Method for reducing residual monomer content in a polymer composition, polymer composition, radically polymerizable composition, polymer production method, polymer and use

Abstract

The invention relates to a method for reducing the residual monomer content in a polymer composition, a polymer composition, a radically polymerizable composition, a polymer production method, a polymer and use.

Description

Technical Field

[0001] This invention relates to the field of polymers, particularly to the field of medical polymers. Specifically, this invention relates to methods for reducing the residual monomer content in polymer compositions, polymer compositions prepared by said methods, compositions capable of free radical polymerization, methods for preparing polymers using said free radical polymerizable compositions, polymers prepared from said free radical polymerizable compositions, and the use of said free radical polymerizable compositions in the preparation of polymers. Background Technology

[0002] Medical polymer materials, also known as medical high molecular weight materials, are a class of synthetic polymer materials with special functions used to manufacture internal and external organs, drug formulations, and medical devices. They are an important component of biomedical materials. Medical polymer materials can possess different physical and chemical properties through control of their composition and structure to meet the needs of various applications. Because they act on the human body, medical polymer materials have higher requirements for their basic properties compared to ordinary polymer materials. For example, medical polymer materials require good biocompatibility, strong chemical stability, excellent physical and mechanical properties, and ease of molding and processing. Among these, biocompatibility is the most critical, and chemical residues, extractables, and leachables are key factors affecting biocompatibility.

[0003] Contact lenses are a type of commonly used medical polymer material, an optical instrument attached to the surface of the cornea to correct refractive errors; they include soft contact lenses and rigid gas permeable (RGP) contact lenses. As a special biomaterial, contact lenses must be compatible with various tissues on the ocular surface. Because they cover the cornea, they reduce the corneal oxygen supply. The oxygen permeability coefficient (DK) is the main parameter measuring the material's ability to allow oxygen to pass through. Since the cornea has no blood vessels, it must obtain nutrients and metabolic substances from tears, aqueous humor, and oxygen dissolved in tears. Corneal hypoxia causes edema of the corneal epithelium and stroma. Therefore, rigid gas permeable (RGP) contact lenses were developed.

[0004] Medical RGP materials are typically composed of siloxane-based methacrylates, methacrylates, or fluorinated methacrylates as the main components, polymerized through free radical copolymerization or other methods. In clinical applications, to impart properties such as resistance to protein deposition, specific toughness and strength, and hydrophilicity, functional olefin-terminated monomers are often added to improve wearing comfort and enhance safety.

[0005] For RGP materials that come into long-term contact with the cornea, improving oxygen permeability and reducing the likelihood of corneal edema is certainly important. However, as a material that comes into direct contact with the cornea, the lens material will be in full contact with eye tissues such as the cornea and conjunctiva during wear. Monomer components in RGP materials that have not fully participated in polymerization, as well as extractable and leachable materials, can be absorbed by the ocular surface through tear exchange or passive diffusion, causing biosafety issues such as irritation and damage to the cornea and other eye tissues.

[0006] RGP materials are copolymerized and cross-linked from various functional monomers. Due to the differences in the polymerization sites and chemical environments of each monomer, it is difficult for different monomers to copolymerize ideally, resulting in some or even a large amount of unpolymerized monomers remaining in the system. Moreover, after the RGP copolymer is formed during the polymerization process, its macromolecular structure makes it difficult to purify it using conventional chemical methods. It is also difficult to remove residual monomers and unknown impurities that have not fully participated in the reaction through post-processing.

[0007] To reduce RGP monomer residue, the art often requires repeated and meticulous adjustments to the formulation, increased complex process control, and longer polymerization reaction times, which increases process complexity and production costs.

[0008] Therefore, from a clinical application perspective, an excellent RGP material must possess low extractable and leachable (chemical residue) content and high oxygen permeability. However, these two points are often contradictory; improving oxygen permeability necessitates adding one or more monomers that promote oxygen permeability to the composition, such as siloxane oligomers and sterically hindered silicon- or fluorine-containing monomers. However, increasing the variety of monomers, especially the presence of oligomers and sterically hindered monomers, increases the complexity of the copolymerization process, leading to further exacerbation of monomer residues. This is why, despite decades of development in rigid contact lenses, only a handful of materials have been approved for clinical use. Currently, the RGP materials used in Class III medical devices marketed in China include: Boston ® Equalens ® II (DK 85), Boston XO ® (DK 100) 、 Boston XO2 ® (DK141), Paragon HDS 100 ® (DK 100), Menicon Z ® (DK 163), Optimum Extreme ® (DK 125), used in the Optimum Infinite contact lens abroad. ®(DK 180), Acuity 200 TM (DK 200) etc.

[0009] In short, the development of highly oxygen-permeable materials is inherently challenging; in addition to considering the DK parameter, physical parameters such as toughness, strength, and water wettability must also be taken into account. Maintaining high oxygen permeability and other physical properties while further reducing monomer residue and mitigating the risks associated with biosafety assessments becomes exceptionally difficult.

[0010] CN112513114A discloses a method for producing ultra-high Dk materials. This method involves polymerizing fluoroalkyl methacrylate, alkyl diol dimethacrylate, a hydrophilic agent such as methacrylic acid, hydroxyalkyl tris(trimethylsiloxy)silane, hydroxyalkyl-terminated polydimethylsiloxane, and styrylethyltris(trimethylsiloxy)silane at a specific temperature under an inert atmosphere and a pressure of at least 25 psi, to prepare RGP materials with a DK greater than 175. Polymerization under inert gas and high pressure poses significant challenges to the production process, molds, and operational safety. This technical solution does not analyze the copolymerization process under high pressure, nor does it provide qualitative or quantitative analysis data on chemical residues.

[0011] CN116515300A discloses a composition of a high oxygen permeability material, which is cured by a special non-free radical curing crosslinking process to prepare a contact lens with a Shore D hardness ≥60 and a DK ≥200. The composition comprises the following components: (a) a hydrogen-containing silicone resin containing SiH groups; (b) a vinyl-containing silicone resin containing unsaturated carbon-carbon double bonds; (c) a catalyst; and (d) a hydrosilylation reaction inhibitor. The structural (D-type, T-type, Q-type) composition ratio of the hydrogen-containing silicone resin and the vinyl-containing silicone resin is specified. The disclosed data shows that this method can prepare materials with a KD greater than 200, but compared to commercially available products like Boston XO... ® (Shore D=81) The material's hardness is significantly low, making it relatively soft and resulting in poor processability. This technical solution also fails to provide residual data on the relevant monomers after polymerization.

[0012] CN106749877A discloses a high oxygen permeability optical lens material composition and its preparation method. The material comprises: 1-30% methacryloyl T-structure siloxane, 30-60% fluorinated methacrylate monomers, 20-40% methacryloyl(trimethylsiloxy)silane, 3-15% hydrophilic monomers, 5-30% methacryloyl-terminated siloxanes, 1-10% crosslinking agent, 0.01-0.5% free radical initiator, and 0.1-5% ultraviolet absorber. The disclosed optical lens material exhibits certain oxygen permeability (105-171), along with good wettability and resistance to protein deposition. CN113698552A, based on the formulation disclosed in CN106749877A, adds a hydrophobic agent and fluorinated silicone methacrylate monomers, comprehensively improving the oxygen transmittance, spectral transmittance, and mechanical properties of the polyacrylate material. However, both patents only disclose methods to improve the oxygen permeability of materials, but do not analyze or confirm the residual status of monomers after copolymerization using these methods.

[0013] Menicon disclosed a method for reducing monomer residues in copolymers used in contact lens materials in patent CN1894620A. However, this method achieves this at the cost of removing hydrophilic monomers from the copolymer formulation. The resulting copolymer is obtained by polymerizing monomers containing polysiloxanes with a special structure. The residual unpolymerized monomer content in the copolymer is ≤3%, DK≥130, and the water absorption rate of the copolymer is ≤0.3%. This material has almost no water wettability, and the purely hydrophobic material has poor wearing comfort and also poses a risk of corneal epithelial cell adhesion. Although the surface of the hydrophobic material can be modified to be hydrophilic through surface treatment technology, the effective period of existing surface modification technology (generally 1-2 months) is much shorter than the service life of RGP contact lenses (1 year). When the surface modification fails, the problems of the hydrophobic material are exposed again. Therefore, this technical solution cannot be applied clinically at present.

[0014] As mentioned above, the development and application of rigid gas permeable (RGP) medical polymer materials must balance high oxygen permeability and low chemical residues (extractable and leachable substances), as these factors jointly determine the safety and effectiveness of RGP materials. Current technologies focus more on simply improving oxygen permeability or reducing monomer residues at the expense of wearing safety and comfort.

[0015] Therefore, there remains a need in the art to provide methods for achieving low chemical residues and thus high biocompatibility in polymer materials, such as medical polymer materials, particularly RGP materials that achieve low chemical residues, while also possessing excellent oxygen permeability and retaining excellent overall properties such as water wettability and processability. Summary of the Invention

[0016] This invention is made in response to the aforementioned problems existing in the prior art.

[0017] In a first aspect, the present invention provides a method for reducing the residual monomer content in a polymer composition (or polymer), said polymer composition being a polymer composition prepared by free radical polymerization using a first composition containing an olefinically unsaturated monomer derived from an isopropylene group (CH2=C(CH3)-) that is capable of free radical polymerization. The polymer composition (or polymer) obtained by the method of the present invention has low chemical residues and therefore high biocompatibility, making it suitable for use as a medical polymer material. Furthermore, this free radical polymerization does not require complex process control.

[0018] In a second aspect, the present invention provides a polymer composition (or polymer) obtained by the method according to the first aspect of the invention.

[0019] In a third aspect, the present invention provides a composition capable of free radical polymerization, the composition comprising a monoalkenyl-functionalized hydrophobic fluorinated monomer component, a monoalkenyl-functionalized hydrophobic silicon-containing monomer component, and a monoalkenyl-functionalized hydrophilic monomer component, wherein the polymer (or polymer composition) obtained by free radical polymerization has low chemical residues and therefore high biocompatibility, making it suitable for use as a medical polymer material. Furthermore, this free radical polymerization does not require complex process control.

[0020] Furthermore, the present invention provides a composition capable of free radical polymerization, the composition comprising a monoalkenyl-functional hydrophobic fluorinated monomer component, a monoalkenyl-functional hydrophobic silicon-containing monomer component, and a monoalkenyl-functional hydrophilic monomer component. The polymer obtained by free radical polymerization has low chemical residue and its polymerization does not require complex process control, while also exhibiting good hardness, oxygen permeability, water wettability, and processability; and therefore, it can be used, for example, to prepare corneal contact lenses, such as rigid gas permeable corneal contact lenses.

[0021] In a fourth aspect, the present invention provides a method for preparing a polymer by subjecting a composition according to a third aspect of the invention to free radical polymerization.

[0022] In a fifth aspect, the present invention provides a polymer obtained by free radical polymerization of a composition according to a third aspect of the present invention.

[0023] In a sixth aspect, the present invention provides the use of compositions according to a third aspect of the invention in the preparation of polymers.

[0024] Specifically, the present invention is achieved by the following:

[0025] 1. A method for reducing the residual monomer content in a polymer composition, said polymer composition being a polymer composition prepared by free radical polymerization using a first composition capable of free radical polymerization, said first composition capable of free radical polymerization comprising a mixture of:

[0026] The first ene unsaturated monomer component is based on the first ene unsaturated monomer, wherein the olefin bond in the first ene unsaturated monomer originates from the isopropenyl group (CH2=C(CH3)-).

[0027] Free radical initiators,

[0028] Optionally, ultraviolet absorbers, and

[0029] Optional, dye;

[0030] The method includes providing a second composition capable of free radical polymerization by replacing a portion of a first olefinically unsaturated monomer component with a second olefinically unsaturated monomer component based on a second olefinically unsaturated monomer: wherein the olefinic bond of the second olefinically unsaturated monomer is derived from vinyl (CH2=CH-);

[0031] The second composition, which is capable of free radical polymerization, is then subjected to free radical polymerization.

[0032] 2. The method according to Project 1, wherein the olefin bond in the first olefin unsaturated monomer is derived from methacryloyloxy, and the olefin bond in the second olefin unsaturated monomer is derived from one or more of the following: acryloyloxy, acryloylamino, N-vinylamino, vinylphenyl.

[0033] 3. The method according to any one of items 1-2, wherein the first olefinically unsaturated monomer and the second olefinically unsaturated monomer have the same alkenyl functionality;

[0034] Preferably, the first olefin unsaturated monomer is a monoalkenyl functional olefin unsaturated monomer, and the second olefin unsaturated monomer is a monoalkenyl functional olefin unsaturated monomer.

[0035] 4. The method described according to any one of items 1-3, wherein...

[0036] The first olefinically unsaturated monomer includes or is a first hydrophobic monomer containing a methacryloyl group, such as a hydrophobic methacrylate monomer, a first hydrophilic monomer containing a methacryloyl group, or any combination thereof; preferably, the first olefinically unsaturated monomer includes or is a first hydrophobic monomer containing a methacryloyl group, such as a hydrophobic methacrylate monomer and a first hydrophilic monomer containing a methacryloyl group, and the second olefinically unsaturated monomer includes or is a second hydrophobic monomer, such as a hydrophobic acrylate monomer, a second hydrophilic monomer, or a combination thereof; preferably, the difference between the first hydrophobic monomer and the second hydrophobic monomer is only that the methacryloyloxy group in the first hydrophobic monomer is replaced with an acryloxy group, vinylphenyl group, or a combination thereof in the second hydrophobic monomer; preferably, the difference between the first hydrophilic monomer and the second hydrophilic monomer is only that the methacryloyloxy group in the first hydrophilic monomer is replaced with an acryloxy group in the second hydrophilic monomer;

[0037] Preferably, the first olefinically unsaturated monomer comprises or is a first hydrophobic fluorinated monomer containing a methacryloyl group, such as a hydrophobic fluorinated alkyl methacrylate monomer, a first hydrophobic silicon-containing monomer containing a methacryloyl group, such as a silicon-containing hydrophobic methacrylate monomer, a first hydrophilic monomer containing a methacryloyl group, or any combination thereof; preferably, the first olefinically unsaturated monomer comprises or is a first hydrophobic fluorinated monomer containing a methacryloyl group, such as a hydrophobic fluorinated alkyl methacrylate monomer, a first hydrophobic silicon-containing monomer containing a methacryloyl group, such as a silicon-containing hydrophobic methacrylate monomer, and a first hydrophilic monomer containing a methacryloyl group, and the second olefinically unsaturated monomer comprises or is a second hydrophobic fluorinated monomer, such as a hydrophobic fluorinated alkyl acrylate. The monomer, the second hydrophobic silicon-containing monomer such as a silicon-containing hydrophobic acrylate monomer and / or a vinylphenyl-containing silane, the second hydrophilic monomer, or a combination thereof; preferably, the difference between the first hydrophobic fluorinated monomer and the second hydrophobic fluorinated monomer is only that the methacryloxy group in the first hydrophobic fluorinated monomer is replaced with the acryloxy group in the second hydrophobic fluorinated monomer; preferably, the difference between the first hydrophobic silicon-containing monomer and the second hydrophobic silicon-containing monomer is only that the methacryloxy group in the first hydrophobic silicon-containing monomer is replaced with the acryloxy group, vinylphenyl group, or a combination thereof in the second hydrophobic silicon-containing monomer; preferably, the difference between the first hydrophilic monomer and the second hydrophilic monomer is only that the methacryloxy group in the first hydrophilic monomer is replaced with the acryloxy group in the second hydrophilic monomer;

[0038] Preferably, the first olefinically unsaturated monomer comprises or is a monoalkenyl-functionalized first hydrophobic fluorinated monomer containing a methacryloyl group, such as a hydrophobic fluorinated alkyl methacrylate monomer, a monoalkenyl-functionalized first hydrophobic silicon-containing monomer containing a methacryloyl group, such as a silicon-containing hydrophobic methacrylate monomer, a monoalkenyl-functionalized first hydrophilic monomer containing a methacryloyl group, or any combination thereof; preferably, the first olefinically unsaturated monomer comprises or is a monoalkenyl-functionalized first hydrophobic fluorinated monomer containing a methacryloyl group, such as a hydrophobic fluorinated alkyl methacrylate monomer, a monoalkenyl-functionalized first hydrophobic silicon-containing monomer containing a methacryloyl group, such as a silicon-containing hydrophobic methacrylate monomer, and a monoalkenyl-functionalized first hydrophilic monomer containing a methacryloyl group, and the second olefinically unsaturated monomer comprises or is a monoalkenyl-functionalized second hydrophobic fluorinated monomer. Examples of the first hydrophobic fluorinated monomer include hydrophobic alkyl acrylate monomers, monoalkenyl-functionalized second hydrophobic silicon-containing monomers such as silicon-containing hydrophobic acrylate monomers, silanes containing vinylphenyl groups or combinations thereof, monoalkenyl-functionalized second hydrophilic monomers or combinations thereof; preferably, the difference between the first hydrophobic fluorinated monomer and the second hydrophobic fluorinated monomer is only that the methacryloxy group in the first hydrophobic fluorinated monomer is replaced with the acryloxy group in the second hydrophobic fluorinated monomer; preferably, the difference between the first hydrophobic silicon-containing monomer and the second hydrophobic silicon-containing monomer is only that the methacryloxy group in the first hydrophobic silicon-containing monomer is replaced with the acryloxy group, vinylphenyl group or combination thereof in the second hydrophobic silicon-containing monomer; preferably, the difference between the first hydrophilic monomer and the second hydrophilic monomer is only that the methacryloxy group in the first hydrophilic monomer is replaced with the acryloxy group in the second hydrophilic monomer.

[0039] 5. The method according to any one of items 1-4, wherein the second composition capable of free radical polymerization comprises:

[0040] (1) A monoalkenyl-functional hydrophobic fluorinated monomer component, which includes or is composed of the following:

[0041] (1-1) Based on the first hydrophobic fluorinated monomer component of fluorinated alkyl methacrylate as the first hydrophobic fluorinated monomer;

[0042] Preferably, the first hydrophobic fluorinated monomer is a C1-C10 fluorinated alkyl methacrylate, more preferably a C1-C6 fluorinated alkyl methacrylate, more preferably a C2-C5 fluorinated alkyl methacrylate, and even more preferably a C2-C3 fluorinated alkyl methacrylate; preferably, the first hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, and 2,2,3,3,3-pentafluoropropyl methacrylate; more preferably, the first hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl methacrylate and hexafluoroisopropyl methacrylate.

[0043] and

[0044] (1-2) Optional second hydrophobic fluorinated monomer component based on fluorinated alkyl acrylate as a second hydrophobic fluorinated monomer;

[0045] Preferably, the fluorinated alkyl group in the second hydrophobic fluorinated monomer is the same as or different from the fluorinated alkyl group in the first hydrophobic fluorinated monomer, and preferably the same;

[0046] Preferably, the second hydrophobic fluorinated monomer is a C1-C10 fluorinated alkyl acrylate, more preferably a C1-C6 fluorinated alkyl acrylate, more preferably a C2-C5 fluorinated alkyl acrylate, and even more preferably a C2-C3 fluorinated alkyl acrylate; preferably, the second hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl acrylate, hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, and 2,2,3,3,3-pentafluoropropyl acrylate; more preferably, the second hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl acrylate and hexafluoroisopropyl acrylate.

[0047] Preferably, the first hydrophobic fluorinated monomer is selected from one or more of hexafluoroisopropyl methacrylate and trifluoroethyl methacrylate, and the second hydrophobic fluorinated monomer is selected from one or more of hexafluoroisopropyl acrylate and trifluoroethyl acrylate; preferably, the first hydrophobic fluorinated monomer is hexafluoroisopropyl methacrylate and the second hydrophobic fluorinated monomer is hexafluoroisopropyl acrylate, or the first hydrophobic fluorinated monomer is trifluoroethyl methacrylate and the second hydrophobic fluorinated monomer is trifluoroethyl acrylate;

[0048] (2) Monoalkenyl-functional hydrophobic silicon-containing monomer components, which include or are composed of the following:

[0049] (2-1) Based on the first hydrophobic silicon-containing monomer component of silicon-containing methacrylate as the first hydrophobic silicon-containing monomer,

[0050] Preferably, the first hydrophobic silicon-containing monomer is a silicon-containing methacrylate of the following formula: CH2=C(CH3)-C(O)-O-L1-Si(R1)m(OR2)3-m L1 is a C1-C10, preferably C3-C6 divalent alkylene group that optionally includes one or more groups selected from ether-O-atom groups and -OH groups; R1 is the same as or different from each other and is independently C1-C6 alkyl, preferably methyl; R2 is the same as or different from each other and is independently C1-C6 alkyl, preferably methyl, or -Si(R3)3, wherein R3 is the same as or different from each other and is independently C1-C6 alkyl, preferably methyl; m is 0, 1, 2, or 3, preferably 0 or 1.

[0051] Preferably, the first hydrophobic silicon-containing monomer is selected from one or more of methacryloyloxypropyltris(trimethylsiloxane)silane and (3-methacryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane;

[0052] and

[0053] (2-2) Optionally, a second hydrophobic silicon-containing monomer component based on a silicon-containing acrylate or a vinylphenyl-containing silane as a second hydrophobic silicon-containing monomer.

[0054] Preferably, the second hydrophobic silicon-containing monomer is CH2=CH-C(O)-O-L2-Si(R4). n (OR5) 3-n Or CH2=CH-Ph-Si(R4) n (OR5) 3-n Ph is a phenylene, for example, 1,4-phenylene; L2 is the same as or different from L1 and is a C1-C10, preferably C3-C6 dialkylene group, optionally including one or more groups of ether-O-atom group or -OH group; R4 is the same as or different from each other and the same as or different from R1 and is independently a C1-C6 alkyl group, preferably methyl; R5 is the same as or different from each other and the same as or different from R2 and is independently a C1-C6 alkyl group, preferably methyl or -Si(R6)3, wherein R6 is the same as or different from each other and the same as or different from R3 and is independently a C1-C6 alkyl group, preferably methyl; n is the same as or different from m and is 0, 1, 2 or 3, preferably 0 or 1;

[0055] Preferably, -Si(R4) n (OR5) 3-n Partially related to -Si(R1)m(OR2) 3-m If some parts are the same or different, the same parts are preferred.

