-120 DEG C for 2-4 h. After the polymerization is completed, the polymerization product is soaked in anhydrous ethanol, and the surface unreacted monomers are removed after being washed three times; after the anhydrous ethanol is completely volatilized, the polymerization product is soaked in deionized water for three times, vacuum dried, and finally the intraocular lens material is obtained.

[0046] The application further provides an intraocular lens which is processed from the intraocular lens material according to any one of the above technical solutions. The processing method is not particularly limited, and can be any method known to those skilled in the art.

[0047] The application provides a multifunctional polymer for synthesizing an intraocular lens material, a preparation method and application thereof. The multifunctional polymer is used as a polymer-type multifunctional crosslinking agent for preparing the intraocular lens material, and can obtain an intraocular lens material with low flash density, high refractive index, low glass transition temperature and good biocompatibility. If specific copolymerization units and copolymerization units derived from glycidyl (meth)acrylate or its derivatives are combined, the effect is better, and the flash density can be reduced to dozens or even 0 / mm 2 Compared with the prior art, the multifunctional polymer obtained by the "controlled polymerization method" has the following advantages: (1) the preparation of the crosslinking agent is carried out in a polymerization manner, and the multifunctionality is easy to obtain, while the operability and reaction efficiency of the multifunctional crosslinking agent prepared by the condensation reaction of a small molecule polyol and an acyl chloride in the prior art can be limited by the solubility of the polyol; (2) the polymerization method is a controlled polymerization, and the functionality and molecular structure (linear or nonlinear) of the polymer can be easily controlled by changing the feed ratio of the polymerization reaction and the structure of the initiator, so that the polymer structure is more abundant and adjustable than the method for preparing the multifunctional crosslinking agent by the condensation reaction of a small molecule polyol and an acyl chloride in the prior art; (3) the polymerization method is a chain addition polymerization, and there is no small molecule by-product, and the organic catalyst can be used under solvent-free or low-solvent and normal temperature conditions, which is more convenient, atom-economic and environmentally friendly than the synthesis method based on the condensation reaction of a hydroxyl group and an acyl chloride in the prior art (which has a by-product, generally requires low-temperature reaction, and needs an acid binding agent and a solvent). DETAILED DESCRIPTION

[0048] The present application discloses a kind of synthetic intraocular lens material multi-functional polymer and its preparation method and application.The person skilled in the art can improve process parameters appropriately according to the content herein.The application needs to be pointed out particularly, all similar substitutions and changes are obvious to the person skilled in the art, and they are regarded as including in the present application.The method and application of the present application have been described by preferred embodiments, and the relevant personnel can obviously change or appropriately change and combine the method and application herein without departing from the content, spirit and scope of the present application, to realize and apply the present application technology.

[0049] The relative molecular weight and molecular weight distribution of functionalized polymer in the following examples are measured by Agilent 1260 Infinity type volume exclusion chromatograph (SEC), the mobile phase is tetrahydrofuran, the column temperature is 35 DEG C, and the flow rate is 1 mL / min;A series of polystyrene or polyethylene oxide standard samples are used as calibration curve.

[0050] Flashing density test: flashing density is obtained by temperature accelerated test, specifically, plate-shaped sample with size of 20mm x 10mm x 1mm is immersed in 45 DEG C deionized water for 24h, then immersed in 37 DEG C deionized water for 2.5h, and then observed and calculated the flashing density by optical microscope. At least 3 or more samples of each material are observed, the magnification is about 10-40 times, and in order to easily observe the flashing, the magnification is adjusted appropriately within the range to observe.

[0051] The following relates to the amount of raw material parts, all refers to molar parts.

[0052] The present application is further described in conjunction with the following examples:

[0053] Example 1

[0054] In inert atmosphere, 1 part of ethylene glycol, 0.1 part of phosphazene base and 0.5 part of triethylboron tetrahydrofuran solution are added to a glass reactor dried at 120 DEG C and restored to room temperature, and then dissolved in toluene. Continue to add 40 parts of GMA, seal the glass reaction container, mix uniformly using a magnetic stirrer, and react at room temperature (25±5 DEG C) for 16h. After the reaction is completed, dilute with dichloromethane and mix with neutral alumina, filter to remove the catalyst, and spin dry the solvent by rotary evaporator. Collect the polymer and dry in a vacuum oven at constant temperature of 50 DEG C for 12h. SEC measurement shows that the molecular weight of the product is 4.6 kg / mol, and the dispersion degree is 1.07. The structure of the obtained multi-functional polymer is as follows:

[0055]

[0056] A mixture of 5.7 parts of 2-phenylethyl acrylate, 4.3 parts of 2-methylphenylethyl acrylate, 0.1 part of azobisisobutyronitrile and 0.2 parts of the above multifunctional polymer as crosslinking agent were mixed uniformly to dissolution. The mixture was injected into a polytetrafluoroethylene mold, and after bubbling in an inert atmosphere for about 30 min, it was cured at 60°C for 2 h and at 100°C for 3 h, and then the mold was slowly cooled to room temperature. The prepared intraocular lens material was soaked in anhydrous ethanol, and after rinsing 3 times to remove the surface unreacted monomers, a Soxhlet extraction operation can be performed if necessary. After the anhydrous ethanol was completely volatilized, it was soaked and rinsed 3 times with deionized water, and vacuum dried. The property evaluation of the obtained intraocular lens material can be seen in Table 1.

[0057] Example 2

[0058] In an inert atmosphere, 1 part of ethylene glycol, 0.05 part of phosphazene base and a solution containing 0.2 part of triethylboron in tetrahydrofuran were added to a glass reactor. After vacuum exhaust, 50 parts of dry ethylene oxide were added at 0°C, and the reaction was continued for 0.5 h. Then, 20 parts of GMA were added and the temperature was raised to 50°C to continue the reaction for 24 h. After the reaction was completed, a large amount of diethyl ether was added for precipitation, the polymer was collected and dried in a vacuum oven at 50°C for 12 h. SEC measurement showed that the product molecular weight was 5.1 kg / mol, and the dispersity was 1.09. The structure of the obtained multifunctional polymer is shown below:

[0059]

[0060] A mixture of 5.6 parts of 2-phenylethyl acrylate, 4.4 parts of 2-methylphenylethyl acrylate, 0.1 part of azobisisobutyronitrile and 0.2 parts of the product of the above multifunctional polymer as crosslinking agent were mixed uniformly to dissolution. The mixture was injected into a polytetrafluoroethylene mold, and after bubbling in an inert atmosphere for about 30 min, it was cured at 60°C for 2 h and at 110°C for 2 h, and then the mold was slowly cooled to room temperature. The prepared intraocular lens material was soaked in anhydrous ethanol, and after rinsing 3 times to remove the surface unreacted monomers, a Soxhlet extraction operation can be performed if necessary. After the anhydrous ethanol was completely volatilized, it was soaked and rinsed 3 times with deionized water, and vacuum dried. The property evaluation of the obtained intraocular lens material can be seen in Table 1.

[0061] Example 3

[0062] This example uses pentaerythritol as an initiator, and other conditions are the same as in Example 2. The structure of the obtained multifunctional polymer is shown below:

[0063]

[0064] Example 1

[0065] Example 4

[0066] In this example, a random copolymer multifunctional polymer was synthesized by feeding GMA in one shot and continuously feeding in EO without any interruption using ethylene glycol as initiator. Other conditions were the same as in Example 2, and the amount of EO was still 50 parts, which was slowly bubbled into the reaction flask and the bubbling was completed after 12 h. The structure of the obtained multifunctional polymer is shown below:

[0067]

[0068] Example 1

[0069] Example 5

[0070] In this example, a random copolymer multifunctional polymer was synthesized by feeding GMA in one shot and continuously feeding in PO without any interruption using ethylene glycol as initiator. Other conditions were the same as in Example 2. The structure of the obtained multifunctional polymer is shown below:

[0071]

[0072] Example 1

[0073] Example 6

[0074] Under inert atmosphere, 30 parts of GMA, 20 parts of phthalic anhydride, 0.1 part of phosphazene base and 1 part of ethylene glycol were added to a glass reactor. After dissolution with tetrahydrofuran, the mixture was homogenized and reacted at 80°C for 10 h. After the reaction was completed, a large amount of methanol was added for precipitation, the polymer was collected and dried in a vacuum oven at 50°C for 12 h. The product molecular weight was measured by SEC to be 7.3 kg / mol with a dispersity of 1.1. The structure of the obtained multifunctional polymer is shown below:

[0075]

[0076] The 6.1 parts of 2-phenylethyl acrylate, 3.9 parts of 2-methylphenylethyl acrylate, 0.1 part of azobisisobutyronitrile and 0.05 parts of the above multifunctional polymer as crosslinking agent were mixed uniformly to dissolution. The mixture was injected into a polytetrafluoroethylene mold, after bubbling in an inert atmosphere for about 30 min, cured at 60°C for 2 h and cured at 120°C for 2 h, and then the mold was slowly cooled to room temperature. Other conditions were the same as Example 2. The obtained intraocular lens material property evaluation can be seen in Table 1.

[0077] Example 7

[0078] Under inert atmosphere, 30 parts of GMA, 20 parts of bicyclo[2.2.2]oct-5-ene-2,3- dicarboxylic anhydride, 0.5 parts of phosphazene base, 0.25 parts of triethylboron and 1 part of ethylene glycol were added to a glass reactor. After dissolution with tetrahydrofuran, the mixture was homogenized and reacted at room temperature for 24 h. After the reaction was completed, a large amount of methanol was added for precipitation, the polymer was collected and dried in a vacuum oven at 50°C for 12 h. The structure of the obtained multifunctional polymer is shown below:

[0079]

[0080] The 5.5 parts of 2-phenylethyl acrylate, 4.5 parts of 2-methylphenylethyl acrylate, 0.1 part of azobisisobutyronitrile and 0.2 parts of the above multifunctional polymer as crosslinking agent were mixed uniformly to dissolution. The mixture was injected into a polytetrafluoroethylene mold, after bubbling in an inert atmosphere for about 20 min, cured at 60°C for 2 h and cured at 120°C for 2 h, and then the mold was slowly cooled to room temperature. Other conditions were the same as Example 2. The obtained intraocular lens material property evaluation can be seen in Table 1.

[0081] Example 8

[0082] Example 4 7.8 parts of 2-phenylethyl acrylate, 2.2 parts of (2-hydroxy)ethyl methacrylate, 0.1 part of azobisisobutyronitrile and 0.2 part of the above multifunctional polymer as crosslinking agent were mixed homogeneously to dissolution. The mixture was injected into a polytetrafluoroethylene mold, bubbled in an inert atmosphere for about 20 min, cured at 60°C for 2 h and cured at 120°C for 2 h, and then the mold was slowly cooled to room temperature. Other conditions were the same as in Example 2. The obtained intraocular lens material was evaluated for its properties as shown in Table 1.

[0083] Comparative Example 1

[0084] In this example, the ring-opening polymerization of GMA and phenyl glycidyl ether was carried out using ethylene glycol as an initiator, a two-component catalyst of 0.05 part of phosphazene base and 0.3 part of triethyl boron. Other conditions were the same as in Example 2. The obtained multifunctional polymer has the following structure:

[0085]

[0086] 6.0 parts of 2-phenylethyl acrylate, 4.0 parts of 2-methylphenylethyl acrylate, 0.1 part of azobisisobutyronitrile and 0.2 part of the above multifunctional polymer as crosslinking agent were mixed homogeneously to dissolution. The mixture was injected into a polytetrafluoroethylene mold, bubbled in an inert atmosphere for about 25 min, cured at 70°C for 2 h and cured at 115°C for 2.5 h, and then the mold was slowly cooled to room temperature. Other conditions were the same as in Example 2. The obtained intraocular lens material was evaluated for its properties as shown in Table 1.

[0087] Comparative Example 2

[0088] In this example, the ring-opening polymerization of GMA and phenyl glycidyl ether was carried out using ethylene glycol as an initiator, a two-component catalyst of 0.05 part of phosphazene base and 0.3 part of triethyl boron. Other conditions were the same as in Example 2. The obtained multifunctional polymer has the following structure:

[0089]

[0090] 6.0 parts of 2-phenylethyl acrylate, 4.0 parts of 2-methylphenylethyl acrylate, 0.1 part of azobisisobutyronitrile and 0.2 part of the above multifunctional polymer as crosslinking agent were mixed homogeneously to dissolution. The mixture was injected into a polytetrafluoroethylene mold, bubbled in an inert atmosphere for about 25 min, cured at 70°C for 2 h and cured at 115°C for 2.5 h, and then the mold was slowly cooled to room temperature. Other conditions were the same as in Example 2. The obtained intraocular lens material was evaluated for its properties as shown in Table 1.