[0056] Preferably, -L2-Si(R4) n (OR5) 3-n Partially related to -L1-Si(R1)m(OR2) 3-m If some parts are the same or different, the same parts are preferred.

[0057] Preferably, the second hydrophobic silicon-containing monomer is selected from one or more of acryloyloxypropyltris(trimethylsiloxane), (3-acryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, and p-vinylphenyltris(trimethylsiloxy)silane;

[0058] Preferably, the first hydrophobic silicon-containing monomer is selected from methacryloyloxypropyltris(trimethylsiloxane)silane, and the second hydrophobic silicon-containing monomer is selected from one or more of acryloyloxypropyltris(trimethylsiloxane)silane and p-vinylphenyltris(trimethylsiloxy)silane, preferably acryloyloxypropyltris(trimethylsiloxane);

[0059] (3) Monoalkenyl-functional hydrophilic monomer components, which include or are composed of the following:

[0060] (3-1) A first hydrophilic monomer component based on a first hydrophilic monomer containing a methacryloyl group;

[0061] Preferably, the first hydrophilic monomer is selected from one or more of methacrylic acid, hydroxyethyl methacrylate, methacrylamide, and N,N-dimethylmethacrylamide;

[0062] and / or

[0063] (3-2) A second hydrophilic monomer component based on a second hydrophilic monomer containing acryloyloxy, acryloylamino and / or N-vinylamino;

[0064] Preferably, the difference between the second hydrophilic monomer and the first hydrophilic monomer is only that the second hydrophilic monomer uses an acryloyl group instead of a methacryloyl group in the first hydrophilic monomer;

[0065] Preferably, the second hydrophilic monomer is selected from one or more of acrylic acid, hydroxyethyl acrylate, acrylamide, N,N-dimethylacrylamide, N-vinylpyrrolidone, and N-methyl-N-vinylacetamide;

[0066] Preferably, the first hydrophilic monomer is selected from methacrylic acid, and the second hydrophilic monomer is selected from one or more of acrylic acid, N-vinylpyrrolidone (NVP) and N,N-dimethylacrylamide, preferably acrylic acid;

[0067] (4) Optionally, a crosslinking agent component based on a diene-functional or higher crosslinking agent;

[0068] Preferably, the crosslinking agent with diene or higher functionality is selected from: alkyl glycol dimethacrylate, preferably neopentyl glycol dimethacrylate; siloxane-containing oligomers, preferably 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane; or any combination thereof; for example, neopentyl glycol dimethacrylate and 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, which are present, for example, in a mass ratio of 10:90-90:10, for example 30:70-70:30, for example 50:50-60:40;

[0069] (5) Free radical initiators, such as azobisisobutyronitrile or azobisisoheptanenitrile;

[0070] (6) Optionally, a UV absorber, such as 2-hydroxy-4-(methacryloyloxy)benzophenone;

[0071] When a first hydrophilic monomer is present, one, two, or three of the following may be present: a second hydrophobic fluorinated monomer, a second hydrophobic silicon-containing monomer, and a second hydrophilic monomer.

[0072] 6. The method according to any one of items 1-5, wherein the second composition capable of free radical polymerization comprises, based on the total mass of the second composition capable of free radical polymerization:

[0073] (1) 30-60% by mass, for example 40-50% by mass, of a monoalkenyl-functional hydrophobic fluorinated monomer component;

[0074] (2) 20-45% by mass, for example 30-40% by mass, of monoalkenyl-functional hydrophobic silicon-containing monomer components;

[0075] (3) 3-20% by mass, for example 5-10% by mass, of a monoalkenyl-functional hydrophilic monomer component;

[0076] (4) Optionally, 1-20% by mass, for example 5-15% by mass, of a crosslinking agent component based on a diene-functionalized or higher crosslinking agent; and

[0077] (5) 0.1-2.0% by mass, for example 0.5-1.0% by mass, of a free radical initiator; and

[0078] (6) Optionally, 0.1-5.0% by mass, for example 0.2-1.0% by mass, for example 0.4-0.6% by mass of a UV absorber.

[0079] 7. The method according to any one of items 4-6, wherein, in the second composition capable of free radical polymerization:

[0080] The presence of a second hydrophobic fluorinated monomer, preferably in a mass ratio of 30:70-80:20, for example 50:50-80:20, or for example 70:30-80:20; and / or

[0081] The presence of a second hydrophobic silicon-containing monomer, preferably in a mass ratio of 30:70-80:20, for example 50:50-75:25, to the first hydrophobic silicon-containing monomer; and / or

[0082] The presence of a first hydrophilic monomer and a second hydrophilic monomer is preferred, with the first hydrophilic monomer and the second hydrophilic monomer present in a mass ratio of 0:100-85:15, for example 25:75-80:20, for example 40:60-75:25.

[0083] 8. The method according to any one of items 4-7, wherein the second composition capable of free radical polymerization contains a second hydrophobic fluorinated monomer, a second hydrophobic silicon-containing monomer, a first hydrophilic monomer, and a second hydrophilic monomer.

[0084] 9. The method according to any one of items 1-8, wherein the method comprises performing a purification step prior to polymerization and before providing the second composition capable of free radical polymerization:

[0085] The first olefinically unsaturated monomer component is purified to increase the content of the first olefinically unsaturated monomer and / or decrease the content of the polymerization inhibitor, for example, to make the content of the first olefinically unsaturated monomer 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor 50 ppm by mass or less; and / or

[0086] The second olefin unsaturated monomer component is purified to increase the content of the second olefin unsaturated monomer and / or decrease the content of the polymerization inhibitor, for example, so that the content of the second olefin unsaturated monomer is 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor is 50 ppm by mass or less.

[0087] 10. The method according to any one of items 4-9, wherein the method comprises performing a purification step prior to polymerization and before providing the second composition capable of free radical polymerization:

[0088] The first hydrophobic fluorinated monomer component is purified to increase the content of the first hydrophobic fluorinated monomer and / or decrease the content of the polymerization inhibitor, for example, to make the content of the first hydrophobic fluorinated monomer 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor 50 ppm by mass or less; and / or

[0089] The second hydrophobic fluorinated monomer component is purified to increase the content of the second hydrophobic fluorinated monomer and / or decrease the content of the polymerization inhibitor, for example, to make the content of the second hydrophobic fluorinated monomer 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor 50 ppm by mass or less; and / or

[0090] The first hydrophobic silicon-containing monomer component is purified to increase the content of the first hydrophobic silicon-containing monomer and / or decrease the content of the polymerization inhibitor, for example, to make the content of the first hydrophobic silicon-containing monomer 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor 50 ppm by mass or less; and / or

[0091] The second hydrophobic silicon-containing monomer component is purified to increase the content of the second hydrophobic silicon-containing monomer and / or decrease the content of the polymerization inhibitor, for example, to make the content of the second hydrophobic silicon-containing monomer 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor 50 ppm by mass or less; and / or

[0092] The first hydrophilic monomer component is purified to increase the content of the first hydrophilic monomer and / or decrease the content of the polymerization inhibitor, for example, to make the content of the first hydrophilic monomer 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor 50 ppm by mass or less; and / or

[0093] The second hydrophilic monomer component is purified to increase the content of the second hydrophilic monomer and / or decrease the content of the polymerization inhibitor, for example, to make the content of the second hydrophilic monomer 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor 50 ppm by mass or less; and / or

[0094] The crosslinking agent component based on diene-functionalized or higher crosslinking agents is purified to increase the crosslinking agent content and / or decrease the polymerization inhibitor content, for example, so that the crosslinking agent content is 98% by mass or more, preferably 99% by mass or more, and / or the polymerization inhibitor content is 50 ppm by mass or less.

[0095] 11. The method according to any one of items 1-10, wherein the first composition capable of free radical polymerization comprises a non-reactive dye in an amount, for example, 0.001-0.5% by mass, such as 0.005-0.01% by mass, and the method further comprises partially or completely replacing the non-reactive dye in the first composition capable of free radical polymerization with a reactive dye, for example, containing an alkenyl group, such as containing a methacryloyl group, said reactive dye being selected, for example, from one or more of 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone, 1,4-bis((2-hydroxyethyl)amino)-9,10-anthradinone bis(2-propeneOIC) ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenethyl)methacrylamide.

[0096] 12. The method according to any one of items 1-11, wherein the polymer is a medical polymer, preferably a polymer used to prepare corneal contact lenses, and more preferably a polymer used to prepare rigid gas permeable corneal contact lenses.

[0097] 13. A method for reducing the residual monomer content in a polymer composition, said polymer composition being a polymer composition prepared by free radical polymerization using a first composition capable of free radical polymerization, said first composition capable of free radical polymerization comprising a mixture of:

[0098] The first ene unsaturated monomer component is based on the first ene unsaturated monomer, wherein the olefin bond in the first ene unsaturated monomer originates from the isopropenyl group (CH2=C(CH3)-).

[0099] Free radical initiators

[0100] Optionally, ultraviolet absorbers, and

[0101] Optional, dye;

[0102] The method includes, prior to polymerization and before combining the components to form the first composition capable of free radical polymerization, performing a purification step of purifying the first olefinic unsaturated monomer component to increase the content of the first olefinic unsaturated monomer and / or decrease the content of the polymerization inhibitor, for example, such that the content of the first olefinic unsaturated monomer is 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor is 50 ppm by mass or less.

[0103] Then free radical polymerization is carried out.

[0104] 14. The method according to item 13, wherein the method comprises: providing a second composition capable of free radical polymerization by replacing a portion of a first olefinically unsaturated monomer component with a second olefinically unsaturated monomer component based on a second olefinically unsaturated monomer: wherein the olefinic bond of the second olefinically unsaturated monomer is derived from vinyl (CH2=CH-);

[0105] The second composition, which is capable of free radical polymerization, is then subjected to free radical polymerization.

[0106] 15. The method according to item 14, wherein the first composition capable of free radical polymerization and the second composition capable of free radical polymerization are as defined in any one of items 2-12.

[0107] 16. A method for reducing the residual monomer content in a polymer composition, said polymer composition being a polymer composition prepared by free radical polymerization using a first composition capable of free radical polymerization, said first composition capable of free radical polymerization comprising a mixture of:

[0108] The first ene unsaturated monomer component is based on the first ene unsaturated monomer, wherein the olefin bond in the first ene unsaturated monomer originates from the isopropenyl group (CH2=C(CH3)-).

[0109] Free radical initiators,

[0110] Optionally, ultraviolet absorbers, and

[0111] Non-reactive staining agents;

[0112] The method includes: partially or completely replacing a non-reactive dye in the first composition capable of free radical polymerization with a reactive dye, for example, containing an alkenyl group or a methacryloyl group, to provide a second composition capable of free radical polymerization, wherein the reactive dye is selected, for example, from one or more of 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone, 1,4-bis((2-hydroxyethyl)amino)-9,10-anthradinone bis(2-propeneOIC) ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenethyl)methacrylamide;

[0113] Then free radical polymerization is carried out.

[0114] 17. The method according to item 16, wherein the amount of dye in the first composition capable of free radical polymerization and the amount of reactive dye in the second composition capable of free radical polymerization are each independently 0.001-0.5% by mass, for example 0.005-0.01% by mass.

[0115] 18. The method according to any one of items 16-17, wherein the method further comprises: providing the second composition capable of free radical polymerization by replacing a portion of the first olefinically unsaturated monomer component with a second olefinically unsaturated monomer component based on a second olefinically unsaturated monomer: wherein the olefinic bond of the second olefinically unsaturated monomer is derived from vinyl (CH2=CH-);

[0116] The second composition, which is capable of free radical polymerization, is then subjected to free radical polymerization.

[0117] 19. The method according to item 18, wherein the first composition capable of free radical polymerization and the second composition capable of free radical polymerization are as defined in any one of items 2-10 and 12.

[0118] 20. A polymer composition obtained by the method according to any one of items 1-19.

[0119] 21. A composition capable of free radical polymerization, comprising:

[0120] (1) A monoalkenyl-functional hydrophobic fluorinated monomer component, which includes or is composed of the following:

[0121] (1-1) Based on the first hydrophobic fluorinated monomer component of fluorinated alkyl methacrylate as the first hydrophobic fluorinated monomer;

[0122] Preferably, the first hydrophobic fluorinated monomer is a C1-C10 fluorinated alkyl methacrylate, more preferably a C1-C6 fluorinated alkyl methacrylate, more preferably a C2-C5 fluorinated alkyl methacrylate, and even more preferably a C2-C3 fluorinated alkyl methacrylate; preferably, the first hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, and 2,2,3,3,3-pentafluoropropyl methacrylate; more preferably, the first hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl methacrylate and hexafluoroisopropyl methacrylate.

[0123] and

[0124] (1-2) Optional second hydrophobic fluorinated monomer component based on fluorinated alkyl acrylate as a second hydrophobic fluorinated monomer;

[0125] Preferably, the fluorinated alkyl group in the second hydrophobic fluorinated monomer is the same as or different from the fluorinated alkyl group in the first hydrophobic fluorinated monomer, and preferably the same;

[0126] Preferably, the second hydrophobic fluorinated monomer is a C1-C10 fluorinated alkyl acrylate, more preferably a C1-C6 fluorinated alkyl acrylate, more preferably a C2-C5 fluorinated alkyl acrylate, and even more preferably a C2-C3 fluorinated alkyl acrylate; preferably, the second hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl acrylate, hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, and 2,2,3,3,3-pentafluoropropyl acrylate; more preferably, the second hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl acrylate and hexafluoroisopropyl acrylate.

[0127] Preferably, the first hydrophobic fluorinated monomer is selected from one or more of hexafluoroisopropyl methacrylate and trifluoroethyl methacrylate, and the second hydrophobic fluorinated monomer is selected from one or more of hexafluoroisopropyl acrylate and trifluoroethyl acrylate; preferably, the first hydrophobic fluorinated monomer is hexafluoroisopropyl methacrylate and the second hydrophobic fluorinated monomer is hexafluoroisopropyl acrylate, or the first hydrophobic fluorinated monomer is trifluoroethyl methacrylate and the second hydrophobic fluorinated monomer is trifluoroethyl acrylate;

[0128] (2) Monoalkenyl-functional hydrophobic silicon-containing monomer components, which include or are composed of the following:

[0129] (2-1) Based on the first hydrophobic silicon-containing monomer component of silicon-containing methacrylate as the first hydrophobic silicon-containing monomer,

[0130] Preferably, the first hydrophobic silicon-containing monomer is a silicon-containing methacrylate of the following formula: CH2=C(CH3)-C(O)-O-L1-Si(R1)m(OR2) 3-m L1 is a C1-C10, preferably C3-C6 divalent alkylene group that optionally includes one or more groups selected from ether-O-atom groups and -OH groups; R1 is the same as or different from each other and is independently C1-C6 alkyl, preferably methyl; R2 is the same as or different from each other and is independently C1-C6 alkyl, preferably methyl, or -Si(R3)3, wherein R3 is the same as or different from each other and is independently C1-C6 alkyl, preferably methyl; m is 0, 1, 2, or 3, preferably 0 or 1.

[0131] Preferably, the first hydrophobic silicon-containing monomer is selected from one or more of methacryloyloxypropyltris(trimethylsiloxane)silane and (3-methacryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane;

[0132] and

[0133] (2-2) Optionally, a second hydrophobic silicon-containing monomer component based on a silicon-containing acrylate or a vinylphenyl-containing silane as a second hydrophobic silicon-containing monomer.

[0134] Preferably, the second hydrophobic silicon-containing monomer is CH2=CH-C(O)-O-L2-Si(R4). n (OR5) 3-n Or CH2=CH-Ph-Si(R4) n (OR5) 3-n Ph is a phenylene, for example, 1,4-phenylene; L2 is the same as or different from L1 and is a C1-C10, preferably C3-C6 dialkylene group, optionally including one or more groups of ether-O-atom group or -OH group; R4 is the same as or different from each other and the same as or different from R1 and is independently a C1-C6 alkyl group, preferably methyl; R5 is the same as or different from each other and the same as or different from R2 and is independently a C1-C6 alkyl group, preferably methyl or -Si(R6)3, wherein R6 is the same as or different from each other and the same as or different from R3 and is independently a C1-C6 alkyl group, preferably methyl; n is the same as or different from m and is 0, 1, 2 or 3, preferably 0 or 1;

[0135] Preferably, -Si(R4) n (OR5) 3-n Partially related to -Si(R1)m(OR2) 3-m If some parts are the same or different, the same parts are preferred.

[0136] Preferably, -L2-Si(R4) n (OR5) 3-n Partially related to -L1-Si(R1)m(OR2) 3-m If some parts are the same or different, the same parts are preferred.

[0137] Preferably, the second hydrophobic silicon-containing monomer is selected from one or more of acryloyloxypropyltris(trimethylsiloxane), (3-acryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, and p-vinylphenyltris(trimethylsiloxy)silane;

[0138] Preferably, the first hydrophobic silicon-containing monomer is selected from methacryloyloxypropyltris(trimethylsiloxane)silane, and the second hydrophobic silicon-containing monomer is selected from one or more of acryloyloxypropyltris(trimethylsiloxane)silane and p-vinylphenyltris(trimethylsiloxy)silane, preferably acryloyloxypropyltris(trimethylsiloxane);

[0139] (3) Monoalkenyl-functional hydrophilic monomer components, which include or are composed of the following:

[0140] (3-1) A first hydrophilic monomer component based on a first hydrophilic monomer containing a methacryloyl group;

[0141] Preferably, the first hydrophilic monomer is selected from one or more of methacrylic acid, hydroxyethyl methacrylate, methacrylamide, and N,N-dimethylmethacrylamide;

[0142] and / or

[0143] (3-2) A second hydrophilic monomer component based on a second hydrophilic monomer containing acryloyloxy, acryloylamino and / or N-vinylamino;

[0144] Preferably, the difference between the second hydrophilic monomer and the first hydrophilic monomer is only that the second hydrophilic monomer uses an acryloyl group instead of a methacryloyl group in the first hydrophilic monomer;

[0145] Preferably, the second hydrophilic monomer is selected from one or more of acrylic acid, hydroxyethyl acrylate, acrylamide, N,N-dimethylacrylamide, N-vinylpyrrolidone, and N-methyl-N-vinylacetamide;

[0146] Preferably, the first hydrophilic monomer is selected from methacrylic acid, and the second hydrophilic monomer is selected from one or more of acrylic acid, N-vinylpyrrolidone (NVP) and N,N-dimethylacrylamide, preferably acrylic acid;

[0147] (4) Optionally, a crosslinking agent component based on a diene-functional or higher crosslinking agent;

[0148] Preferably, the crosslinking agent with diene or higher functionality is selected from: alkyl glycol dimethacrylate, preferably neopentyl glycol dimethacrylate; siloxane-containing oligomers, preferably 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane; or any combination thereof; for example, neopentyl glycol dimethacrylate and 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, which are present, for example, in a mass ratio of 10:90-90:10, for example 30:70-70:30, for example 50:50-60:40;

[0149] (5) Free radical initiators, such as azobisisobutyronitrile or azobisisoheptanenitrile;

[0150] (6) Optionally, a UV absorber, such as 2-hydroxy-4-(methacryloyloxy)benzophenone;

[0151] The composition thereon satisfies one, two, or three of the following conditions (1)-(3):

[0152] (1) When a first hydrophilic monomer is present, one, two, or three of the following are present: a second hydrophobic fluorinated monomer, a second hydrophobic silicon-containing monomer, and a second hydrophilic monomer; and / or

[0153] (2) The content of the first hydrophobic fluorinated monomer in the first hydrophobic fluorinated monomer component, and / or the content of the second hydrophobic fluorinated monomer in the second hydrophobic fluorinated monomer component, and / or the content of the first hydrophobic silicon-containing monomer in the first hydrophobic silicon-containing monomer component, and / or the content of the second hydrophobic silicon-containing monomer in the second hydrophobic silicon-containing monomer component, the content of the first hydrophilic monomer in the first hydrophilic monomer component, and / or the content of the second hydrophilic monomer in the second hydrophilic monomer component, and / or the content of the crosslinking agent in the crosslinking agent component based on a diene-functionalized or higher crosslinking agent, are each independently 98% by mass or more, preferably 99% by mass or more; and / or

[0154] The content of the polymerization inhibitor in each of the first hydrophobic fluorinated monomer component, and / or the second hydrophobic fluorinated monomer component, and / or the first hydrophobic silicon-containing monomer component, and / or the second hydrophobic silicon-containing monomer component, and / or the first hydrophilic monomer component, and / or the second hydrophilic monomer component, and / or the crosslinking agent component is independently less than 50 ppm by mass; and / or

[0155] (3) The composition includes a dyeing agent, and part or all of the dyeing agent is a reactive dye containing an alkenyl group, such as a methacryloyl group, for example selected from one or more reactive dyes selected from 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone, 1,4-bis((2-hydroxyethyl)amino)-9,10-anthradinone bis(2-propeneOIC) ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenylethyl)methacrylamide.

[0156] 22. The composition according to item 21, wherein the composition comprises, based on the total mass of the composition:

[0157] (1) 30-60% by mass, for example 40-50% by mass, of a monoalkenyl-functional hydrophobic fluorinated monomer component;

[0158] (2) 20-45% by mass, for example 30-40% by mass, of monoalkenyl-functional hydrophobic silicon-containing monomer components;

[0159] (3) 3-20% by mass, for example 5-10% by mass, of a monoalkenyl-functional hydrophilic monomer component;

[0160] (4) Optionally, 1-20% by mass, for example 5-15% by mass, of a crosslinking agent component based on a diene-functionalized or higher crosslinking agent; and

[0161] (5) 0.1-2.0% by mass, for example 0.5-1.0% by mass of free radical initiators;

[0162] (6) Optionally, 0.1-5.0% by mass, for example 0.2-1.0% by mass, for example 0.4-0.6% by mass of a UV absorber; and

[0163] (7) Optionally, 0.001-0.5% by mass, for example 0.005-0.01% by mass of a staining agent.

[0164] 23. The composition according to any one of items 21-22, wherein in said composition:

[0165] The presence of a second hydrophobic fluorinated monomer, preferably in a mass ratio of 30:70-80:20, for example 50:50-80:20, or for example 70:30-80:20; and / or

[0166] The presence of a second hydrophobic silicon-containing monomer, preferably in a mass ratio of 30:70-80:20, for example 50:50-75:25, to the first hydrophobic silicon-containing monomer; and / or

[0167] The presence of a first hydrophilic monomer and a second hydrophilic monomer is preferred, with the first hydrophilic monomer and the second hydrophilic monomer present in a mass ratio of 0:100-85:15, for example 25:75-80:20, for example 40:60-75:25.

[0168] 24. The composition according to any one of items 21-23, wherein a second hydrophobic fluorinated monomer, a second hydrophobic silicon-containing monomer, a first hydrophilic monomer, and a second hydrophilic monomer are present.

[0169] 25. The composition according to any one of items 21-24, wherein the composition is a composition for preparing a medical polymer, preferably a composition for preparing a corneal contact lens, and more preferably a rigid gas-permeable corneal contact lens.

[0170] 26. A method for preparing a polymer, comprising: providing a composition according to any one of items 21-24, and subjecting the composition to free radical polymerization.

[0171] 27. A polymer obtained by the method of item 26, preferably a medical polymer, more preferably a polymer for use in corneal contact lenses, and preferably a rigid gas-permeable corneal contact lens.

[0172] 28. Use of the composition of any one of items 21-25 in the preparation of a polymer, preferably a medical polymer, more preferably a polymer for use in a corneal contact lens, and preferably a rigid gas-permeable corneal contact lens.

[0173] The applicant discovered that polymers (or polymer compositions) prepared by free radical polymerization of olefinic unsaturated monomers in which the olefinic bonds are derived from isopropenyl groups, particularly methacryloyl groups (e.g., methacryloyloxy groups), have a high residual monomer content. By partially replacing the olefinic unsaturated monomers with olefinic unsaturated monomers in which the olefinic bonds are derived from vinyl groups, particularly from acryloyloxy, acryloylamino, N-vinylamino, or vinylphenyl groups, the residual monomer content in the prepared polymers (or polymer compositions) can be significantly reduced. The resulting polymers therefore exhibit high biocompatibility and are suitable for use as medical polymer materials. Furthermore, this free radical polymerization does not require complex process control. By further adjusting the composition of the composition, the prepared polymers can simultaneously achieve desired properties such as hardness, oxygen permeability, water wettability, and processability.

[0174] Specifically, when preparing polymers using a fluoroalkyl methacrylate as a monoalkenyl-functional hydrophobic fluorinated monomer component, a methacrylate-type silicon-containing monomer as a monoalkenyl-functional hydrophobic monomer component, and a methacrylamide-containing compound as a monoalkenyl-functional hydrophilic monomer component via free radical polymerization, the polymer is prepared by partially replacing the fluoroalkyl methacrylate with a fluoroalkyl acrylate (e.g., a fluoroalkyl acrylate having the same fluoroalkyl moiety) for the monoalkenyl-functional hydrophobic fluorinated monomer component, and / or partially replacing the methacrylate-type silicon-containing monomer with an acrylate-type or other vinyl-type silicon-containing monomer (e.g., containing vinylbenzene) for the monoalkenyl-functional hydrophobic silicon-containing monomer component. The polymer prepared by using methacryloyl groups (especially acrylate or other vinyl-type silicon monomers having the same silicon functional moiety), and / or partially replacing compounds containing methacryloyl groups with compounds containing acryloyl, acrylamido, or N-vinylamide groups for monoalkenyl-functional hydrophilic monomer components, compared to using only fluoroalkyl methacrylates for monoalkenyl-functional hydrophobic monomer components, only methacrylate-type silicon monomers for monoalkenyl-functional hydrophobic monomer components, and only compounds containing methacryloyl groups for monoalkenyl-functional hydrophilic monomer components, exhibits significantly reduced chemical residues and therefore high biocompatibility, making it suitable for use as a medical polymer material. Furthermore, this free radical polymerization does not require complex process control. Moreover, by controlling the composition of the composition, the prepared polymer can simultaneously achieve good hardness, oxygen permeability, water wettability, and processability; and therefore, it can be used to prepare, for example, rigid gas permeable contact lenses. Alternatively or additionally, the chemical residues of the prepared polymer can be further reduced by using reactive monomers with higher purity and lower polymerization inhibitor content and / or by using reactive dyes (e.g., instead of conventional dyes). Detailed Implementation

[0175] Unless otherwise specified, in this application, temperature refers to room temperature (25°C) and pressure refers to atmospheric pressure.

[0176] In this application, unless otherwise specified, the expression "%" used when referring to the content or concentration of components in the composition means "mass %".

[0177] Unless otherwise specified, in this application, when referring to the content or concentration of components in the composition, it is calculated based on the composition.

[0178] In this application, unless otherwise specified, even if the term “about” is not used to modify numerical values, the numerical value shall be understood to be modified by “about”; the term “about” includes a deviation of ±5% from the stated numerical value, that is, for the numerical value a, whether or not it is modified by “about”, it shall be understood to represent a range of a ±5%a, that is, 0.95a to 1.05a.

[0179] In this application, the term "isopropenyl" refers to CH2=C(CH3)-, "vinyl" refers to CH2=CH-, "methacryloyloxy" refers to CH2=C(CH3)-C(O)-O-, "acryloyloxy" refers to CH2=CH-C(O)-O-, and "acryloylamino" refers to... "N-Vinylamido" refers to "Vinylphenyl" refers to CH2=CH-Ph-, where Ph is phenylene, such as 1,4-phenylene.

[0180] In this application, the terms “first” and “second” are not intended to be restrictive and are not intended to imply that other elements (e.g., compounds) must be present in the target object in addition to the stated elements (e.g., compounds). In other words, they may indicate the presence or absence of other elements besides the stated elements; they are used only to distinguish one compound, monomer, component, or composition from another compound, monomer, component, or composition.

[0181] In this application, the terms "fluorine-containing" or "silicon-containing" mean that the stated compound includes fluorine or silicon elements in addition to C, H, and O. When a "fluorine-containing" compound (e.g., a monomer) and a "silicon-containing" compound (e.g., a monomer) are mentioned simultaneously in the same paragraph of the specification, it means that the two are mutually exclusive; that is, a "fluorine-containing" compound does not contain silicon, and a "silicon-containing" compound does not contain fluorine. In particular, a fluorine-containing compound may be a compound composed of carbon, hydrogen, oxygen, and fluorine, and a silicon-containing compound may be a compound composed of carbon, hydrogen, oxygen, and silicon.

[0182] This invention relates to a method for reducing the residual monomer content in a polymer composition, a polymer composition, a composition capable of free radical polymerization, a method for preparing a polymer using the composition capable of free radical polymerization, a polymer prepared from the composition capable of free radical polymerization, and the use of the composition capable of free radical polymerization in the preparation of polymers.

[0183] The present invention will be described in detail below.

[0184] Methods for reducing the residual monomer content in polymer compositions

[0185] In a first aspect, the present invention relates to a method for reducing the residual monomer content in a polymer composition (or polymer), said polymer composition (or polymer) being a polymer composition (or polymer) prepared by free radical polymerization using a first composition capable of free radical polymerization, said first composition capable of free radical polymerization comprising a mixture thereof:

[0186] The first ene unsaturated monomer component is based on the first ene unsaturated monomer, wherein the olefin bond in the first ene unsaturated monomer originates from the isopropenyl group (CH2=C(CH3)-).

[0187] Free radical initiators,

[0188] Optionally, ultraviolet absorbers, and

[0189] Optional, dye;

[0190] The method includes:

[0191] (1) A second composition capable of free radical polymerization is provided by replacing a portion of the first olefinically unsaturated monomer component with a second olefinically unsaturated monomer component based on the following: wherein the olefinic bond of the second olefinically unsaturated monomer originates from vinyl (CH2=CH-); then the second composition capable of free radical polymerization is subjected to free radical polymerization; and / or

[0192] (2) Prior to polymerization, before combining the components to form the first composition capable of free radical polymerization, the following purification steps are performed: purifying the first olefinically unsaturated monomer component to increase the content of the first olefinically unsaturated monomer and / or decrease the content of the polymerization inhibitor, for example, such that the content of the first olefinically unsaturated monomer is 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor is 50 ppm by mass or less; then free radical polymerization is carried out; and / or

[0193] (3) When the dye in the first composition capable of free radical polymerization is a non-reactive dye, the non-reactive dye in the first composition capable of free radical polymerization is partially or completely replaced with a reactive dye, for example, containing an alkenyl group or a methacryloyl group, to provide a second composition capable of free radical polymerization, wherein the reactive dye is selected, for example, from one or more of 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone, 1,4-bis((2-hydroxyethyl)amino)-9,10-anthradinone bis(2-propeneOIC) ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenethyl)methacrylamide.

[0194] The free radical polymerization can be carried out under suitable conditions. For example, the temperature of the free radical polymerization can be 40-120°C, such as 60-90°C. The free radical polymerization can be carried out in bulk, solution, slurry, suspension, or emulsion polymerization, especially in a bulk manner. The polymerization can be carried out in an inert atmosphere (e.g., nitrogen or argon) or an air atmosphere. The free radical polymerization can be carried out under conditions well known to those skilled in the art, and therefore will not be described in detail here.

[0195] The first to third embodiments (1)-(3) of the method will be described below.

[0196] First Implementation Method

[0197] In a first embodiment of a first aspect of the present invention, the present invention relates to a method for reducing the residual monomer content in a polymer composition (or polymer), said polymer composition (or polymer) being a polymer composition (or polymer) prepared by free radical polymerization using a first composition capable of free radical polymerization, said first composition capable of free radical polymerization comprising a mixture of:

[0198] The first ene unsaturated monomer component is based on the first ene unsaturated monomer, wherein the olefin bond in the first ene unsaturated monomer originates from the isopropenyl group (CH2=C(CH3)-).

[0199] Free radical initiators,

[0200] Optionally, ultraviolet absorbers, and

[0201] Optional, dye;

[0202] The method includes:

[0203] (1) A second composition capable of free radical polymerization is provided by replacing a portion of the first olefinically unsaturated monomer component with a second olefinically unsaturated monomer component based on the following: wherein the olefinic bond of the second olefinically unsaturated monomer is derived from vinyl (CH2=CH-); and then the second composition capable of free radical polymerization is subjected to free radical polymerization.

[0204] In this application, unless otherwise specified, the term "...monomer component based on...monomer X" means that the monomer component primarily comprises the mentioned monomer compound, for example, at least 90% by mass based on the total weight of the monomer component, such as the mentioned monomer compound in amounts of: 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, 99.9% by mass. In addition to the mentioned monomer compound, the monomer component may further include impurities, byproducts generated during the preparation, storage, and transportation of the compound, as well as polymerization inhibitors added for stability during storage and transportation (to prevent polymerization). This definition also applies to other monomer components capable of free radical polymerization, including crosslinking agent components and reactive dye components.

[0205] The method includes replacing a portion of a first olefinically unsaturated monomer component with a second olefinically unsaturated monomer component. The replacement ratio of the first olefinically unsaturated monomer component and the first olefinically unsaturated monomer (i.e., the mass of the second olefinically unsaturated monomer component relative to the sum of the masses of the first and second olefinically unsaturated monomer components after replacement, and the mass of the second olefinically unsaturated monomer relative to the sum of the masses of the first and second olefinically unsaturated monomer components) is not particularly limited and can be appropriately selected according to the desired properties of the polymer (or polymer composition), for example, each can be independently 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26) 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 60, 61, 62, 63, 64, 65, 66, 67, 6 8, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, 99.8, 99.9% by mass, or a range defined by any two of these.

[0206] The applicant discovered that when monomers with olefin bonds derived from isopropenyl CH2=C(CH3)- are partially replaced with monomers with olefin bonds derived from vinyl (CH2=CH-), for example, when monomers with olefin bonds derived from methacryloyl, such as methacryloyloxy, are partially replaced with monomers with olefin bonds derived from acryloyloxy, acryloamido, N-vinylamido, and / or vinylphenyl, the residual monomer content in the prepared polymer (or polymer composition) can be significantly reduced.

[0207] Preferably, the olefin bond in the first olefin unsaturated monomer may be derived from methacryloyloxy, and the olefin bond in the second olefin unsaturated monomer may be derived from one or more of the following: acryloyloxy, acryloylamino, N-vinylamino, vinylphenyl.

[0208] Preferably, the first olefinic unsaturated monomer and the second olefinic unsaturated monomer may have the same or different, preferably the same, alkenyl functional degree; for example, both the first olefinic unsaturated monomer and the second olefinic unsaturated monomer may be monoalkenyl functional olefinic unsaturated monomers.

[0209] Preferably, the first olefinic unsaturated monomer may include or be a first hydrophobic monomer containing a methacryloyl group, such as a hydrophobic methacrylate monomer, a first hydrophilic monomer containing a methacryloyl group, or any combination thereof.

[0210] For example, the first olefinic unsaturated monomer may include or be a first hydrophobic monomer containing a methacryloyl group, such as a hydrophobic methacrylate monomer and a first hydrophilic monomer containing a methacryloyl group, and the second olefinic unsaturated monomer may include or be a second hydrophobic monomer, such as a hydrophobic acrylate monomer, a second hydrophilic monomer, or a combination thereof, preferably a combination thereof.

[0211] Preferably, the difference between the first hydrophobic monomer and the second hydrophobic monomer is only that the methacryloyloxy group in the first hydrophobic monomer is replaced with the acryloyloxy group, vinylphenyl group, or a combination thereof in the second hydrophobic monomer.

[0212] Preferably, the difference between the first hydrophilic monomer and the second hydrophilic monomer is only that the methacryloyloxy group in the first hydrophilic monomer is replaced by the acryloxy group in the second hydrophilic monomer.

[0213] Preferably, the first olefinic unsaturated monomer may include or be a first hydrophobic fluorinated monomer containing a methacryloyl group, such as a hydrophobic fluorinated alkyl methacrylate monomer, a first hydrophobic silicon monomer containing a methacryloyl group, such as a silicon-containing hydrophobic methacrylate monomer, a first hydrophilic monomer containing a methacryloyl group, or any combination thereof.

[0214] For example, the first olefinic unsaturated monomer may include or be a first hydrophobic fluorinated monomer containing a methacryloyl group, such as a hydrophobic fluorinated alkyl methacrylate monomer, a first hydrophobic silicon monomer containing a methacryloyl group, such as a silicon-containing hydrophobic methacrylate monomer, and a first hydrophilic monomer containing a methacryloyl group, and the second olefinic unsaturated monomer may include or be a second hydrophobic fluorinated monomer, such as a hydrophobic fluorinated alkyl acrylate monomer, a second hydrophobic silicon monomer, such as a silicon-containing hydrophobic acrylate monomer, and / or a vinylphenyl-containing silane, a second hydrophilic monomer, or a combination thereof, preferably a combination thereof.

[0215] Preferably, the difference between the first hydrophobic fluorinated monomer and the second hydrophobic fluorinated monomer is only that the methacryloyloxy group in the first hydrophobic fluorinated monomer is replaced by the acryloxy group in the second hydrophobic fluorinated monomer.

[0216] Preferably, the difference between the first hydrophobic silicon-containing monomer and the second hydrophobic silicon-containing monomer is only that the methacryloyloxy group in the first hydrophobic silicon-containing monomer is replaced with the acryloyloxy group, vinylphenyl group, or a combination thereof in the second hydrophobic silicon-containing monomer.

[0217] Preferably, the difference between the first hydrophilic monomer and the second hydrophilic monomer is only that the methacryloyloxy group in the first hydrophilic monomer is replaced by the acryloxy group in the second hydrophilic monomer.

[0218] Preferably, the first olefinically unsaturated monomer may include or be a first hydrophobic fluorinated monomer containing a methacryl group that is monoalkenyl-functional, such as a hydrophobic fluoroalkyl methacrylate monomer, a first hydrophobic silicon monomer containing a methacryl group that is monoalkenyl-functional, such as a silicon-containing hydrophobic methacrylate monomer, a first hydrophilic monomer containing a methacryl group that is monoalkenyl-functional, or any combination thereof.

[0219] For example, the first olefinically unsaturated monomer may include or be a first hydrophobic fluorinated monomer containing a methacryloyl group with monoalkenyl functionality, such as a hydrophobic fluoroalkyl methacrylate monomer, a first hydrophobic silicon monomer containing a methacryloyl group with monoalkenyl functionality, such as a silicon-containing hydrophobic methacrylate monomer, and a first hydrophilic monomer containing a methacryloyl group with monoalkenyl functionality, and the second olefinically unsaturated monomer may include or be a second hydrophobic fluorinated monomer containing a monoalkenyl functionality, such as a hydrophobic fluoroalkyl acrylate monomer, a second hydrophobic silicon monomer containing a monoalkenyl functionality, such as a silicon-containing hydrophobic acrylate monomer, a silane containing a vinylphenyl group or a combination thereof, a second hydrophilic monomer with monoalkenyl functionality, or a combination thereof, preferably a combination thereof.

[0220] Preferably, the difference between the first hydrophobic fluorinated monomer and the second hydrophobic fluorinated monomer is only that the methacryloyloxy group in the first hydrophobic fluorinated monomer is replaced by the acryloxy group in the second hydrophobic fluorinated monomer.

[0221] Preferably, the difference between the first hydrophobic silicon-containing monomer and the second hydrophobic silicon-containing monomer is only that the methacryloyloxy group in the first hydrophobic silicon-containing monomer is replaced with the acryloyloxy group, vinylphenyl group, or a combination thereof in the second hydrophobic silicon-containing monomer.

[0222] Preferably, the difference between the first hydrophilic monomer and the second hydrophilic monomer is only that the methacryloyloxy group in the first hydrophilic monomer is replaced by the acryloxy group in the second hydrophilic monomer.

[0223] Preferably, when the first olefinically unsaturated monomer may include or be a first hydrophobic monomer containing a methacryloyl group, such as a hydrophobic methacrylate monomer and / or a first hydrophilic monomer containing a methacryloyl group, the mass ratio of the first hydrophobic monomer to (first hydrophobic monomer + first hydrophilic monomer) in the first composition or the first olefinically unsaturated monomer, the mass ratio of the second hydrophobic monomer to (first hydrophobic monomer + second hydrophobic monomer) in the second composition, and the mass ratio of the second hydrophilic monomer to (first hydrophilic monomer + second hydrophilic monomer) are not particularly limited and can be appropriately selected according to the intended purpose, for example, they can each be independently 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 2 0, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 60, 61, 62, 63, 64, 65 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, 99.8, 99.9, 100% by mass, or a range defined by any two of these.

[0224] Preferably, the mass ratio of the second hydrophobic monomer to (the first hydrophobic monomer + the second hydrophobic monomer) can be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50% by mass, or a range defined by any two of these. Preferably, the mass ratio of the second hydrophilic monomer to (the first hydrophilic monomer + the second hydrophilic monomer) can be 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 5 8, 59, 60, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, 99.8, 99.9, 100% by mass, or a range defined by any two of these. Within the preferred range, while significantly reducing the residual monomer content in the prepared polymer (or polymer composition) and improving its biocompatibility, the prepared polymer can also simultaneously achieve good hardness, oxygen permeability, water wettability, and processability, achieving a better balance of properties.

[0225] Preferably, when the first olefinically unsaturated monomer includes or is a first hydrophobic fluorinated monomer containing a methacryloyl group, such as a hydrophobic fluorinated alkyl methacrylate monomer, a first hydrophobic silicon monomer containing a methacryloyl group, such as a silicon-containing hydrophobic methacrylate monomer, and / or a first hydrophilic monomer containing a methacryloyl group, the mass ratio of the first hydrophobic fluorinated monomer to (first hydrophobic fluorinated monomer + first hydrophobic silicon monomer + first hydrophilic monomer) in the first composition or the first olefinically unsaturated monomer, the mass ratio of the first hydrophobic silicon monomer to (first hydrophobic fluorinated monomer + first hydrophilic monomer) is... The mass ratio of aqueous silicon-containing monomer + first hydrophilic monomer, the mass ratio of first hydrophilic monomer / (first hydrophobic fluorinated monomer + first hydrophobic silicon-containing monomer + first hydrophilic monomer), the mass ratio of second hydrophobic fluorinated monomer / (first hydrophobic fluorinated monomer + second hydrophobic fluorinated monomer), the mass ratio of second hydrophobic silicon-containing monomer / (first hydrophobic silicon-containing monomer + second hydrophobic silicon-containing monomer), the mass ratio of (second hydrophobic fluorinated monomer + second hydrophobic silicon-containing monomer) / (first hydrophobic fluorinated monomer + second hydrophobic fluorinated monomer + first hydrophobic silicon-containing monomer + second... The mass ratio of the hydrophobic silicon-containing monomer and the mass ratio of the second hydrophilic monomer to (first hydrophilic monomer + second hydrophilic monomer) can each be independently set to 0, 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47. 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, 99.8, 99.9, 100% by mass, or a range defined by any two of these.

[0226] Preferably, the mass ratio of the second hydrophobic fluorinated monomer to (the first hydrophobic fluorinated monomer + the second hydrophobic fluorinated monomer) and the mass ratio of the second hydrophobic silicon-containing monomer to (the first hydrophobic silicon-containing monomer + the second hydrophobic silicon-containing monomer) in the second composition can each independently be 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70% by mass, or a range defined by any two thereof. Preferably, the mass ratio of (second hydrophobic fluorinated monomer + second hydrophobic silicon monomer) / (first hydrophobic fluorinated monomer + second hydrophobic fluorinated monomer + first hydrophobic silicon monomer + second hydrophobic silicon monomer) can be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50% by mass, or a range defined by any two of these. Preferably, the mass ratio of the second hydrophilic monomer to (the first hydrophilic monomer + the second hydrophilic monomer) can be 15, 16, 17, 18, 19, 20, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 6. 0, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.5, 99.8, 99.9, 100% by mass, or a range defined by any two of these. Within the preferred range, while significantly reducing the residual monomer content in the prepared polymer (or polymer composition) and improving its biocompatibility, the prepared polymer can also simultaneously achieve good hardness, oxygen permeability, water wettability, and processability, achieving a better balance of properties.