[0091] Table 1

[0092]

[0093] Table 1 lists the basic performance indexes of the intraocular lens materials obtained in Examples 1-8 and Comparative Examples 1-2. It can be seen that the intraocular lens materials of Examples 1-8 have lower breaking strength, better toughness, no fold after being folded 180°, and can restore the original shape after several seconds, high refractive index, low glass transition temperature, and good biocompatibility. At the same time, the density of the amorphous phase is low, and the optical performance is good. The density of the amorphous phase of Comparative Examples 1-2 is significantly increased.

[0094] The above merely describes the preferred specific embodiments of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can make equivalent replacements or changes within the technical range disclosed by the present application and according to the technical scheme and inventive concept of the present application, which should be covered within the protection scope of the present application.

Claims

1. A multifunctional polymer for synthetic intraocular lens material, characterized by, having a structure of Formula I; wherein, the x is an integer from 2 to 8; the y is an integer from 1 to 4; R1is H, C1to C5alkyl, C6to C10aryl, or C2to C8alkanoyl; 10 R1is H, C1to C5alkyl, C6to C10aryl, or C2to C8alkanoyl; the R2 is H or methyl; the A is a group having a structure of Formula I-1, Formula I-2 or Formula I-3; wherein, the n is an integer from 0 to 10; the M1 is a substituted or unsubstituted C1-C5 alkyl; M2 is either substituted or unsubstituted C3-C4. 10 Alkyl, substituted or unsubstituted C6-C 12 Aryl or substituted or unsubstituted C3-C 10 Cycloalkenyl.

2. The multifunctional polymer for synthetic use of an intraocular lens material according to claim 1, characterized by, the M2 is a group having a structure of Formula I-2-a: wherein, the R4 and R5 are independently H, methyl, ethyl or phenyl; or, the M2 is a substituted or unsubstituted phenyl; or said M2is a substituted or unsubstituted C7to C 10 cycloalkenyl.

3. The multifunctional polymer for synthetic use of an intraocular lens material according to claim 1, characterized by, said group having the structure of Formula I-2 is selected from or 4. The multifunctional polymer for synthetic use of an intraocular lens material according to claim 1, characterized by, which has one of the structures of Formula a to Formula g: In formula f and formula g, m = (n + x) / 2, and n = x.

5. The method for producing a multifunctional polymer for synthetic material of an intraocular lens as claimed in any one of claims 1 to 4, characterized by, comprising the following steps: polymerizing, under the action of a catalyst, a compound of active hydrogen, a first co-monomer and optionally a second co-monomer to obtain a multifunctional polymer for synthesizing intraocular lens material; said active hydrogen compound is selected from one or more of water, a C1-C5 alkyl monohydric alcohol, a C6-C10 aryl monohydric phenol, or a C2-C8 alkyl monohydric carboxylic acid; 10 said active hydrogen compound is selected from one or more of water, a C1-C5 alkyl monohydric alcohol, a C6-C10 aryl monohydric phenol, or a C2-C8 alkyl monohydric carboxylic acid; said first comonomer is selected from The second comonomer is selected from one or more of CO2.

6. The production method according to claim 5, wherein the compound of active hydrogen is selected from ethylene glycol or pentaerythritol; the second co-monomer is selected from oxirane, oxetane or phthalic anhydride; the catalyst is selected from an organic base or a combination with organic boron.

7. The preparation method according to claim 5, characterized in that, The temperature of the polymerization reaction is from 0 to 100℃; the time of the polymerization reaction is from 0.5 to 300h.

8. Use of the multifunctional polymer for synthesizing intraocular lens material according to any one of claims 1 to 4 as a crosslinking agent for preparing intraocular lens material.

9. An intraocular lens material, characterized by which is obtained by polymerization of raw materials comprising the multifunctional polymer for synthesizing intraocular lens material according to any one of claims 1 to 4, at least two main monomers and optionally an ultraviolet absorber; the main monomer is selected from (meth)acrylate containing aromatic ring and optionally hydrophilic (meth)acrylate.

10. An intraocular lens, characterized in that which is processed from the intraocular lens material according to claim 9.

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