[0227] Preferably, the second composition capable of free radical polymerization may include:

[0228] (1) A monoalkenyl-functional hydrophobic fluorinated monomer component, which may include or be composed of the following:

[0229] (1-1) Based on the first hydrophobic fluorinated monomer component of fluorinated alkyl methacrylate as the first hydrophobic fluorinated monomer;

[0230] and

[0231] (1-2) Optional second hydrophobic fluorinated monomer component based on fluorinated alkyl acrylate as a second hydrophobic fluorinated monomer;

[0232] (2) A monoalkenyl-functional hydrophobic silicon-containing monomer component, which may include or be composed of the following:

[0233] (2-1) Based on the first hydrophobic silicon-containing methacrylate as the first hydrophobic silicon-containing monomer component;

[0234] and

[0235] (2-2) Optionally, a second hydrophobic silicon-containing monomer component based on a silicon-containing acrylate or a silane containing a vinylphenyl group as a second hydrophobic silicon-containing monomer.

[0236] (3) A monoalkenyl-functional hydrophilic monomer component, which may include or be composed of the following:

[0237] (3-1) A first hydrophilic monomer component based on a first hydrophilic monomer containing a methacryloyl group;

[0238] and / or

[0239] (3-2) A second hydrophilic monomer component based on a second hydrophilic monomer containing acryloyloxy, acryloylamino and / or N-vinylamino;

[0240] (4) Optionally, a crosslinking agent component based on a diene-functional or higher crosslinking agent;

[0241] (5) Free radical initiators;

[0242] (6) Optionally, a UV absorber;

[0243] When a first hydrophilic monomer is present, one, two, or three of the following may be present: a second hydrophobic fluorinated monomer, a second hydrophobic silicon-containing monomer, and a second hydrophilic monomer.

[0244] The second composition may include a monoalkenyl-functionalized hydrophobic fluorinated monomer component. The amount of the monoalkenyl-functionalized hydrophobic fluorinated monomer component is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the second composition may include 30-60% by mass, such as 40-50% by mass, for example, amounts of the monoalkenyl-functionalized hydrophobic fluorinated monomer component as follows: 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60% by mass, or a range defined by any two thereof.

[0245] The monoalkenyl-functional hydrophobic fluorinated monomer component may include, or be composed of, a first hydrophobic fluorinated monomer component based on a fluorinated alkyl methacrylate as a first hydrophobic fluorinated monomer, and optionally, a second hydrophobic fluorinated monomer component based on a fluorinated alkyl acrylate as a second hydrophobic fluorinated monomer.

[0246] The applicant discovered that when the monoalkenyl-functional hydrophobic fluorinated monomer component further includes a second hydrophobic fluorinated monomer in addition to the first hydrophobic fluorinated monomer, the chemical residue (total amount of residual monomer) in the polymer prepared under the same polymerization conditions can be reduced compared to the case where the monoalkenyl-functional hydrophobic fluorinated monomer component uses only the first hydrophobic fluorinated monomer.

[0247] There are no particular restrictions on the number of carbon atoms of the fluorinated alkyl group in the fluorinated alkyl methacrylate, which is the first hydrophobic fluorinated monomer, and the number of carbon atoms of the fluorinated alkyl acrylate, which is the second hydrophobic fluorinated monomer. For example, they can each be independently 1-20, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or a range defined by any two of them.

[0248] Preferably, the first hydrophobic fluorinated monomer may be a C1-C10 fluorinated alkyl methacrylate. The first hydrophobic fluorinated monomer may be a single compound or a mixture of two or more compounds.

[0249] For example, the number of carbon atoms in the fluorinated alkyl group can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or any range thereof, i.e., the alkyl group can be methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (e.g., n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl), hexyl (e.g., n-hexyl, isohexyl, sec-hexyl, tert-hexyl, neohexyl), heptyl (e.g., n-heptyl, isohexyl, sec-heptyl, tert-heptyl, neoheptyl), octyl (e.g., n-octyl, isooctyl, sec-octyl, tert-octyl, neooctyl), nonyl (e.g., n-nonyl, isononyl, sec-nonyl, tert-nonyl, neononyl), decyl (e.g., n-decyl, isodexyl, sec-decyl, tert-decyl, neodecyl), or any combination thereof.

[0250] There is no particular limitation on the number of fluorine substituents in the fluorinated alkyl group, and for an alkyl group having n carbon atoms, the number of fluorine substituents can, for example, range from 1 to 2n+1. That is, for a carbon number of 1, the number of fluorine substituents can be 1, 2, or 3; for a carbon number of 10, the number of fluorine substituents can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, or 23; for any integer n between 1 and 10 carbon atoms, the number of fluorine substituents can be 1 or any value below the value corresponding to 2n+1 listed for a carbon number of 10.

[0251] Preferably, the first hydrophobic fluorinated monomer is a C1-C6 fluorinated alkyl methacrylate, more preferably a C2-C5 fluorinated alkyl methacrylate, and more preferably a C2-C3 fluorinated alkyl methacrylate. For example, the first hydrophobic fluorinated monomer may be one or more selected from trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, and 2,2,3,3,3-pentafluoropropyl methacrylate.

[0252] Preferably, the second composition contains a second hydrophobic fluorinated monomer component. When present, the amount of the second hydrophobic fluorinated monomer is not particularly limited relative to the total mass of the first and second hydrophobic fluorinated monomers and can be appropriately selected according to the intended purpose. For example, when the total mass of the first and second hydrophobic fluorinated monomers is 100 parts by mass, the second hydrophobic fluorinated monomer can be present in the following amounts: 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43. 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 70, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 parts by mass, or a range defined by any two of these. Preferably, the first hydrophobic fluorinated monomer and the second hydrophobic fluorinated monomer can be present in a mass ratio of 30:70-80:20; within this preferred range, the prepared polymer has significantly reduced monomer residue; and furthermore, it can also have good hardness, oxygen permeability, static contact angle, and water absorption rate, and can improve at least one of hardness and oxygen permeability. More preferably, the first hydrophobic fluorinated monomer and the second hydrophobic fluorinated monomer can be present in a mass ratio of 50:50-80:20, for example, 70:30-80:20; within this more preferred range, the prepared polymer can have further improved hardness.

[0253] The second hydrophobic fluorinated monomer can be a fluorinated alkyl ester of acrylic acid. The description above regarding the number of carbon atoms and fluorine substituents in the fluorinated alkyl group of the first hydrophobic fluorinated monomer also applies here. This will not be repeated here. The second hydrophobic fluorinated monomer can be a single compound or a mixture of two or more compounds.

[0254] The fluorinated alkyl group in the second hydrophobic fluorinated monomer may be the same as or different from the fluorinated alkyl group in the first hydrophobic fluorinated monomer, but is preferably the same. When the fluorinated alkyl group in the second hydrophobic fluorinated monomer is the same as the fluorinated alkyl group in the first hydrophobic fluorinated monomer, it is more helpful to reduce the monomer residue in the prepared polymer.

[0255] Preferably, the second hydrophobic fluorinated monomer may be a C1-C10 fluorinated alkyl acrylate, more preferably a C1-C6 fluorinated alkyl acrylate, more preferably a C2-C5 fluorinated alkyl acrylate, and more preferably a C2-C3 fluorinated alkyl acrylate. Preferably, the second hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl acrylate, hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, and 2,2,3,3,3-pentafluoropropyl acrylate. More preferably, the second hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl acrylate and hexafluoroisopropyl acrylate.

[0256] Preferably, the first hydrophobic fluorinated monomer is selected from one or more of hexafluoroisopropyl methacrylate and trifluoroethyl methacrylate; and the second hydrophobic fluorinated monomer is selected from one or more of hexafluoroisopropyl acrylate and trifluoroethyl acrylate; for example, the first hydrophobic fluorinated monomer is hexafluoroisopropyl methacrylate and the second hydrophobic fluorinated monomer is hexafluoroisopropyl acrylate, or the first hydrophobic fluorinated monomer is trifluoroethyl methacrylate and the second hydrophobic fluorinated monomer is trifluoroethyl acrylate.

[0257] The second composition may include a monoalkenyl-functionalized hydrophobic silicon-containing monomer component. The amount of the monoalkenyl-functionalized hydrophobic silicon-containing monomer component is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the second composition may include 20-45% by mass, such as 30-40% by mass, for example, amounts of the following monoalkenyl-functionalized hydrophobic fluorinated monomer component: 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45% by mass, or a range defined by any two thereof.

[0258] The monoalkenyl-functional hydrophobic silicon-containing monomer component may include or consist of the following: a first hydrophobic silicon-containing monomer component based on a first hydrophobic silicon-containing monomer and optionally a second hydrophobic silicon-containing monomer component based on a second hydrophobic silicon-containing monomer.

[0259] The applicant discovered that when the monoalkenyl-functional hydrophobic silicon-containing monomer component further includes a second hydrophobic silicon-containing monomer in addition to the first hydrophobic silicon-containing monomer, compared to the case where the monoalkenyl-functional hydrophobic silicon-containing monomer component uses only the first hydrophobic silicon-containing monomer, it is possible to reduce the chemical residue (residual monomer content) in the polymer prepared under the same polymerization conditions. Furthermore, compared to the case where only a portion of the first hydrophobic fluorinated monomer is replaced with the second hydrophobic fluorinated monomer, replacing the same amount of the first hydrophobic silicon-containing monomer with the second hydrophobic silicon-containing monomer can more significantly reduce the chemical residue (residual monomer content) in the polymer prepared under the same polymerization conditions.

[0260] Preferably, the first hydrophobic silicon-containing monomer is represented by the following formula: CH2=C(CH3)-C(O)-O-L1-Si(R1)m(OR2) 3-m L1 is a C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10), preferably C3-C6 dialkylene group, optionally including one or more groups selected from ether-O-atom groups and -OH groups, such as methylene, ethylene, n- or iso-propylene, n-, iso- or tert-butylene, n-, iso- or tert-pentylene, n-, iso- or tert-hexylene, n-, iso- or tert-heptylene, n-, iso- or tert-octylene, n-, iso- or tert-nonylene, or n-, iso- or tert-decylene; R1 may be the same as or different from each other and each is independently a C1-C6 alkyl group (e.g., Methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (e.g., n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl), hexyl (e.g., n-hexyl, isohexyl, sec-hexyl, tert-hexyl, neohexyl)), preferably methyl, R2 may be the same as or different from each other and each is independently a C1-C6 alkyl group (e.g., methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (e.g., n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl), hexyl (e.g., n-hexyl, isohexyl, sec-hexyl, tert-hexyl, neohexyl)) or - Si(R3)3, wherein R3 are the same or different from each other and are each independently C1-C6 alkyl (e.g., methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (e.g., n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl), hexyl (e.g., n-hexyl, isohexyl, sec-hexyl, tert-hexyl, neohexyl)), preferably methyl, and m is 0, 1, 2, or 3, preferably 0 or 1.

[0261] The first hydrophobic silicon-containing monomer can be a single compound or a mixture of two or more compounds.

[0262] Preferably, the first hydrophobic silicon-containing monomer is selected from one or more of methacryloyloxypropyltris(trimethylsiloxane)silane and (3-methacryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane.

[0263] Preferably, the second composition contains a second hydrophobic silicon-containing monomer component. When present, the amount of the second hydrophobic silicon-containing monomer is not particularly limited relative to the total mass of the first and second hydrophobic silicon-containing monomers and can be appropriately selected according to the intended purpose. For example, when the total mass of the first and second hydrophobic silicon-containing monomers is 100 parts by mass, the second hydrophobic silicon-containing monomer can be present in the following amounts: 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43. 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 70, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99 parts by mass, or a range defined by any two of these. Preferably, the first hydrophobic silicon-containing monomer and the second hydrophobic silicon-containing monomer are present in a mass ratio of 30:70-80:20; within this preferred range, the prepared polymer has significantly reduced monomer residue; and furthermore, it can also have good hardness, oxygen permeability, static contact angle, and water absorption rate, and can improve at least one of hardness and oxygen permeability. More preferably, the first hydrophobic silicon-containing monomer and the second hydrophobic silicon-containing monomer are present in a mass ratio of 50:50-75:25; within this more preferred range, the prepared polymer can have further improved hardness.

[0264] Preferably, the second hydrophobic silicon-containing monomer is represented by the following formula: CH2=CH-C(O)-O-L2-Si(R4) n (OR5) 3-n Or CH2=CH-Ph-Si(R4) n (OR5) 3-nPh is a phenylene, such as 1,4-phenylene, and L2 may be the same as or different from L1 and is a C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10), preferably C3-C6 dialkylene (e.g., methylene, ethylene, n- or isopropylene, n-, iso- or tert-butylene, n-, iso- or tert-pentylene, n-, iso- or tert-hexylene, n-, iso- or tert-heptylene, n-, iso- or tert-octylene, n-, iso- or tert-nonylene, or n-, iso- or tert-decylene) group, optionally including one or more groups selected from ether-O-atom groups and -OH groups. Alternatively, R4 may be phenylene; R4 may be the same as or different from each other and the same as or different from R1, and each may independently be a C1-C6 alkyl group (e.g., methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (e.g., n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl), hexyl (e.g., n-hexyl, isohexyl, sec-hexyl, tert-hexyl, neohexyl)), preferably methyl; R5 may be the same as or different from each other. The R6 groups are identical or different from each other and are C1-C6 alkyl groups (e.g., methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (e.g., n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl), hexyl (e.g., n-hexyl, isohexyl, sec-hexyl, tert-hexyl, neohexyl)) or -Si(R6)3, wherein the R6 groups are identical or different from each other and are C1-C6 alkyl groups (e.g., methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isopropyl, sec-hexyl, tert-hexyl, neohexyl)) or -Si(R6)3, wherein the R6 groups are identical or different from each other and are C1-C6 alkyl groups (e.g., C1-C6 alkyl ... R3 may be the same or different and each independently is a C1-C6 alkyl group (e.g., methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (e.g., n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl), hexyl (e.g., n-hexyl, isohexyl, sec-hexyl, tert-hexyl, neohexyl)), preferably methyl, and n and m may be the same or different and are 0, 1, 2, or 3, preferably 0 or 1.

[0265] The second hydrophobic silicon-containing monomer can be a single compound or a mixture of two or more compounds.

[0266] Preferably, -Si(R4) n (OR5) 3-n Partially related to -Si(R1) m (OR2) 3-m The components may be partially the same or different, but are preferably the same. Preferably, at least a portion, such as all, of the -Si(R4) in the second hydrophobic silicon-containing monomer is present. n (OR5) 3-n Partially related to -Si(R1) in the first hydrophobic silicon-containing monomer. m (OR2) 3-m Partially identical. When the first and second hydrophobic silicon-containing monomers contain -Si(R4)...n (OR5) 3-n Partially related to -Si(R1) in the first hydrophobic silicon-containing monomer. m (OR2) 3-m When the components are partially identical, it helps to reduce the monomer residue in the prepared polymer.

[0267] Preferably, -L2-Si(R4) n (OR5) 3-n Partially compatible with -L1-Si(R1) m (OR2) 3-m Some may be the same or different. Preferably, at least a portion, such as all, of the -L2-Si(R4) in the second hydrophobic silicon-containing monomer. n (OR5) 3-n Partially related to -L1-Si(R1) in the first hydrophobic silicon-containing monomer. m (OR2) 3-m Partially the same. When the second hydrophobic silicon-containing monomer contains -L2-Si(R4) n (OR5) 3-n Partially related to -L1-Si(R1) in the first hydrophobic silicon-containing monomer. m (OR2) 3-m When the components are partially identical, it helps to reduce the monomer residue in the prepared polymer.

[0268] Preferably, the second hydrophobic silicon-containing monomer is selected from one or more of acryloyloxypropyltris(trimethylsiloxane), (3-acryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, and p-vinylphenyltris(trimethylsiloxy)silane.

[0269] Preferably, the first hydrophobic silicon-containing monomer is selected from methacryloyloxypropyltris(trimethylsiloxane)silane, and the second hydrophobic silicon-containing monomer is selected from one or more of acryloyloxypropyltris(trimethylsiloxane)silane and p-vinylphenyltris(trimethylsiloxy)silane, preferably acryloyloxypropyltris(trimethylsiloxane)silane.

[0270] The second composition may include a monoalkenyl-functional hydrophilic monomer component. The amount of the monoalkenyl-functional hydrophilic monomer component is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the second composition may include 3-20% by mass, such as 5-10% by mass, for example, amounts of the monoalkenyl-functional hydrophilic monomer component in the following quantities: 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20% by mass, or a range defined by any two thereof.

[0271] The monoalkenyl-functional hydrophilic monomer component may include or consist of: a first hydrophilic monomer component based on a first hydrophilic monomer containing a methacrylyl group and / or a second hydrophilic monomer component based on a second hydrophilic monomer containing an acrylyl group, an acrylamide group, and / or an N-vinylamide group. The second hydrophilic monomer containing an acrylyl group, an acrylamide group, and / or an N-vinylamide group may be a hydrophilic monomer containing an acrylyl group, a hydrophilic monomer containing an acrylamide group, a hydrophilic monomer containing an N-vinylamide group, or any combination thereof.

[0272] The applicant discovered that when a portion or all of the first hydrophilic monomer in the monoalkenyl-functional hydrophilic monomer component is replaced by a second hydrophilic monomer, the chemical residue (residual monomer content) in the polymer prepared under the same polymerization conditions can be reduced compared to the case where only the first hydrophilic monomer is used in the monoalkenyl-functional hydrophilic monomer component.

[0273] The first hydrophilic monomer may be a hydrophilic compound containing a methacryloyl group. The first hydrophilic monomer may be a single compound or a mixture of two or more compounds.

[0274] Preferably, the first hydrophilic monomer may be one or more selected from methacrylic acid, hydroxyethyl methacrylate, methacrylamide, and N,N-dimethylmethacrylamide.

[0275] In this embodiment, the second hydrophilic monomer is a hydrophilic compound containing an acryloyl group, an acrylamido group, and / or an N-vinylamide group. The second hydrophilic monomer may be a single compound or a mixture of two or more compounds.

[0276] When a second hydrophilic monomer is present, the amount of the second hydrophilic monomer relative to the total mass of the first and second hydrophilic monomers is not particularly limited and can be appropriately selected according to the intended purpose. For example, when the total mass of the first and second hydrophilic monomers is 100 parts by mass, the second hydrophilic monomer can be present in the following amounts: 0.1, 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45. 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 70, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100 parts by weight, or a range defined by any two of these. Preferably, the first hydrophilic monomer and the second hydrophilic monomer are present in a mass ratio of 0:100-85:15, for example, 25:75-80:20; within this preferred range, the prepared polymer has significantly reduced monomer residue; and furthermore, it can also have good hardness, oxygen permeability, static contact angle, and water absorption, and can improve at least one of hardness and oxygen permeability. More preferably, the first hydrophilic monomer and the second hydrophilic monomer are present in a mass ratio of 40:60-75:25; within this more preferred range, the prepared polymer can have improved hardness and processability.

[0277] Preferably, the second hydrophilic monomer has similar or identical functional groups to the first hydrophilic monomer except for the alkenyl moiety. For example, the only difference between the second and first hydrophilic monomers is that the second hydrophilic monomer uses an acryloyl group instead of a methacryloyl group in the first hydrophilic monomer. When the second and first hydrophilic monomers have similar or identical functional groups except for the alkenyl moiety, it helps to reduce monomer residue in the prepared polymer.

[0278] Preferably, the second hydrophilic monomer is selected from one or more of acrylic acid, hydroxyethyl acrylate, acrylamide, N,N-dimethylacrylamide, N-vinylpyrrolidone, and N-methyl-N-vinylacetamide.

[0279] Preferably, the first hydrophilic monomer is selected from methacrylic acid, and the second hydrophilic monomer is selected from one or more of acrylic acid, N-vinylpyrrolidone (NVP) and N,N-dimethylacrylamide, preferably acrylic acid.

[0280] When a first hydrophilic monomer is present in the second composition, one, two, or three of the following: a second hydrophobic fluorinated monomer, a second hydrophobic silicon-containing monomer, and a second hydrophilic monomer, preferably all three; in this case, compared to the case where only the first hydrophobic fluorinated monomer, the first hydrophobic silicon-containing monomer, and the first hydrophilic monomer are present, the chemical residue (residual monomer content) in the polymer prepared under the same polymerization conditions can be reduced; when two or three of the following: a second hydrophobic fluorinated monomer, a second hydrophobic silicon-containing monomer, and a second hydrophilic monomer are present (i.e. all), the chemical residue (residual monomer content) in the polymer prepared under the same polymerization conditions can be reduced even more significantly.

[0281] In the second composition, when a second hydrophilic monomer is present but a first hydrophilic monomer is absent, a second hydrophobic fluorinated monomer and / or a second hydrophobic silicon-containing monomer may be absent, or one or both of the second hydrophobic fluorinated monomer and the second hydrophobic silicon-containing monomer may be present. In the absence of the first hydrophilic monomer, when one or both of the second hydrophobic fluorinated monomer and the second hydrophobic silicon-containing monomer are present in addition to the first hydrophobic fluorinated monomer, the first hydrophobic silicon-containing monomer, and the second hydrophilic monomer, the chemical residue (residual monomer content) in the polymer prepared under the same polymerization conditions can be reduced compared to the corresponding case where only the first hydrophobic fluorinated monomer, the first hydrophobic silicon-containing monomer, and the second hydrophilic monomer are present; when both (i.e., all) of the second hydrophobic fluorinated monomer and the second hydrophobic silicon-containing monomer are present, the chemical residue (residual monomer content) in the polymer prepared under the same polymerization conditions can be reduced even more significantly.

[0282] The first and second compositions may optionally include a crosslinking agent component based on a diene-functionalized or higher crosslinking agent. When the first and second compositions further include a crosslinking agent, the mechanical properties of the prepared polymer can be improved. The amount of the crosslinking agent component is not particularly limited and can be appropriately selected depending on the intended purpose. For example, the first and second compositions may each include 1-20% by mass, preferably 5-15% by mass, for example, amounts of the crosslinking agent component as follows: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20% by mass, or a range defined by any two thereof.

[0283] Preferably, the crosslinking agent is selected from alkyl glycol dimethacrylate, more preferably neopentyl glycol dimethacrylate; siloxane-containing oligomers, more preferably 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane; or any combination thereof; for example, neopentyl glycol dimethacrylate and 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, in a ratio of, for example, 10:90-90:10. For example, a mass ratio of 20:80-80:20, 30:70-70:30, 40:60-60:40, 50:50-60:40, 45:55-55:45, or 50:50 exists. For example, when the total mass of neopentyl glycol dimethacrylate and 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane is 100 parts by mass, neopentyl glycol dimethacrylate... Esters and esters may be present in the following amounts: 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 70, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100 parts by weight, or a range defined by any two of these.

[0284] The first and second compositions may include a free radical initiator. The amount of the initiator is not particularly limited; for example, the first and second compositions may include 0.1-2.0% by mass, such as 0.5-1.0% by mass, for example, amounts of the initiator as follows: 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0% by mass, or a range defined by any two thereof.

[0285] The initiator is not particularly limited and can be a commonly used free radical initiator in the art, such as azobisisobutyronitrile or azobisisoheptanenitrile.

[0286] Depending on the intended use (e.g., for improving anti-aging properties), the first and second compositions may each further comprise a UV absorber, for example, 0.1-5.0% by mass, for example, 0.2-1.0% by mass, for example, 0.4-0.6% by mass of a UV absorber, for example, in amounts of the following: 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0% by mass, or a range defined by any two thereof. The UV absorber is not particularly limited; for example, the UV absorber may be 2-hydroxy-4-(methacryloyloxy)benzophenone.

[0287] Preferably, the second composition may include, based on the total mass of the second composition:

[0288] (1) 30-60% by mass, for example 40-50% by mass, of a monoalkenyl-functional hydrophobic fluorinated monomer component;

[0289] (2) 20-45% by mass, for example 30-40% by mass, of monoalkenyl-functional hydrophobic silicon-containing monomer components;

[0290] (3) 3-20% by mass, for example 5-10% by mass, of a monoalkenyl-functional hydrophilic monomer component;

[0291] (4) Optionally, 1-20% by mass, for example 5-15% by mass, of a crosslinking agent component based on a diene-functionalized or higher crosslinking agent; and

[0292] (5) 0.1-2.0% by mass, for example 0.5-1.0% by mass of free radical initiators.

[0293] (6) Optionally, 0.1-5.0% by mass, for example 0.2-1.0% by mass, for example 0.4-0.6% by mass of an ultraviolet absorber; and

[0294] (7) Optionally, 0.001-0.5% by mass, for example 0.005-0.01% by mass of a staining agent.

[0295] The applicant discovered that by adjusting the composition of the second composition within the above-mentioned range, the prepared polymer can simultaneously achieve good hardness, oxygen permeability, water wettability and processability; and therefore, it can be used to prepare, for example, rigid gas permeable contact lenses.

[0296] During storage or purification, monomers produced by free radical polymerization often polymerize due to factors such as light and heat. Adding a small amount of polymerization inhibitor can prevent this destructive reaction. Considering transportation and storage stability, monomer suppliers are hesitant to reduce the amount of polymerization inhibitor added. Therefore, for polymers prepared by free radical polymerization using olefinic unsaturated monomers (including the first and second olefinic unsaturated monomers mentioned herein) (including hydrophobic monomers mentioned herein (including the first and second hydrophobic monomers, the first and second hydrophobic fluorinated monomers, and the first and second hydrophobic silicon-containing monomers) and hydrophilic monomers (including the first and second hydrophilic monomers)), the monomer components used will also have high levels of impurities (including oligomers and polymers that may be generated during monomer polymerization during storage and transportation) and polymerization inhibitor content. These monomers typically have relatively high molecular weights and boiling points, and even when purified by methods such as distillation, the final purified product will still contain a certain amount of impurities and polymerization inhibitors.

[0297] The applicant further discovered that, alternatively or additionally, when the reactive monomers, including the first and second olefinically unsaturated monomers described herein, the hydrophobic monomers involved (including the first and second hydrophobic monomers, the first and second hydrophobic fluorinated monomers, and the first and second hydrophobic silicon-containing monomers) and the hydrophilic monomers (including the first and second hydrophilic monomers), and the crosslinking agents that may be present, have higher purity and lower inhibitor content (i.e., are provided in the form of raw materials with higher purity and lower inhibitor content), it is possible to further reduce the chemical residues (residual monomer content) in the polymers prepared under the same polymerization conditions.

[0298] Therefore, preferably, the method may include a purification step prior to polymerization, before providing the second composition capable of free radical polymerization:

[0299] (1) Purifying the first olefinically unsaturated monomer component to increase the content of the first olefinically unsaturated monomer and / or decrease the content of the polymerization inhibitor, for example, to make the content of the first olefinically unsaturated monomer 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor 50 ppm by mass or less; and / or

[0300] (2) Purify the second olefin unsaturated monomer component to increase the content of the second olefin unsaturated monomer and / or decrease the content of the polymerization inhibitor, for example, so that the content of the second olefin unsaturated monomer is 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor is 50 ppm by mass or less.

[0301] More preferably, the method may include a purification step prior to polymerization, before providing the second composition capable of free radical polymerization, as follows:

[0302] a) Purifying the first hydrophobic fluorinated monomer component to increase the content of the first hydrophobic fluorinated monomer and / or decrease the content of the polymerization inhibitor, for example, such that the content of the first hydrophobic fluorinated monomer is 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or

[0303] b) Purifying the second hydrophobic fluorinated monomer component to increase the content of the second hydrophobic fluorinated monomer and / or decrease the content of the polymerization inhibitor, for example, to make the content of the second hydrophobic fluorinated monomer 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor 50 ppm by mass or less; and / or

[0304] c) Purifying the first hydrophobic silicon-containing monomer component to increase the content of the first hydrophobic silicon-containing monomer and / or decrease the content of the polymerization inhibitor, for example, such that the content of the first hydrophobic silicon-containing monomer is 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or

[0305] d) Purifying the second hydrophobic silicon-containing monomer component to increase the content of the second hydrophobic silicon-containing monomer and / or decrease the content of the polymerization inhibitor, for example, such that the content of the second hydrophobic silicon-containing monomer is 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or

[0306] e) Purifying the first hydrophilic monomer component to increase the content of the first hydrophilic monomer and / or decrease the content of the polymerization inhibitor, for example, such that the content of the first hydrophilic monomer is 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or

[0307] f) Purifying the second hydrophilic monomer component to increase the content of the second hydrophilic monomer and / or decrease the content of the polymerization inhibitor, for example, to make the content of the second hydrophilic monomer 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor 50 ppm by mass or less; and / or

[0308] g) Purify the crosslinking agent component based on diene-functionalized or higher crosslinking agents to increase the crosslinking agent content and / or decrease the polymerization inhibitor content, for example, so that the crosslinking agent content is 98% by mass or more, preferably 99% by mass or more, and / or the polymerization inhibitor content is 50 ppm by mass or less.

[0309] More preferably, the method includes performing any one, two, three, four, five, six, or all of the purification steps a)-h) above, preferably all of them, to reduce the monomer content of the corresponding monomer components and / or crosslinking agent components (e.g., any one, two, three, four, five, six, or all of the first hydrophobic fluorinated monomer component, the second hydrophobic fluorinated monomer component, the first hydrophobic silicon-containing monomer component, the second hydrophobic silicon-containing monomer component, the first hydrophilic monomer component, the second hydrophilic monomer component, and the crosslinking agent component). The content of crosslinking agent is independently increased to 98% by mass or more, preferably 99% by mass or more; and / or the content of polymerization inhibitor in the corresponding monomer components (e.g., any one, two, three, four, five, six, or seven, or all, preferably all, of the first hydrophobic fluorinated monomer component, the second hydrophobic fluorinated monomer component, the first hydrophobic silicon-containing monomer component, the second hydrophobic silicon-containing monomer component, the first hydrophilic monomer component, the second hydrophilic monomer component, and the crosslinking agent component) is independently reduced to 50 ppm by mass or less.

[0310] Depending on the intended use (e.g., in the field of RGP materials, for distinguishing between left and right eye RGP lenses), the first composition may further include a dye, such as a non-reactive dye, in an amount of, for example: 0.001-0.5% by mass, for example 0.005-0.01% by mass, for example 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5% by mass, or a range defined by any two thereof.

[0311] In this document, unless otherwise specified, "non-reactive dye" means a dye that does not participate in the polymerization reaction; "reactive dye" means a dye that participates in the polymerization reaction, such as a reactive dye containing an alkenyl group or a methacryloyl group.

[0312] The applicant found that, alternatively or additionally, when a reactive dye is used to partially or completely replace a non-reactive dye, the residual monomer content in the prepared polymer can be further reduced; although the reduction is relatively small due to the relatively low dye dosage in the composition.

[0313] Therefore, preferably, the dye is selected from reactive dyes containing, for example, an alkenyl group, such as a methacryloyl group, such as one or more selected from 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone, 1,4-bis((2-hydroxyethyl)amino)-9,10-anthradinone bis(2-propeneOIC) ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenylethyl)methacrylamide.

[0314] Second Implementation Method

[0315] In a second embodiment of the first aspect of the present invention, the present invention provides a method for reducing the residual monomer content in a polymer composition (or polymer), said polymer composition (or polymer) being a polymer composition (or polymer) prepared by free radical polymerization using a first composition capable of free radical polymerization, said first composition capable of free radical polymerization comprising a mixture of the following:

[0316] The first ene unsaturated monomer component is based on the first ene unsaturated monomer, wherein the olefin bond in the first ene unsaturated monomer originates from the isopropenyl group (CH2=C(CH3)-).

[0317] Free radical initiators

[0318] Optionally, ultraviolet absorbers, and

[0319] Optional, dye;

[0320] The method includes (2) performing a purification step prior to polymerization, before combining the components to form the first composition capable of free radical polymerization, by purifying the first olefinic unsaturated monomer component to increase the content of the first olefinic unsaturated monomer and / or decrease the content of the polymerization inhibitor, for example, such that the content of the first olefinic unsaturated monomer is 98% by mass or more, preferably 99% by mass or more, and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and then performing free radical polymerization.

[0321] Preferably, the method may further include: providing a second composition capable of free radical polymerization by replacing a portion of the first olefinically unsaturated monomer component with a second olefinically unsaturated monomer component based on a second olefinically unsaturated monomer: wherein the olefinic bond of the second olefinically unsaturated monomer is derived from vinyl (CH2=CH-);

[0322] The second composition, which is capable of free radical polymerization, is then subjected to free radical polymerization.

[0323] All descriptions above regarding the first embodiment of the first aspect of the present invention (including descriptions of the composition of the first and second compositions, and descriptions of purification steps for various components) are applicable here and can be combined with the above-described methods and preferred embodiments of the second embodiment to constitute further preferred embodiments of the second embodiment, which will not be repeated here.

[0324] Third Implementation Method

[0325] In a third embodiment of the first aspect of the present invention, the present invention provides a method for reducing the residual monomer content in a polymer composition, said polymer composition being a polymer composition prepared by free radical polymerization using a first composition capable of free radical polymerization, said first composition capable of free radical polymerization comprising a mixture of the following:

[0326] The first ene unsaturated monomer component is based on the first ene unsaturated monomer, wherein the olefin bond in the first ene unsaturated monomer originates from the isopropenyl group (CH2=C(CH3)-).

[0327] Free radical initiators

[0328] Optionally, ultraviolet absorbers, and

[0329] Non-reactive staining agents;

[0330] The method includes: (3) partially or completely replacing the non-reactive dye in the first composition capable of free radical polymerization with, for example, a reactive dye containing an alkenyl group or a methacryloyl group to provide a second composition capable of free radical polymerization, wherein the reactive dye is selected, for example, from one or more of 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone, 1,4-bis((2-hydroxyethyl)amino)-9,10-anthradinone bis(2-propeneOIC) ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenylethyl)methacrylamide;

[0331] Then free radical polymerization is carried out.

[0332] The amount of dye in the second composition capable of free radical polymerization may be, for example, 0.001-0.5% by mass, such as 0.005-0.01% by mass.

[0333] Preferably, the method may further include: providing the second composition capable of free radical polymerization by replacing a portion of the first olefinically unsaturated monomer component with a second olefinically unsaturated monomer component based on a second olefinically unsaturated monomer: wherein the olefinic bond of the second olefinically unsaturated monomer is derived from vinyl (CH2=CH-);

[0334] The second composition, which is capable of free radical polymerization, is then subjected to free radical polymerization.

[0335] All descriptions above regarding the first embodiment of the first aspect of the present invention (including descriptions of the composition of the first and second compositions, and descriptions of purification steps for various components) are applicable here and can be combined with the above-described methods and preferred embodiments of the third embodiment to constitute further preferred embodiments of the third embodiment, which will not be repeated here.

[0336] By using the method of the present invention, partially replacing olefinically unsaturated monomers with olefinically unsaturated monomers whose olefinic bonds are derived from isopropenyl groups, particularly methacryloyl groups (e.g., methacryloyloxy groups), with olefinically unsaturated monomers whose olefinic bonds are derived from vinyl groups, particularly acryloyloxy, acryloylamino, N-vinylamino, and vinylphenyl groups, the residual monomer content in the prepared polymer (or polymer composition) can be significantly reduced. The prepared polymer therefore exhibits high biocompatibility, making it suitable for use as a medical polymer material. Furthermore, this free radical polymerization does not require complex process control. By further adjusting the composition of the second composition, the prepared polymer can also simultaneously achieve desired properties such as hardness, oxygen permeability, water wettability, and processability.

[0337] polymer composition

[0338] The second aspect of the present invention relates to a polymer composition (or polymer) obtained by the method according to the first aspect of the present invention.

[0339] The polymer according to the second aspect of the invention may be a medical polymer, particularly a polymer for use in corneal contact lenses, such as a polymer for use in rigid gas permeable contact lenses.

[0340] All descriptions above relating to the first aspect of the invention are applicable here.

[0341] Compositions capable of free radical polymerization

[0342] A third aspect of the present invention relates to compositions capable of free radical polymerization, said compositions comprising:

[0343] (1) A monoalkenyl-functional hydrophobic fluorinated monomer component, which includes or is composed of the following:

[0344] (1-1) Based on the first hydrophobic fluorinated monomer component of fluorinated alkyl methacrylate as the first hydrophobic fluorinated monomer;

[0345] Preferably, the first hydrophobic fluorinated monomer is a C1-C10 fluorinated alkyl methacrylate, more preferably a C1-C6 fluorinated alkyl methacrylate, more preferably a C2-C5 fluorinated alkyl methacrylate, and even more preferably a C2-C3 fluorinated alkyl methacrylate; preferably, the first hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, and 2,2,3,3,3-pentafluoropropyl methacrylate; more preferably, the first hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl methacrylate and hexafluoroisopropyl methacrylate.

[0346] and

[0347] (1-2) Optional second hydrophobic fluorinated monomer component based on fluorinated alkyl acrylate as a second hydrophobic fluorinated monomer;

[0348] Preferably, the fluorinated alkyl group in the second hydrophobic fluorinated monomer is the same as or different from the fluorinated alkyl group in the first hydrophobic fluorinated monomer, and preferably the same;

[0349] Preferably, the second hydrophobic fluorinated monomer is a C1-C10 fluorinated alkyl acrylate, more preferably a C1-C6 fluorinated alkyl acrylate, more preferably a C2-C5 fluorinated alkyl acrylate, and even more preferably a C2-C3 fluorinated alkyl acrylate; preferably, the second hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl acrylate, hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, and 2,2,3,3,3-pentafluoropropyl acrylate; more preferably, the second hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl acrylate and hexafluoroisopropyl acrylate.

[0350] Preferably, the first hydrophobic fluorinated monomer is selected from one or more of hexafluoroisopropyl methacrylate and trifluoroethyl methacrylate, and the second hydrophobic fluorinated monomer is selected from one or more of hexafluoroisopropyl acrylate and trifluoroethyl acrylate; preferably, the first hydrophobic fluorinated monomer is hexafluoroisopropyl methacrylate and the second hydrophobic fluorinated monomer is hexafluoroisopropyl acrylate, or the first hydrophobic fluorinated monomer is trifluoroethyl methacrylate and the second hydrophobic fluorinated monomer is trifluoroethyl acrylate;

[0351] (2) Monoalkenyl-functional hydrophobic silicon-containing monomer components, which include or are composed of the following:

[0352] (2-1) Based on the first hydrophobic silicon-containing monomer component of silicon-containing methacrylate as the first hydrophobic silicon-containing monomer,

[0353] Preferably, the first hydrophobic silicon-containing monomer is a silicon-containing methacrylate of the following formula: CH2=C(CH3)-C(O)-O-L1-Si(R1)m(OR2) 3-m L1 is a C1-C10, preferably C3-C6 divalent alkylene group that optionally includes one or more groups selected from ether-O-atom groups and -OH groups; R1 is the same as or different from each other and is independently C1-C6 alkyl, preferably methyl; R2 is the same as or different from each other and is independently C1-C6 alkyl, preferably methyl, or -Si(R3)3, wherein R3 is the same as or different from each other and is independently C1-C6 alkyl, preferably methyl; m is 0, 1, 2, or 3, preferably 0 or 1.

[0354] Preferably, the first hydrophobic silicon-containing monomer is selected from one or more of methacryloyloxypropyltris(trimethylsiloxane)silane and (3-methacryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane;

[0355] and

[0356] (2-2) Optionally, a second hydrophobic silicon-containing monomer component based on a silicon-containing acrylate or a vinylphenyl-containing silane as a second hydrophobic silicon-containing monomer.

[0357] Preferably, the second hydrophobic silicon-containing monomer is CH2=CH-C(O)-O-L2-Si(R4). n (OR5) 3-n Or CH2=CH-Ph-Si(R4) n (OR5) 3-n Ph is a phenylene, for example, 1,4-phenylene; L2 is the same as or different from L1 and is a C1-C10, preferably C3-C6 dialkylene group, optionally including one or more groups of ether-O-atom group or -OH group; R4 is the same as or different from each other and the same as or different from R1 and is independently a C1-C6 alkyl group, preferably methyl; R5 is the same as or different from each other and the same as or different from R2 and is independently a C1-C6 alkyl group, preferably methyl or -Si(R6)3, wherein R6 is the same as or different from each other and the same as or different from R3 and is independently a C1-C6 alkyl group, preferably methyl; n is the same as or different from m and is 0, 1, 2 or 3, preferably 0 or 1;

[0358] Preferably, -Si(R4) n (OR5) 3-n Partially related to -Si(R1)m(OR2) 3-m If some parts are the same or different, the same parts are preferred.

[0359] Preferably, -L2-Si(R4) n (OR5) 3-n Partially related to -L1-Si(R1)m(OR2) 3-m If some parts are the same or different, the same parts are preferred.

[0360] Preferably, the second hydrophobic silicon-containing monomer is selected from one or more of acryloyloxypropyltris(trimethylsiloxane), (3-acryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, and p-vinylphenyltris(trimethylsiloxy)silane;

[0361] Preferably, the first hydrophobic silicon-containing monomer is selected from methacryloyloxypropyltris(trimethylsiloxane)silane, and the second hydrophobic silicon-containing monomer is selected from one or more of acryloyloxypropyltris(trimethylsiloxane)silane and p-vinylphenyltris(trimethylsiloxy)silane, preferably acryloyloxypropyltris(trimethylsiloxane);

[0362] (3) Monoalkenyl-functional hydrophilic monomer components, which include or are composed of the following:

[0363] (3-1) A first hydrophilic monomer component based on a first hydrophilic monomer containing a methacryloyl group;

[0364] Preferably, the first hydrophilic monomer is selected from one or more of methacrylic acid, hydroxyethyl methacrylate, methacrylamide, and N,N-dimethylmethacrylamide;

[0365] and / or

[0366] (3-2) A second hydrophilic monomer component based on a second hydrophilic monomer containing acryloyloxy, acryloylamino and / or N-vinylamino;

[0367] Preferably, the difference between the second hydrophilic monomer and the first hydrophilic monomer is only that the second hydrophilic monomer uses an acryloyl group instead of a methacryloyl group in the first hydrophilic monomer;

[0368] Preferably, the second hydrophilic monomer is selected from one or more of acrylic acid, hydroxyethyl acrylate, acrylamide, N,N-dimethylacrylamide, N-vinylpyrrolidone, and N-methyl-N-vinylacetamide;

[0369] Preferably, the first hydrophilic monomer is selected from methacrylic acid, and the second hydrophilic monomer is selected from one or more of acrylic acid, N-vinylpyrrolidone (NVP) and N,N-dimethylacrylamide, preferably acrylic acid;

[0370] (4) Optionally, a crosslinking agent component based on a diene-functional or higher crosslinking agent;

[0371] Preferably, the crosslinking agent with a diene function or higher is selected from: alkyl glycol dimethacrylate, preferably neopentyl glycol dimethacrylate; siloxane-containing oligomers, preferably 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane; for example, neopentyl glycol dimethacrylate and 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, which are present, for example, in a mass ratio of 10:90-90:10, for example 30:70-70:30, for example 50:50-60:40;

[0372] (5) Free radical initiators, such as azobisisobutyronitrile or azobisisoheptanenitrile;

[0373] (6) Optionally, a UV absorber, such as 2-hydroxy-4-(methacryloyloxy)benzophenone; and

[0374] (7) Optionally, 0.001-0.5% by mass, for example 0.005-0.01% by mass of a staining agent;

[0375] The composition may satisfy one, two, or three of the following conditions (i)-(iii):

[0376] (i) When a first hydrophilic monomer is present, one, two, or three of the following are present: a second hydrophobic fluorinated monomer, a second hydrophobic silicon-containing monomer, and a second hydrophilic monomer; and / or

[0377] (ii) The content of the first hydrophobic fluorinated monomer in the first hydrophobic fluorinated monomer component, and / or the content of the second hydrophobic fluorinated monomer in the second hydrophobic fluorinated monomer component, and / or the content of the first hydrophobic silicon-containing monomer in the first hydrophobic silicon-containing monomer component, and / or the content of the second hydrophobic silicon-containing monomer in the second hydrophobic silicon-containing monomer component, the content of the first hydrophilic monomer in the first hydrophilic monomer component, and / or the content of the second hydrophilic monomer in the second hydrophilic monomer component, and / or the content of the crosslinking agent in the crosslinking agent component based on a diene-functionalized or higher crosslinking agent, are each independently 98% by mass or more, preferably 99% by mass or more; and / or

[0378] The content of the polymerization inhibitor in each of the first hydrophobic fluorinated monomer component, and / or the second hydrophobic fluorinated monomer component, and / or the first hydrophobic silicon-containing monomer component, and / or the second hydrophobic silicon-containing monomer component, and / or the first hydrophilic monomer component, and / or the second hydrophilic monomer component, and / or the crosslinking agent component is independently less than 50 ppm by mass; and / or

[0379] (iii) The composition further comprises a reactive staining agent, for example, a reactive staining agent containing an alkenyl group, such as a reactive staining agent containing a methacryloyl group, selected, for example, from one or more reactive staining agents selected from 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone, 1,4-bis((2-hydroxyethyl)amino)-9,10-anthradinone bis(2-propeneOIC) ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenethyl)methacrylamide, in an amount, for example, 0.001-0.5% by mass, for example, 0.005-0.01% by mass.

[0380] Preferably, the composition may include, based on the total mass of the composition:

[0381] (1) 30-60% by mass, for example 40-50% by mass, of a monoalkenyl-functional hydrophobic fluorinated monomer component;

[0382] (2) 20-45% by mass, for example 30-40% by mass, of monoalkenyl-functional hydrophobic silicon-containing monomer components;

[0383] (3) 3-20% by mass, for example 5-10% by mass, of a monoalkenyl-functional hydrophilic monomer component;

[0384] (4) Optionally, 1-20% by mass, for example 5-15% by mass, of a crosslinking agent component based on a diene-functionalized or higher crosslinking agent; and

[0385] (5) 0.1-2.0% by mass, for example 0.5-1.0% by mass, of a free radical initiator; and

[0386] (6) Optionally, 0.1-5.0% by mass, for example 0.2-1.0% by mass, for example 0.4-0.6% by mass of a UV absorber.

[0387] Preferably, in the composition:

[0388] The presence of a second hydrophobic fluorinated monomer, preferably in a mass ratio of 30:70-80:20, for example 50:50-80:20, or for example 70:30-80:20; and / or

[0389] The presence of a second hydrophobic silicon-containing monomer, preferably in a mass ratio of 30:70-80:20, for example 50:50-75:25, to the first hydrophobic silicon-containing monomer; and / or

[0390] The presence of a first hydrophilic monomer and a second hydrophilic monomer is preferred, with the first hydrophilic monomer and the second hydrophilic monomer present in a mass ratio of 0:100-85:15, for example 25:75-80:20, for example 40:60-75:25.

[0391] Preferably, the composition contains a second hydrophobic fluorinated monomer, a second hydrophobic silicon-containing monomer, a first hydrophilic monomer, and a second hydrophilic monomer.

[0392] The composition is particularly suitable for preparing medical polymers requiring high biocompatibility. In particular, by controlling the composition within the above-mentioned range, the prepared polymer can simultaneously achieve good hardness, oxygen permeability, water wettability, and processability; and therefore, it can be used to prepare, for example, rigid gas permeable contact lenses.

[0393] All the features, aspects, and effects described above regarding the method of the first aspect of the present invention, including all descriptions of the composition of the second composition, such as all descriptions of the monoalkenyl-functional hydrophobic fluorinated monomer component and the first hydrophobic fluorinated monomer component and optionally the second hydrophobic fluorinated monomer component contained therein, the monoalkenyl-functional hydrophobic silicon-containing monomer component and the first hydrophobic silicon-containing monomer component and optionally the second hydrophobic silicon-containing monomer component contained therein, the monoalkenyl-functional hydrophilic monomer component and the first hydrophilic monomer component and / or the second hydrophilic monomer component contained therein, the crosslinking agent component and the crosslinking agent, dyeing agent, free radical initiator, ultraviolet absorber, etc. contained therein, are applicable to the composition of the third aspect of the present invention, and will not be repeated here.

[0394] The polymer prepared using the composition of the third aspect of the present invention may have any one or more of the following performance indicators (1)-(8), for example, 1, 2, 3, 4, 5, 6 or 7, or all of them:

[0395] (1) Known total residual monomer (mass%): 3.7 or lower, for example 3.7, 3.6, 3.5, 3.4, 3.3, 3.2, 3.1, 3.0, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0, or a range defined by any two thereof;

[0396] (2) Total amount of unknown impurities remaining (mass%): 2.4 or less, for example 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0, or a range defined by any two of these;

[0397] (3) Total residual monomers (mass %): 6.0 or lower, e.g., 6.0, 5.9, 5.8, 5.7, 5.6, 5.5, 5.4, 5.3, 5.2, 5.1, 5.0, 4.9, 4.8, 4.7, 4.6, 4.5, 4.4, 4.3, 4.2, 4.1, 4.0, 3.9, 3.8, 3.7, 3.6, 3.5, 3.4, 3.3, 3.2, 3.1, 3.0, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0, or a range defined by any two of these.

[0398] (4) Hardness (Shore D): 75 or higher, such as 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, or a range defined by any two of them;

[0399] (5) Oxygen permeability coefficient DK (barerr): 10⁹ or higher, for example, 10⁹, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 14 9, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189 or higher, or a range defined by any two of these;

[0400] (6) Static contact angle (°): 45 or lower, for example 45, 44, 43, 42, 41, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26 or lower, or a range defined by any two of them;

[0401] (7) Water absorption rate (%): 0.23 or higher, for example 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41 or higher, or a range defined by any two of these;

[0402] (8) Visible spectral transmittance (%): 89 or higher, such as 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or even 100, or a range defined by any two of them.

[0403] In this application, known monomer residue refers to the residual unpolymerized monomer corresponding to the monomer used to prepare the polymer; unknown impurity residue refers to other residues besides known monomer residue; and total residual monomer refers to the sum of known monomer residue and unknown impurity residue.

[0404] Compared to compositions in which the monoalkenyl-functionalized hydrophobic fluorinated monomer component uses only fluorinated alkyl methacrylates (e.g., C1-C10), the monoalkenyl-functionalized hydrophobic silicon-containing monomer component uses only methacrylate-type silicon-containing monomers, and the monoalkenyl-functionalized hydrophilic monomer component uses only compounds containing methacryloyl groups, the polymer prepared using the composition of the third aspect of the present invention has a significantly reduced residual monomer content and therefore exhibits high biocompatibility, making it suitable for use as a medical polymer material. Furthermore, this free radical polymerization does not require complex process control. Moreover, by controlling the composition, the prepared polymer can simultaneously achieve good hardness, oxygen permeability, water wettability, and processability; and therefore, it can be used to prepare, for example, rigid gas permeable contact lenses.

[0405] Therefore, preferably, the composition is a composition for preparing medical polymers. In particular, the composition can be used to prepare corneal contact lenses, such as rigid gas permeable contact lenses.

[0406] Polymer preparation methods

[0407] A fourth aspect of the present invention relates to a method for preparing a polymer, comprising providing a composition according to a third aspect of the present invention, and subjecting the composition to free radical polymerization.

[0408] All descriptions above regarding the method of the first aspect, the polymer composition of the second aspect, and the composition of the third aspect of the present invention are applicable here and will not be repeated here.

[0409] polymer

[0410] The fifth aspect of the present invention relates to polymers obtained by free radical polymerization of compositions according to the third aspect of the present invention or polymers obtained by polymerization methods according to the fourth aspect of the present invention.

[0411] Therefore, the polymer according to the fifth aspect of the invention can be a medical polymer, particularly a polymer for use in corneal contact lenses, such as a polymer for use in rigid gas permeable contact lenses.

[0412] All descriptions above relating to the third and fourth aspects of the invention are applicable here.

[0413] use

[0414] The sixth aspect of the invention relates to the use of the compositions of the third aspect of the invention in the preparation of polymers, such as medical polymers, particularly polymers for use in corneal contact lenses, such as polymers for use in rigid gas permeable contact lenses.

[0415] All descriptions above relating to the first to fifth aspects of the present invention are applicable here and will not be repeated here.

[0416] Example

[0417] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are only for illustrating the present invention and should not be regarded as limiting the scope of the present invention.

[0418] Experimental materials

[0419] The supplier information for the experimental raw materials used in the examples is shown in Table 1 below:

[0420] Table 1

[0421]

[0422]

[0423] Test methods

[0424] Monomer residue testing

[0425] The spare button-shaped sheets (hereinafter referred to as button sheets) prepared in each embodiment were processed into optical lenses with a diameter of 11 mm and a thickness of 0.22 mm using a precision lathe. The lenses were extracted with 10 mL of dichloromethane in a shaker at 37°C for 48 h. The resulting dichloromethane extract was analyzed by gas chromatography (detector FID, column type DB200, injection port temperature 280°C, detector temperature 300°C, flow rate 1.0 mL / min, column temperature: initial temperature 30°C, hold for 5 min, increase to 250°C at a rate of 10°C / min, hold for 8 min, increase to 300°C at a rate of 10°C / min, hold for 10 min). A standard curve prepared from the monomers of each copolymer component was used to quantify the concentration of unpolymerized monomers in the dichloromethane extract, thereby calculating the residual amount of known unpolymerized monomers. The residual amount of unknown monomers was calculated using a reference solution of one of the known monomers as a control.

[0426] Hardness (Shore D)

[0427] The spare clips prepared in each embodiment were machined into samples with a diameter of 12 mm, a thickness of 3 mm, and flat, parallel, and polished front and back surfaces using a precision lathe. Two of the above samples were stacked together to form a sample with a thickness of 6 mm. Three independent measurements were performed using a Shore D type hardness tester (model C022) equipped with an indenter specified in GB / T2411-2008 at an environment of 20 ℃±5 ℃, and the arithmetic mean of the three measurements was calculated.

[0428] Oxygen permeability coefficient (Dk)

[0429] The spare clips prepared in each embodiment were machined into four optical lenses with a diameter of 11 mm and different thicknesses (0.04~0.4 mm) using a precision lathe. These optical lenses were then mounted on a polarographic oxygen sensor, which consisted of a 4 mm diameter gold cathode and a silver ring anode. The entire probe with the test sample was placed in a heating chamber at 35℃±0.5℃, with water provided to maintain a relative humidity of at least 98% for the exposed surface of the test sample. Stable current values ​​were read and recorded. The t / Dk of the four samples with significantly different thickness (t) values ​​was calculated, and a linear regression was performed on t / Dk relative to t. The reciprocal of the regression slope was the sample's Dk. All units were standardized to 10. -11 (cm) 2 / s[mLO2 / (mL•mmHg]).

[0430] static contact angle

[0431] The spare contact lenses prepared in each embodiment were machined into lenses with a diameter of 12 mm and a thickness of 4 mm using a precision lathe. The surfaces were machined and polished to match the finished contact lens lenses. Before measurement, the samples were deeply rinsed in a standard PBS buffer solution (containing 8.300 g sodium chloride, 0.528 g sodium dihydrogen phosphate (containing 2 molecules of water of crystallization), and 5.993 g disodium hydrogen phosphate (containing 12 molecules of water of crystallization) per L of water). They were then placed in the standard PBS buffer solution for at least 24 h to reach equilibration. Measurements were then performed using a contact angle measuring device from Ramé-Hart Instruments Co., and the values ​​displayed on the device were read. Five independent measurements were taken, with 10 contact angle readings recorded for each measurement. The arithmetic mean of the 50 readings was recorded as the "contact angle" of the sample surface.

[0432] Water absorption rate

[0433] The spare clips prepared in each embodiment were machined into clips with a diameter of 11 mm and a thickness of 4 mm using a precision lathe. Each group weighed 6-7 g. After drying to constant weight, the weight (g) of each group was measured. Each group was immersed in a container containing 20 mL of 0.9% sodium chloride solution for 7 days, and then the surface moisture was quickly wiped dry. The wet weight (g) of each group was measured. The water absorption rate of each clip was calculated using the following formula: Water absorption rate = (Wet weight - Initial weight) / Initial weight × 100%.

[0434] Visible spectral transmittance

[0435] The spare clips prepared in each embodiment were machined into lenses with a diameter of 11 mm and a thickness of 0.22 mm using a precision lathe. Testing was performed using a Shimadzu UV-2600i UV-Vis spectrophotometer. The sample was placed on a sample holder, and its position was adjusted to ensure that light passed through the center of the sample and that the light was perpendicular to the sample. The transmitted light intensity was measured, and the transmitted light intensity and incident light intensity were recorded. The average transmittance of the visible spectrum was calculated according to the formula given in GB / T11417.5. The transmittance of the sample was calculated under standard illuminators D65 and A. Three independent measurements were performed, and the arithmetic mean of the three measurements was calculated.

[0436] Example 1

[0437] The copolymer is synthesized according to the feeding ratio (mass percentage) shown in Table 2 and the following operating process.

[0438] The purchased monomers were removed from a 2-8°C refrigerator (see Table 1 for specific material purity and inhibitor content information) and placed at room temperature for 2 hours. The monomers were then transferred to a nitrogen-atmosphere operating chamber, ensuring the oxygen content was below 0.5%. Using a precision analytical balance, according to the specific formulation of Example 1 shown in Table 2, HFPMA (hexafluoroisopropyl methacrylate), M-TRIS (methacryloyloxypropyltris(trimethylsiloxane)silane), MAA (methacrylic acid), AIBN (azobisisobutyronitrile), NPGDMA (neopentyl glycol dimethacrylate), DIMER (1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane), HECB (2-hydroxy-4-(methacryloyloxy)benzophenone), and Green 6# (a blended dye) were directly dissolved and mixed uniformly under a nitrogen atmosphere to obtain the reaction solution.

[0439] Cool the resulting reaction solution to below -10°C, and immediately connect the reaction solution using a three-way valve connected to nitrogen and a negative pressure device. Repeatedly replace the reaction solution atmosphere with nitrogen for at least 1 minute. Then, seal the reaction solution and let it stand at room temperature for 30 minutes. Inject the above mixture into a polypropylene molding mold (140mm diameter, 20mm depth), with removable polypropylene sealing plugs at both the bottom and top. Transfer to a nitrogen-filled oxygen-free oven, controlling the oxygen content to below 0.1%, maintain at 40°C for 2 hours, raise the temperature to 60°C and maintain for 8 hours, raise the temperature to 90°C and maintain for 12 hours, then slowly cool to room temperature (20°C every hour) to complete the free radical copolymerization. At room temperature, remove the polypropylene sealing plugs from both the top and bottom of the mold, eject the rod-shaped material from the polypropylene mold using a tool, and use a CNC lathe to cut the rod into button-shaped sheets (button sheets) with a diameter of 12.7mm and a thickness of 4.25mm for later use (polymerization conditions - method A).

[0440] The prepared button clips were tested. The test results are shown in Table 2.

[0441] Examples 2-7

[0442] The polymerization and preparation of the button sheets were carried out in the same manner as in Example 1, except that, for the polymerization raw materials, other fluorinated monomers of different types and amounts (see Table 1 for information on the purity of the specific materials and the content of the polymerization inhibitor) were used instead of HFPMA or TFEMA, according to the specific formulations shown in Table 2.

[0443] The prepared button clips were tested. The test results are shown in Table 2.

[0444] Table 2

[0445]

[0446] Compared to Example 1, Examples 2-5 used 35, 25, 15, and 10 parts by mass of HFPA to replace an equal part by mass of HFPMA, respectively. As a result, the residual amount of fluorinated monomers like HFPMA was significantly reduced. Simultaneously, the residual amount of other monomers (M-TRIS, MAA) in the copolymerization system was also reduced to varying degrees, resulting in a significant reduction in the total amount of known monomer residues compared to Example 1. The total amount of unknown impurities was also slightly reduced, thus significantly reducing the total amount of residual monomers compared to Example 1. Examples 3 and 4 showed the most significant reduction in the residual amount of various monomers. This indicates that partially replacing methacrylate-terminated monomers with acrylate-terminated monomers can improve the copolymerization environment of the system and reduce the amount of residual monomers. Furthermore, Examples 2-5 achieved oxygen permeability, contact angle, and water absorption data that were essentially the same as in Example 1. Compared to Example 1, Examples 2-5 improved at least one, or even both, the hardness and oxygen permeability. With increasing acrylate monomer content, the oxygen permeability generally increased, but the hardness decreased.

[0447] Compared to Example 7, Example 6 used 15 parts by weight of TFEA to replace an equal part by weight of TFEMA. As a result, the residual amount of TFEMA-type fluorinated monomers was significantly reduced, and the residual amount of other monomers (M-TRIS, MAA) that constituted a large proportion of the copolymerization system was also significantly reduced. This resulted in a significant reduction in the total amount of known monomer residues compared to Example 7, while the total amount of unknown impurities was also slightly reduced. Therefore, the total amount of residual monomers was significantly reduced compared to Example 7. This demonstrates that partially replacing methacrylate-terminated monomers with acrylate-terminated monomers can improve the copolymerization environment of the system and reduce monomer residues. Furthermore, Example 6 achieved substantially the same contact angle and water absorption rate data as Example 7, and also achieved better hardness and oxygen permeability.

[0448] Examples 8-12

[0449] The polymerization and button chip preparation were carried out in the same manner as in Example 1, except that, for the polymerization raw materials, different types and amounts of other silicon-containing monomers (see Table 1 for information on the purity of specific materials and the content of polymerization inhibitors) were used instead of M-TRIS according to the specific formulations shown in Table 3.

[0450] The prepared button clips were tested. The test results are shown in Table 3.

[0451] Table 3

[0452]

[0453] Compared to Example 1, Examples 8-10 used 20, 15, and 10 parts by mass of TIS to replace an equal part by mass of M-TRIS, respectively. As a result, the residual amount of M-TRIS-type siloxane monomers was significantly reduced, and the residual amount of other monomers (HFPMA, MAA) in the copolymerization system was also reduced to varying degrees. This resulted in a significant reduction in the total amount of known monomers compared to Example 1 (and a more significant reduction compared to Examples 2-6). Simultaneously, the total amount of unknown impurities was also slightly reduced, thus significantly reducing the total amount of residual monomers compared to Example 1. This indicates that partially replacing methacrylic acid-terminated silicon-containing monomers with acrylic acid-terminated silicon-containing monomers can improve the copolymerization environment of the system and reduce the amount of residual monomers. Furthermore, Examples 8-10 achieved essentially the same oxygen permeability coefficient, contact angle, and water absorption rate as Example 1. Compared to Example 1, Examples 8-10 improved at least one, or even both, hardness and oxygen permeability coefficient. In Examples 8-10, with increasing acrylate monomer content, the oxygen permeability coefficient slightly decreased, the static contact angle slightly increased, and the hardness slightly decreased (however, the decrease in hardness was relatively weaker compared to Examples 2-6). Examples 9 and 10 showed particularly significant reductions in various monomer residues, with the total known monomer residues being <2%, and compared to Example 1, the hardness, oxygen permeability coefficient, contact angle, and water absorption rate remained unchanged or even slightly improved.

[0454] Examples 11-12 used vinyl-terminated siloxane monomers with different structures but the same functional side chains as M-TRIS, namely vinylphenyltris(trimethylsiloxy)silane (TTMS), to replace M-TRIS. The results showed that, compared to Example 1, Examples 11 and 12 also significantly reduced the total amount of known monomers remaining (the reduction trend was slightly smaller compared to Examples 9 and 10); at the same time, the total amount of unknown impurities remaining was also slightly reduced, thus resulting in a significant reduction in the total amount of residual monomers compared to Example 1. This indicates that partially replacing methacrylic acid-terminated silicon-containing monomers with vinyl-terminated silicon-containing monomers can also improve the copolymerization environment of the system and reduce the amount of residual monomers. Furthermore, compared to Example 1, Examples 11-12 achieved a significantly higher oxygen permeability coefficient, but the hardness was relatively reduced, and the static contact angle increased.

[0455] Examples 13-20

[0456] The polymerization and preparation of the button sheets were carried out in the same manner as in Example 1, except that, for the polymerization raw materials, different types and amounts of other hydrophilic monomers (see Table 1 for information on the purity of the specific materials and the content of the polymerization inhibitor) were used instead of MAA according to the specific formulations shown in Table 4.

[0457] The prepared button clips were tested. The test results are shown in Table 4.

[0458] Table 4

[0459]

[0460] Compared to Example 1, Examples 13-16 used 7, 4, 3, and 2 parts by mass of AA to replace an equal part by mass of MAA, respectively. As a result, the monomer residue of MAA was significantly reduced, and the residue of other monomers (HFPMA, M-TRIS) that constituted a large proportion of the copolymerization system was also significantly reduced. This resulted in a significant reduction in the total amount of known monomer residue compared to Example 1, as well as a significant reduction in the total amount of unknown impurities. The total amount of known impurities in Examples 14 and 15 was controlled to within 1%. This indicates that partially replacing methacrylic acid-type hydrophilic monomers with acrylic acid-type hydrophilic monomers can improve the copolymerization environment of the system and reduce monomer residue. However, compared to Example 1, the polymer prepared in Example 13, which completely replaced MAA with AA, showed a significant decrease in both hardness and oxygen permeability. Compared to Example 1, Examples 14-16, which use AA to partially replace MAA, improve at least one or even both of the hardness and oxygen permeability of Examples 8-10, and achieve contact angle and water absorption data that are substantially consistent with those of Example 1. The copolymers prepared in Examples 15-16 have significantly higher hardness than those in Example 1, showing good processability.

[0461] Examples 17-20 used hydrophilic monomers N-vinylpyrrolidone (NVP) and N,N-dimethylacrylamide (DMAA) with the same side chain function as MAA to completely or partially replace MAA. As a result, a strong effect was also shown in reducing the residual known hydrophobic monomers (HFPMA, M-TRIS), resulting in a significant reduction in the total amount of known monomers remaining compared to Example 1, while the total amount of unknown impurities remaining was also slightly reduced. Thus, the total amount of residual monomers was significantly reduced compared to Example 1: Examples 17-20 could also control the residual known monomers to around 1%, or even less than 1%. Compared to Example 1, Examples 17-19 showed improved hardness, which is believed to be due to the rigid pyrrolidone ring linked to the vinyl group in NVP. The presence of the rigid ring hinders the rotation of the overall macromolecular chain segments after copolymerization, making the chain segments harder and thus increasing the hardness of the corresponding material. Furthermore, compared to Example 1, Examples 17-19 could essentially maintain or even improve the oxygen permeability coefficient; however, the water absorption rate of this series of materials was lower than in other examples. However, the material in Example 19 was brittle during lathe machining, indicating that using NVP alone still has a certain impact on the mechanical properties of the material. Example 20 shows that, compared to NVP, DMAA replacing part of MAA has slightly weaker control over residual impurities, and the copolymer is also slightly less hard, but it can slightly improve the oxygen permeability coefficient of the copolymer.

[0462] Examples 21-22

[0463] The polymerization and preparation of the button sheets were carried out in the same manner as in Example 1, except that: for the polymerization raw materials, according to the specific formulation shown in Table 5, the corresponding raw materials were weighed according to the mass percentage (equivalent to pure feed) (the purity of the specific materials and the content of the polymerization inhibitor are shown in Table 1).

[0464] The prepared button clips were tested. The test results are shown in Table 5.

[0465] Table 5

[0466]

[0467] As can be seen from the table above, compared with Example 1, by partially replacing HFPMA with FPMA, partially replacing M-TRIS with TRIS, and partially replacing MAA with AA or completely replacing it with NVP, the residual amount of known monomers was significantly reduced, and it was slightly better than Examples 15 and 19. Moreover, compared with Example 1, the total amount of unknown impurities was also slightly reduced, thus the total amount of residual monomers was significantly reduced compared with Example 1. In addition, compared with Example 1, Examples 21-22 slightly improved the oxygen permeability coefficient while maintaining or improving the hardness, and maintained a static contact angle and water absorption rate that were basically the same as those of Example 1.

[0468] As described above, Example 19 used 7% NVP, a hydrophilic monomer, to replace 7% MAA. As a result, although the monomer residue was significantly reduced, the material was hard and brittle, which was not conducive to processing. Compared with Example 19, in Example 22, by further partially replacing HFPMA with FPMA and partially replacing M-TRIS with TRIS, the hardness of the copolymer prepared was adjusted to a suitable range, and the processing performance of the material was significantly improved.

[0469] Examples 23-24

[0470] The polymerization and preparation of the button sheets were carried out in the same manner as in Example 1, except that: for the polymerization raw materials, the corresponding raw materials were weighed according to the specific formulation shown in Table 6 by mass percentage (equivalent to pure feed) (the purity of the specific materials and the content of the polymerization inhibitor are shown in Table 1).

[0471] In the following text, when “mixed monomers” is mentioned, it refers to the following mixture: NPGDMA 7%, TTMS 9%, DIMER 8%, HECB 0.49%, Green6 # 0.01%, where “%” refers to the mass in the formulation.

[0472] The prepared button clips were tested. The test results are shown in Table 6.

[0473] Table 6

[0474]

[0475] Compared to Example 23, Example 24 used TRIS to replace part of M-TRIS and AA to replace part of MAA. As a result, the total residual amount of known monomers, the total residual amount of unknown monomers, and the total residual amount of monomers decreased from 3.7%, 2.8%, and 6.5% in Example 23 to 0.7%, 2.4%, and 3.1%, respectively. At the same time, compared with Example 23, the oxygen permeability coefficient in Example 24 was significantly improved, while exhibiting excellent hardness and water absorption, and the static contact angle was slightly reduced.

[0476] Examples 25-26

[0477] Polymerization and buttoncap preparation were carried out in the same manner as in Example 21, except that: polymerization was performed using different curing equipment and curing procedures. In Example 25, after the reaction solution was injected into the molding die, it was transferred to a forced-air drying oven, held at 40°C for 2 hours, then heated to 60°C and held for 24 hours, then heated to 90°C and held for 12 hours, and then slowly cooled to room temperature (10°C every hour) under controlled conditions, thereby completing the free radical copolymerization (polymerization conditions - method B); in Example 26, it was transferred to a constant temperature water bath, held at 40°C for 2 hours, then heated to 60°C and held for 48 hours, then heated to 70°C and held for 12 hours, and then slowly cooled to room temperature (10°C every hour) under controlled conditions, thereby completing the free radical copolymerization (polymerization conditions - method C). The purity of the specific materials used in Examples 25-26 and the content of the polymerization inhibitor are shown in Table 1.

[0478] The prepared button clips were tested. The test results are shown in Table 7.

[0479] Table 7

[0480]

[0481] Curing method B uses a forced-air drying oven instead of a nitrogen-filled oxygen-free oven. Because of the reduced air circulation, the chain initiation stage is slower; therefore, the holding time at 60℃ is extended for curing method B. Water bath curing has the advantages of uniform temperature and rapid heat dissipation, but it is limited by the generation of water vapor at high temperatures. Therefore, the temperature of the high-temperature section was lowered and the holding time was extended when setting the curing program, thus determining curing method C.

[0482] Comparing the test data of Examples 21 with those of 25 and 26, it can be determined that the method of controlling the residual monomer content by the composition of hydrophobic fluorinated monomers, hydrophobic silicon-containing monomers and hydrophilic monomers is still effective under various curing conditions.

[0483] The schemes and test data of Examples 1-26 show that by controlling the composition of hydrophobic fluorinated monomers, hydrophobic silicon monomers and hydrophilic monomers, the total amount of known monomers, the total amount of unknown impurities and the total amount of residual monomers in the obtained polymer can be effectively reduced. Furthermore, the physical parameters such as oxygen permeability, wettability, mechanical properties and processing properties of RGP copolymers can be optimized, thereby further expanding the application scope of the present invention.

[0484] Examples 27-28

[0485] The polymerization and preparation of the button sheets were carried out in the same manner as in Example 1, except that: for the polymerization raw materials, the raw materials with the purity and polymerization inhibitor content shown in Table 8 were weighed according to the mass percentage (equivalent to pure feed).

[0486] The raw materials used in Examples 27 and 28 were obtained by further purifying the monomers used in Example 1 (the purity and inhibitor content of the specific materials are shown in Table 1). The monomers used in Example 27 were monomers that had undergone one purification of the commercially available monomers used in Example 1, and the monomers used in Example 28 were monomers that had undergone two or more purifications of the commercially available monomers used in Example 1. For solid materials at room temperature (initiators, dyes, and UV absorbers), the recrystallization method was used for purification. For liquid materials at room temperature (fluorinated monomers, silicon-containing monomers, hydrophilic monomers, and crosslinking agents), vacuum distillation was used for purification.

[0487] The prepared button clips were tested. The test results are shown in Table 8.

[0488] Table 8

[0489]

[0490] The test data from Examples 1, 27, and 28 in the table above show that increasing the purity of the monomer and reducing the content of the monomer inhibitor can significantly reduce the residue of unknown impurities. Furthermore, this effect on reducing unknown impurities shows a clear increasing trend as the inhibitor content gradually decreases. Examples 27 and 28 had the same monomer purity but different inhibitor contents. In Example 28, the total inhibitor content for each monomer was controlled below 50 ppm, significantly lower than in Example 27. As a result, the total residue of unknown impurities could be controlled below 0.3%. It was also found that increasing the purity of the polymerizable monomer and reducing the inhibitor content can also reduce the amount of known monomer residue, although this reduction is not very significant. This indicates that the presence of impurities in the monomer has a certain impact on the polymerization process of the copolymer.

[0491] Examples 29-33

[0492] The polymerization and preparation of the button sheets were carried out in the same manner as in Example 1, except that: for the polymerization raw materials, according to the formulation composition shown in Table 10, the corresponding raw materials with the purity and polymerization inhibitor content shown in Table 9 were weighed according to the mass percentage (equivalent to pure feed).

[0493] The prepared button clips were tested. The test results are shown in Table 10.

[0494] Table 9

[0495]

[0496] Table 10

[0497]

[0498] Compared to Examples 4, 9, 14, 21, and 24, which used raw materials with lower purity and higher inhibitor content, the performance parameters of the copolymerized materials obtained from Examples 29-33, which used raw materials with higher purity and lower inhibitor content, showed no significant differences in hardness, oxygen permeability, contact angle, and water absorption. However, the total amount of unknown impurities remaining in the prepared copolymers showed a significant change, with an average decrease of 2%, consistent with the technical effect demonstrated in Example 28. Simultaneously, compared to Examples 4, 9, 14, 21, and 24, the amount of known monomers remaining in the copolymers prepared in Examples 29-33 was also slightly reduced. This further illustrates that controlling the purity of monomers and the content of inhibitors can significantly improve the amount of unknown impurities remaining in the copolymer and reduce the amount of known monomers remaining, thereby significantly reducing the total amount of residual monomers. Example 33 is an ultra-high oxygen permeability material; after solving the chemical residue problem, its true DK value can reach 187, and its hydrophilicity and processability are not reduced.

[0499] Examples 34-37

[0500] The polymerization and buttonhole preparation were carried out in the same manner as in Example 32, except that, for the polymerization raw materials, in Examples 34-37, 0.005% RB246, 0.005% RP247, 0.01% RY8739, 0.005% RB246 and 0.007% RY8739 were used instead of 0.01% Green 6# in Example 32, thereby preparing ice blue, ice purple, bright yellow and ice green RGP materials respectively.

[0501] The prepared RGP material was tested. The test results are shown in Table 11 below.

[0502] Table 11

[0503]

[0504] In clinical applications, RGP (Rubber Gel Permeable) materials often incorporate colorants such as masterbatches to enhance product identification. Especially in recent years, with the increasing popularity of orthokeratology lenses, personalized fitting and custom-made RGP products are becoming more common. Because the fitting parameters and processing data for the left and right eyes are not entirely consistent, clinical practice often relies on the color of the product to distinguish between the left and right lenses. Therefore, RGP materials are manufactured in different colors to increase identification and address the issue of color differentiation.

[0505] There are two methods for adding dyes: direct dyes and reactive dyes. Direct dyes color the carrier through physical blending, offering a simple dyeing method, a complete color spectrum, and low cost. However, their wash fastness and aging fastness are relatively poor. Reactive dyes, also known as reactive colorants, contain one or more active groups in their molecular structure. Under appropriate conditions, they can chemically react with the carrier to form covalent bonds. Reactive dyes are strong, but the coloring method is complex, the range of colors available is limited, and the cost is high.

[0506] Currently, most RGP materials used in Class III medical devices marketed in China employ physical blending of direct staining agents; a typical example is Boston XO. ® The blue colorant used in the material is D&C Green 6#, and the green colorant is a combination of D&C Green 6# and Yellow 18#. Paragon HDS 100 is also used. ® The same dyes used are blends of D&C Green 6# and Yellow 18#. Although the amount of direct dye added in this type of blend is very small, generally less than 100 ppm (0.01%), because these dyes interact with the copolymer materials through physical action, prolonged contact with the cornea can cause the lens to fade due to material aging, tear erosion, and other interactions. Furthermore, during wear, the lens may be absorbed by the ocular surface through tear exchange or passive diffusion, posing biosafety concerns.

[0507] Examples 34-37 demonstrate how using dyes with polymerizable reactive groups (reactive dyes) instead of direct blending dyes improves the biocompatibility of RGP materials in one step. Reactive dyes contain vinyl or (methyl)vinyl end-capsulation and can participate in free radical copolymerization reactions. Unlike existing physical blending dyes used in RGP materials, reactive dyes are incorporated into the copolymer of the material through covalent chemical reactions. Therefore, reactive dyes offer higher dyeing efficiency and stability, fundamentally avoiding the biocompatibility risks caused by dye fading or the interaction of dissolved dye with the cornea during the use or wearing of RGP materials.

[0508] Although reactive dyes can participate in the polymerization reaction, their addition amount is very low (0.005%-0.012%), theoretically having little impact on the performance of polymer segments. This is verified by comparing the physicochemical properties of Examples 34-37 with those of Example 32. RB246 and RP247 are dimethicone-terminated reactive dyes, which also act as partial crosslinking agents during copolymerization, making the reaction between segments more stable and further reducing the content of oligomers in unknown impurities. However, due to their relatively low addition amount, this reduction trend is not very significant. In Examples 34, 35, and 37, the total amount of unknown impurities in the formulations using RB246 and RP247 dyes can be controlled below 0.3%, slightly lower than the 0.4% in Example 36. The total amount of residual monomers in Examples 34-37 is less than 1%, showing good biocompatibility and further demonstrating the feasibility and effectiveness of the monomer residue control strategy of this invention. In addition, compared with Example 32, Examples 34-37 can slightly improve at least one of the oxygen permeability coefficient and contact angle. Moreover, the visible spectral transmittance of the dyed material is above 93%, which is higher than the minimum spectral transmittance of 89% required for the visible light region of contact lenses in GB11417.3. This series of materials shows good light transmittance.

[0509] Although specific embodiments of the invention have been described in detail, those skilled in the art will understand that various modifications and substitutions can be made to those details based on all the teachings disclosed, and all such changes are within the scope of protection of the invention. The full scope of the invention is given by the appended claims and any equivalents thereof.

Claims

1. A method for reducing the residual monomer content in a polymer composition, the method comprising: A second composition capable of free radical polymerization is provided by replacing a portion of the first olefinically unsaturated monomer component in a first composition capable of free radical polymerization with a second olefinically unsaturated monomer component based on a second olefinically unsaturated monomer as follows: wherein the olefinic bond of the second olefinically unsaturated monomer is derived from an acryloyloxy group, and wherein the second olefinically unsaturated monomer comprises a second hydrophobic silicon-containing monomer and optionally comprises a second hydrophobic fluorinated monomer, a second hydrophilic monomer, or a combination thereof. Then, the second composition capable of free radical polymerization is subjected to free radical polymerization; The first composition capable of free radical polymerization comprises a mixture of the following: The first ene unsaturated monomer component is based on the first ene unsaturated monomer, wherein the olefin bond in the first ene unsaturated monomer originates from the methacryloyloxy group. Free radical initiators Optionally, ultraviolet absorbers, and Optional, dye; The first olefinic unsaturated monomers include a first hydrophobic fluorinated monomer containing a methacryloyl group, a first hydrophobic silicon-containing monomer containing a methacryloyl group, and a first hydrophilic monomer containing a methacryloyl group. The mass ratio of the second hydrophobic silicon-containing monomer to (the first hydrophobic silicon-containing monomer + the second hydrophobic silicon-containing monomer) is 25-60% by mass, and When a second hydrophobic fluorinated monomer is present, the mass ratio of the second hydrophobic fluorinated monomer to (the first hydrophobic fluorinated monomer + the second hydrophobic fluorinated monomer) is 25-60% by mass. When a second hydrophilic monomer is present, the mass ratio of the second hydrophilic monomer to (the first hydrophilic monomer + the second hydrophilic monomer) is 35-70 by mass.

2. The method according to claim 1, wherein the first olefinically unsaturated monomer and the second olefinically unsaturated monomer have the same alkenyl functionality.

3. The method according to claim 1, wherein the first olefinically unsaturated monomer is a monoalkenyl-functional olefinically unsaturated monomer, and the second olefinically unsaturated monomer is a monoalkenyl-functional olefinically unsaturated monomer.

4. The method according to claim 1, wherein the difference between the first hydrophilic monomer and the second hydrophilic monomer is only that the methacryloyloxy group in the first hydrophilic monomer is replaced by the acryloxy group in the second hydrophilic monomer.

5. The method according to claim 1, wherein the first olefinic unsaturated monomer is a first hydrophobic fluorinated monomer containing a methacryloyl group, a first hydrophobic silicon-containing monomer containing a methacryloyl group, and a first hydrophilic monomer containing a methacryloyl group.

6. The method according to any one of claims 1-5, wherein the first hydrophobic fluorinated monomer containing a methacryloyl group is a hydrophobic fluorinated alkyl methacrylate monomer.

7. The method according to any one of claims 1-5, wherein the first hydrophobic silicon-containing monomer containing a methacryloyl group is a silicon-containing hydrophobic methacrylate monomer.

8. The method according to claim 1, wherein the second olefinic unsaturated monomer is: a second hydrophobic silicon-containing monomer; and optionally, a second hydrophobic fluorine-containing monomer, a second hydrophilic monomer, or a combination thereof.

9. The method according to claim 1 or 8, wherein the second hydrophobic fluorinated monomer is a hydrophobic fluorinated alkyl acrylate monomer.

10. The method according to claim 1 or 8, wherein the second hydrophobic silicon-containing monomer is a silicon-containing hydrophobic acrylate monomer.

11. The method according to claim 1, wherein the difference between the first hydrophobic fluorinated monomer and the second hydrophobic fluorinated monomer is only that the methacryloyloxy group in the first hydrophobic fluorinated monomer is replaced with the acryloyloxy group in the second hydrophobic fluorinated monomer.

12. The method according to claim 1, wherein the difference between the first hydrophobic silicon-containing monomer and the second hydrophobic silicon-containing monomer is only that the methacryloyloxy group in the first hydrophobic silicon-containing monomer is replaced with the acryloyloxy group in the second hydrophobic silicon-containing monomer.

13. The method according to claim 1, wherein the first olefinically unsaturated monomer comprises a first hydrophobic fluorinated monomer containing a methacryloyl group that is monoalkenyl-functional, a first hydrophobic silicon-containing monomer containing a methacryloyl group that is monoalkenyl-functional, a first hydrophilic monomer containing a methacryloyl group that is monoalkenyl-functional, or any combination thereof, and the second olefinically unsaturated monomer comprises a second hydrophobic silicon-containing monomer that is monoalkenyl-functional and optionally comprises a second hydrophobic fluorinated monomer that is monoalkenyl-functional, a second hydrophilic monomer that is monoalkenyl-functional, or a combination thereof.

14. The method according to claim 13, wherein the first olefinically unsaturated monomer comprises a first hydrophobic fluorinated monomer containing a methacryl group that is monoalkenyl functional, a first hydrophobic silicon-containing monomer containing a methacryl group that is monoalkenyl functional, and a first hydrophilic monomer containing a methacryl group that is monoalkenyl functional.

15. The method according to claim 13, wherein the first olefinically unsaturated monomer is a first hydrophobic fluorinated monomer containing a methacryl group that is monoalkenyl functional, a first hydrophobic silicon-containing monomer containing a methacryl group that is monoalkenyl functional, or a first hydrophilic monomer containing a methacryl group that is monoalkenyl functional.

16. The method according to any one of claims 13-15, wherein the first hydrophobic fluorinated monomer containing a methacryl group and having a monoalkenyl functional group is a hydrophobic fluorinated alkyl methacrylate monomer.

17. The method according to any one of claims 13-15, wherein the first hydrophobic silicon-containing monomer containing a methacryl group and having a monoalkenyl functionality is a silicon-containing hydrophobic methacrylate monomer.

18. The method according to claim 13, wherein the second olefinically unsaturated monomer is: a monoalkenyl-functional second hydrophobic silicon-containing monomer; and optionally, a monoalkenyl-functional second hydrophobic fluorinated monomer, a monoalkenyl-functional second hydrophilic monomer, or a combination thereof.

19. The method according to claim 13 or 18, wherein the monoalkenyl-functional second hydrophobic fluorinated monomer is a hydrophobic fluorinated alkyl acrylate monomer.

20. The method according to claim 13 or 18, wherein the monoalkenyl-functional second hydrophobic silicon-containing monomer is a silicon-containing hydrophobic acrylate monomer.

21. The method according to claim 13, wherein the difference between the first hydrophobic fluorinated monomer containing a methacryloyl group and the second hydrophobic fluorinated monomer containing a methacryloyl group is only that the methacryloyloxy group in the first hydrophobic fluorinated monomer containing a methacryloyl group is replaced with the acryloyloxy group in the second hydrophobic fluorinated monomer containing a methacryloyl group.

22. The method according to claim 13, wherein the difference between the first hydrophobic silicon-containing monomer containing a methacryl group and the second hydrophobic silicon-containing monomer containing a methacryl group is only that the methacryloxy group in the first hydrophobic silicon-containing monomer containing a methacryl group is replaced with the acryloyloxy group in the second hydrophobic silicon-containing monomer containing a methacryl group.

23. The method according to claim 13, wherein the difference between the monoalkenyl-functional first hydrophilic monomer containing a methacryloyl group and the monoalkenyl-functional second hydrophilic monomer is only that the methacryloyloxy group in the monoalkenyl-functional first hydrophilic monomer containing a methacryloyl group is replaced with the acryloyloxy group in the monoalkenyl-functional second hydrophilic monomer.

24. The method of claim 1, wherein the second composition capable of free radical polymerization comprises: (1) Monoalkenyl-functional hydrophobic fluorinated monomer components, including: (1-1) Based on the first hydrophobic fluorinated monomer component of fluorinated alkyl methacrylate as the first hydrophobic fluorinated monomer; and (1-2) Optional second hydrophobic fluorinated monomer component based on fluorinated alkyl acrylate as a second hydrophobic fluorinated monomer; (2) Monoalkenyl-functionalized hydrophobic silicon-containing monomer components, including: (2-1) Based on the first hydrophobic silicon-containing methacrylate as the first hydrophobic silicon-containing monomer component; and (2-2) Based on the second hydrophobic silicon-containing monomer component of silicon-containing acrylate as the second hydrophobic silicon-containing monomer; (3) Monoalkenyl-functional hydrophilic monomer components, including: (3-1) A first hydrophilic monomer component based on a first hydrophilic monomer containing a methacryloyl group; and / or (3-2) A second hydrophilic monomer component based on a second hydrophilic monomer containing an acryloxy group; (4) Optionally, a crosslinking agent component based on a diene-functional or higher crosslinking agent; (5) Free radical initiators; (6) Optionally, a UV absorber; When a first hydrophilic monomer is present, one, two, or three of the following may be present: a second hydrophobic fluorinated monomer, a second hydrophobic silicon-containing monomer, and a second hydrophilic monomer.

25. The method according to claim 24, wherein the monoalkenyl-functionalized hydrophobic fluorinated monomer component comprises the following: (1-1) Based on the first hydrophobic fluorinated monomer component of the fluorinated alkyl methacrylate as the first hydrophobic fluorinated monomer; and (1-2) Optional second hydrophobic fluorinated monomer component based on fluorinated alkyl acrylate as a second hydrophobic fluorinated monomer.

26. The method according to claim 24 or 25, wherein the first hydrophobic fluorinated monomer is a C1-C10 fluorinated alkyl methacrylate.

27. The method according to claim 24 or 25, wherein the first hydrophobic fluorinated monomer is a C1-C6 fluorinated alkyl methacrylate.

28. The method according to claim 24 or 25, wherein the first hydrophobic fluorinated monomer is a C2-C5 fluorinated alkyl methacrylate.

29. The method according to claim 24 or 25, wherein the first hydrophobic fluorinated monomer is a C2-C3 fluorinated alkyl methacrylate.

30. The method according to claim 24 or 25, wherein the first hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, and 2,2,3,3,3-pentafluoropropyl methacrylate.

31. The method according to claim 24 or 25, wherein the first hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl methacrylate and hexafluoroisopropyl methacrylate.

32. The method according to claim 24 or 25, wherein the fluorinated alkyl group in the second hydrophobic fluorinated monomer is the same as or different from the fluorinated alkyl group in the first hydrophobic fluorinated monomer.

33. The method according to claim 24 or 25, wherein the fluorinated alkyl group in the second hydrophobic fluorinated monomer is the same as the fluorinated alkyl group in the first hydrophobic fluorinated monomer.

34. The method according to claim 24 or 25, wherein the second hydrophobic fluorinated monomer is a C1-C10 fluorinated alkyl ester of acrylic acid.

35. The method according to claim 24 or 25, wherein the second hydrophobic fluorinated monomer is a C1-C6 fluorinated alkyl ester of acrylic acid.

36. The method according to claim 24 or 25, wherein the second hydrophobic fluorinated monomer is a C2-C5 fluorinated alkyl ester of acrylic acid.

37. The method according to claim 24 or 25, wherein the second hydrophobic fluorinated monomer is a C2-C3 fluorinated alkyl ester of acrylic acid.

38. The method according to claim 24 or 25, wherein the second hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl acrylate, hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, and 2,2,3,3,3-pentafluoropropyl acrylate.

39. The method according to claim 24 or 25, wherein the second hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl acrylate and hexafluoroisopropyl acrylate.

40. The method according to claim 24 or 25, wherein the first hydrophobic fluorinated monomer is selected from one or more of hexafluoroisopropyl methacrylate and trifluoroethyl methacrylate, and the second hydrophobic fluorinated monomer is selected from one or more of hexafluoroisopropyl acrylate and trifluoroethyl acrylate.

41. The method according to claim 24 or 25, wherein the first hydrophobic fluorinated monomer is hexafluoroisopropyl methacrylate and the second hydrophobic fluorinated monomer is hexafluoroisopropyl acrylate, or the first hydrophobic fluorinated monomer is trifluoroethyl methacrylate and the second hydrophobic fluorinated monomer is trifluoroethyl acrylate.

42. The method according to claim 24, wherein the monoalkenyl-functionalized hydrophobic silicon-containing monomer component comprises the following: (2-1) Based on the first hydrophobic silicon-containing methacrylate as the first hydrophobic silicon-containing monomer component, and (2-2) Based on silicon-containing acrylates as the second hydrophobic silicon-containing monomer.

43. The method according to claim 24 or 42, wherein the first hydrophobic silicon-containing monomer is a silicon-containing methacrylate of the following formula: CH2=C(CH3)-C(O)-O-L1-Si(R1)m(OR2) 3-m L1 is a C1-C10 divalent alkylene group that optionally includes one or more groups selected from ether-O-atom groups and -OH groups; R1 is the same as or different from each other and is independently C1-C6 alkyl; R2 is the same as or different from each other and is independently C1-C6 alkyl or -Si(R3)3, wherein R3 is the same as or different from each other and is independently C1-C6 alkyl; and m is 0, 1, 2, or 3.

44. The method of claim 43, wherein L1 is a C3-C6 dialkylene group that optionally includes one or more groups selected from ether-O-atom groups and -OH groups.

45. The method of claim 43, wherein each of R1 is independently methyl.

46. ​​The method of claim 43, wherein each of R2 is independently methyl or -Si(R3)3.

47. The method of claim 43, wherein each of R3 is independently methyl.

48. The method of claim 43, wherein m is 0 or 1.

49. The method according to claim 24, wherein the first hydrophobic silicon-containing monomer is selected from one or more of methacryloyloxypropyltris(trimethylsiloxane)silane and (3-methacryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane.

50. The method according to claim 43, wherein the second hydrophobic silicon-containing monomer is CH2=CH-C(O)-O-L2-Si(R4). n (OR5) 3-n L2 may be the same as or different from L1 and is a C1-C10 divalent alkylene group that optionally includes one or more groups of ether-O-atom group or -OH group; R4 may be the same as or different from each other and the same as or different from R1 and each independently is a C1-C6 alkyl; R5 may be the same as or different from each other and the same as or different from R2 and each independently is a C1-C6 alkyl or -Si(R6)3, wherein R6 may be the same as or different from each other and the same as or different from R3 and each independently is a C1-C6 alkyl; n may be the same as or different from m and is 0, 1, 2 or 3.

51. The method of claim 50, wherein L2 is a C3-C6 dialkylene group optionally comprising one or more groups selected from ether-O-atom groups and -OH groups.

52. The method of claim 50, wherein each of R4 is independently methyl.

53. The method of claim 50, wherein each of R5 is independently methyl or -Si(R6)3.

54. The method of claim 50, wherein each of R6 is independently methyl.

55. The method of claim 50, wherein n is 0 or 1.

56. The method of claim 50, wherein -Si(R4) n (OR5) 3-n Partially related to -Si(R1)m(OR2) 3-m Some parts are the same or different.

57. The method of claim 50, wherein -L2-Si(R4) n (OR5) 3-n Partially related to -L1-Si(R1)m(OR2) 3-m Some parts are the same or different.

58. The method of claim 24, wherein the second hydrophobic silicon-containing monomer is selected from one or more of acryloyloxypropyltris(trimethylsiloxane)silane and (3-acryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane.

59. The method of claim 24, wherein the first hydrophobic silicon-containing monomer is selected from methacryloyloxypropyltris(trimethylsiloxane), and the second hydrophobic silicon-containing monomer is selected from acryloyloxypropyltris(trimethylsiloxane).

60. The method according to claim 24, wherein the monoalkenyl-functional hydrophilic monomer component comprises: (3-1) A first hydrophilic monomer component based on a first hydrophilic monomer containing a methacryloyl group; and / or (3-2) A second hydrophilic monomer component based on a second hydrophilic monomer containing an acryloxy group.

61. The method according to claim 24 or 60, wherein the first hydrophilic monomer is selected from one or more of methacrylic acid, hydroxyethyl methacrylate, methacrylamide, and N,N-dimethylmethacrylamide.

62. The method according to claim 24 or 60, wherein the second hydrophilic monomer is selected from one or more of acrylic acid and hydroxyethyl acrylate.

63. The method according to claim 24 or 60, wherein the first hydrophilic monomer is selected from methacrylic acid, and the second hydrophilic monomer is selected from acrylic acid.

64. The method according to claim 24 or 60, wherein the crosslinking agent with a diene or higher functional group is selected from: alkyl diol dimethacrylate; siloxane-containing oligomers; or any combination thereof.

65. The method of claim 64, wherein the alkyl diol dimethacrylate is selected from neopentyl glycol dimethacrylate.

66. The method of claim 64, wherein the siloxane-containing oligomer is selected from 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane.

67. The method according to claim 24, wherein the crosslinking agent with a diene function or above is a mixture of neopentyl glycol dimethacrylate and 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane.

68. The method according to claim 67, wherein neopentyl glycol dimethacrylate and 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane are present in a mass ratio of 10:90 to 90:

10.

69. The method according to claim 67, wherein neopentyl glycol dimethacrylate and 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane are present in a mass ratio of 30:70 to 70:

30.

70. The method according to claim 67, wherein neopentyl glycol dimethacrylate and 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane are present in a mass ratio of 50:50 to 60:

40.

71. The method according to claim 24, wherein the free radical initiator is azobisisobutyronitrile or azobisisoheptanenitrile.

72. The method according to claim 24, wherein the ultraviolet absorber is 2-hydroxy-4-(methacryloyloxy)benzophenone.

73. The method according to claim 24, wherein, The second composition capable of free radical polymerization comprises, based on the total mass of the second composition capable of free radical polymerization: (1) 30-60% by mass of monoalkenyl-functional hydrophobic fluorinated monomer components; (2) 20-45% by mass of monoalkenyl-functional hydrophobic silicon-containing monomer components; (3) 3-20% by mass of monoalkenyl-functional hydrophilic monomer components; (4) Optionally, 1-20% by mass of a crosslinking agent component based on a diene-functionalized or higher crosslinking agent; (5) 0.1-2.0% by mass of a free radical initiator; and (6) Optionally, 0.1-5.0% by mass of a UV absorber.

74. The method according to claim 73, wherein, The second composition capable of free radical polymerization comprises, based on the total mass of the second composition capable of free radical polymerization, 40-50% by mass of a monoalkenyl-functional hydrophobic fluorinated monomer component.

75. The method according to claim 73, wherein, The second composition capable of free radical polymerization comprises, based on the total mass of the second composition capable of free radical polymerization, 30-40% by mass of a monoalkenyl-functional hydrophobic silicon-containing monomer component.

76. The method according to claim 73, wherein, The second composition capable of free radical polymerization comprises, based on the total mass of the second composition capable of free radical polymerization, 5-10% by mass of a monoalkenyl-functional hydrophilic monomer component.

77. The method according to claim 73, wherein, The second composition capable of free radical polymerization comprises, based on the total mass of the second composition capable of free radical polymerization, 5-15% by mass of a crosslinking agent component based on a diene-functionalized or higher crosslinking agent.

78. The method according to claim 73, wherein, The second composition capable of free radical polymerization comprises, based on the total mass of the second composition capable of free radical polymerization, 0.5-1.0% by mass of a free radical initiator.

79. The method according to claim 73, wherein, The second composition capable of free radical polymerization comprises, based on the total mass of the second composition capable of free radical polymerization, 0.2-1.0% by mass of a UV absorber.

80. The method according to claim 73, wherein, The second composition capable of free radical polymerization comprises, based on the total mass of the second composition capable of free radical polymerization, 0.4-0.6% by mass of a UV absorber.

81. The method according to claim 1, wherein, A second hydrophobic fluorinated monomer is present in the second composition that can undergo free radical polymerization.

82. The method according to claim 1, wherein, The second composition capable of free radical polymerization contains a second hydrophilic monomer and optionally a first hydrophilic monomer.

83. The method according to claim 1, wherein the second composition capable of free radical polymerization contains a second hydrophobic fluorinated monomer, a second hydrophobic silicon-containing monomer, a first hydrophilic monomer, and a second hydrophilic monomer.

84. The method of claim 1, wherein the method comprises performing a purification step prior to polymerization and before providing the second composition capable of free radical polymerization: Purify the first hydrophobic fluorinated monomer component to increase the content of the first hydrophobic fluorinated monomer and / or decrease the content of the polymerization inhibitor; and / or Purify the second hydrophobic fluorinated monomer component to increase the content of the second hydrophobic fluorinated monomer and / or decrease the content of the polymerization inhibitor; and / or Purify the first hydrophobic silicon-containing monomer component to increase the content of the first hydrophobic silicon-containing monomer and / or decrease the content of the polymerization inhibitor; and / or Purify the second hydrophobic silicon-containing monomer component to increase the content of the second hydrophobic silicon-containing monomer and / or decrease the content of the polymerization inhibitor; and / or Purify the first hydrophilic monomer component to increase the content of the first hydrophilic monomer and / or decrease the content of the polymerization inhibitor; and / or Purify the second hydrophilic monomer component to increase the content of the second hydrophilic monomer and / or decrease the content of the polymerization inhibitor; and / or The crosslinking agent component based on diene-functionalized or higher crosslinking agents is purified to increase the crosslinking agent content and / or decrease the polymerization inhibitor content.

85. The method of claim 1, wherein the method comprises performing a purification step prior to polymerization, before providing the second composition capable of free radical polymerization: The first hydrophobic fluorinated monomer component is purified to increase the content of the first hydrophobic fluorinated monomer and / or decrease the content of the polymerization inhibitor, so that the content of the first hydrophobic fluorinated monomer is 98% by mass or more and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or The second hydrophobic fluorinated monomer component is purified to increase the content of the second hydrophobic fluorinated monomer and / or decrease the content of the polymerization inhibitor, so that the content of the second hydrophobic fluorinated monomer is 98% by mass or more and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or The first hydrophobic silicon-containing monomer component is purified to increase the content of the first hydrophobic silicon-containing monomer and / or decrease the content of the polymerization inhibitor, so that the content of the first hydrophobic silicon-containing monomer is 98% by mass or more and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or The second hydrophobic silicon-containing monomer component is purified to increase the content of the second hydrophobic silicon-containing monomer and / or decrease the content of the polymerization inhibitor, so that the content of the second hydrophobic silicon-containing monomer is 98% by mass or more and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or The first hydrophilic monomer component is purified to increase the content of the first hydrophilic monomer and / or decrease the content of the polymerization inhibitor, such that the content of the first hydrophilic monomer is 98% by mass or more and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or The second hydrophilic monomer component is purified to increase the content of the second hydrophilic monomer and / or decrease the content of the polymerization inhibitor, so that the content of the second hydrophilic monomer is 98% by mass or more and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or The crosslinking agent component based on diene-functionalized or higher crosslinking agents is purified to increase the crosslinking agent content and / or decrease the polymerization inhibitor content, so that the crosslinking agent content is 98% by mass or more and / or the polymerization inhibitor content is 50 ppm by mass or less.

86. The method of claim 1, wherein the method comprises performing a purification step prior to polymerization and before providing the second composition capable of free radical polymerization: The first hydrophobic fluorinated monomer component is purified to increase the content of the first hydrophobic fluorinated monomer and / or decrease the content of the polymerization inhibitor, so that the content of the first hydrophobic fluorinated monomer is 99% by mass or more and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or The second hydrophobic fluorinated monomer component is purified to increase the content of the second hydrophobic fluorinated monomer and / or decrease the content of the polymerization inhibitor, so that the content of the second hydrophobic fluorinated monomer is 99% by mass or more and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or The first hydrophobic silicon-containing monomer component is purified to increase the content of the first hydrophobic silicon-containing monomer and / or decrease the content of the polymerization inhibitor, so that the content of the first hydrophobic silicon-containing monomer is 99% by mass or more and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or The second hydrophobic silicon-containing monomer component is purified to increase the content of the second hydrophobic silicon-containing monomer and / or decrease the content of the polymerization inhibitor, so that the content of the second hydrophobic silicon-containing monomer is 99% by mass or more and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or The first hydrophilic monomer component is purified to increase the content of the first hydrophilic monomer and / or decrease the content of the polymerization inhibitor, such that the content of the first hydrophilic monomer is 99% by mass or more and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or The second hydrophilic monomer component is purified to increase the content of the second hydrophilic monomer and / or decrease the content of the polymerization inhibitor, so that the content of the second hydrophilic monomer is 99% by mass or more and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or The crosslinking agent component based on diene-functionalized or higher crosslinking agents is purified to increase the crosslinking agent content and / or decrease the polymerization inhibitor content, so that the crosslinking agent content is 99% by mass or more and / or the polymerization inhibitor content is 50 ppm by mass or less.

87. The method of claim 1, wherein the first composition capable of free radical polymerization comprises a non-reactive dye, and the method further comprises partially or completely replacing the non-reactive dye in the first composition capable of free radical polymerization with a reactive dye containing an alkenyl group.

88. The method of claim 87, wherein the first composition capable of free radical polymerization comprises 0.001-0.5% by mass of a non-reactive dye.

89. The method of claim 87, wherein the first composition capable of free radical polymerization comprises 0.005-0.01% by mass of a non-reactive dye.

90. The method of claim 87, wherein the reactive staining agent is a reactive staining agent containing a methacryloyl group.

91. The method according to claim 87, wherein the reactive dye is selected from one or more of 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone, 1,4-bis((2-hydroxyethyl)amino)-9,10-anthradinone bis(2-propeneOIC) ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenylethyl)methacrylamide.

92. The method according to claim 1, wherein the polymer is a medical polymer.

93. The method of claim 92, wherein the polymer is a polymer used for manufacturing corneal contact lenses.

94. The method of claim 92, wherein the polymer is a polymer used to manufacture rigid gas permeable contact lenses.

95. The method according to claim 1, wherein the mass ratio of the second hydrophobic silicon-containing monomer to (the first hydrophobic silicon-containing monomer + the second hydrophobic silicon-containing monomer) is 30-50 by mass.

96. The method according to claim 1, wherein when a second hydrophobic fluorinated monomer is present, the mass ratio of the second hydrophobic fluorinated monomer to (the first hydrophobic fluorinated monomer + the second hydrophobic fluorinated monomer) is 30-50 by mass.

97. The method according to claim 1, wherein when a second hydrophilic monomer is present, the mass ratio of the second hydrophilic monomer to (the first hydrophilic monomer + the second hydrophilic monomer) is 40-60 by mass.

98. A composition capable of free radical polymerization, comprising: (1) Monoalkenyl-functional hydrophobic fluorinated monomer components, including: (1-1) Based on the first hydrophobic fluorinated monomer component of fluorinated alkyl methacrylate as the first hydrophobic fluorinated monomer; and (1-2) Optional second hydrophobic fluorinated monomer component based on fluorinated alkyl acrylate as a second hydrophobic fluorinated monomer; (2) Monoalkenyl-functionalized hydrophobic silicon-containing monomer components, including: (2-1) Based on the first hydrophobic silicon-containing methacrylate as the first hydrophobic silicon-containing monomer component; and (2-2) The second hydrophobic silicon-containing monomer component is based on the silane of silicon-containing acrylate as the second hydrophobic silicon-containing monomer. (3) Monoalkenyl-functional hydrophilic monomer components, including: (3-1) A first hydrophilic monomer component based on a first hydrophilic monomer containing a methacryloyl group; and / or (3-2) A second hydrophilic monomer component based on a second hydrophilic monomer containing an acryloxy group; (4) Optionally, a crosslinking agent component based on a diene-functional or higher crosslinking agent; (5) Free radical initiators; and (6) Optionally, a UV absorber; When a first hydrophilic monomer is present, one, two, or three of the following are present: a second hydrophobic fluorinated monomer, a second hydrophobic silicon-containing monomer, and a second hydrophilic monomer; and The mass ratio of the second hydrophobic silicon-containing monomer to (the first hydrophobic silicon-containing monomer + the second hydrophobic silicon-containing monomer) is 25-60% by mass, and When a second hydrophobic fluorinated monomer is present, the mass ratio of the second hydrophobic fluorinated monomer to (the first hydrophobic fluorinated monomer + the second hydrophobic fluorinated monomer) is 25-60% by mass. When a second hydrophilic monomer is present, the mass ratio of the second hydrophilic monomer to (the first hydrophilic monomer + the second hydrophilic monomer) is 35-70 by mass.

99. The composition according to claim 98, wherein the monoalkenyl-functionalized hydrophobic fluorinated monomer component comprises the following: (1-1) Based on the first hydrophobic fluorinated monomer component of fluorinated alkyl methacrylate as the first hydrophobic fluorinated monomer; and (1-2) Optional second hydrophobic fluorinated monomer component based on fluorinated alkyl acrylate as a second hydrophobic fluorinated monomer.

100. The composition according to claim 98 or 99, wherein the first hydrophobic fluorinated monomer is a C1-C10 fluorinated alkyl methacrylate.

101. The composition according to claim 98 or 99, wherein the first hydrophobic fluorinated monomer is a C1-C6 fluorinated alkyl methacrylate.

102. The composition according to claim 98 or 99, wherein the first hydrophobic fluorinated monomer is a C2-C5 fluorinated alkyl methacrylate.

103. The composition according to claim 98 or 99, wherein the first hydrophobic fluorinated monomer is a C2-C3 fluorinated alkyl methacrylate.

104. The composition according to claim 98 or 99, wherein the first hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, and 2,2,3,3,3-pentafluoropropyl methacrylate.

105. The composition according to claim 98 or 99, wherein the first hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl methacrylate and hexafluoroisopropyl methacrylate.

106. The composition according to claim 98 or 99, wherein the fluorinated alkyl group in the second hydrophobic fluorinated monomer is the same as or different from the fluorinated alkyl group in the first hydrophobic fluorinated monomer.

107. The composition according to claim 98 or 99, wherein the fluorinated alkyl group in the second hydrophobic fluorinated monomer is the same as the fluorinated alkyl group in the first hydrophobic fluorinated monomer.

108. The composition according to claim 98 or 99, wherein the second hydrophobic fluorinated monomer is a C1-C10 fluorinated alkyl ester of acrylic acid.

109. The composition according to claim 98 or 99, wherein the second hydrophobic fluorinated monomer is a C1-C6 fluorinated alkyl ester of acrylic acid.

110. The composition according to claim 98 or 99, wherein the second hydrophobic fluorinated monomer is a C2-C5 fluorinated alkyl ester of acrylic acid.

111. The composition according to claim 98 or 99, wherein the second hydrophobic fluorinated monomer is a C2-C3 fluorinated alkyl ester of acrylic acid.

112. The composition according to claim 98 or 99, wherein the second hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl acrylate, hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, and 2,2,3,3,3-pentafluoropropyl acrylate.

113. The composition according to claim 98 or 99, wherein the second hydrophobic fluorinated monomer is selected from one or more of trifluoroethyl acrylate and hexafluoroisopropyl acrylate.

114. The composition according to claim 98 or 99, wherein the first hydrophobic fluorinated monomer is selected from one or more of hexafluoroisopropyl methacrylate and trifluoroethyl methacrylate, and the second hydrophobic fluorinated monomer is selected from one or more of hexafluoroisopropyl acrylate and trifluoroethyl acrylate.

115. The composition according to claim 98 or 99, wherein the first hydrophobic fluorinated monomer is hexafluoroisopropyl methacrylate and the second hydrophobic fluorinated monomer is hexafluoroisopropyl acrylate, or the first hydrophobic fluorinated monomer is trifluoroethyl methacrylate and the second hydrophobic fluorinated monomer is trifluoroethyl acrylate.

116. The composition according to claim 98, wherein the monoalkenyl-functional hydrophobic silicon-containing monomer component comprises the following: (2-1) Based on the first hydrophobic silicon-containing methacrylate as the first hydrophobic silicon-containing monomer component, and (2-2) Based on a silicon-containing acrylate or a second hydrophobic silicon-containing monomer component containing a vinylphenyl silane as a second hydrophobic silicon-containing monomer.

117. The composition according to claim 98 or 116, wherein the first hydrophobic silicon-containing monomer is a silicon-containing methacrylate of the following formula: CH2=C(CH3)-C(O)-O-L1-Si(R1)m(OR2) 3-m L1 is a C1-C10 divalent alkylene group that optionally includes one or more groups selected from ether-O-atom groups and -OH groups; R1 is the same as or different from each other and is independently C1-C6 alkyl; R2 is the same as or different from each other and is independently C1-C6 alkyl or -Si(R3)3, wherein R3 is the same as or different from each other and is independently C1-C6 alkyl; and m is 0, 1, 2, or 3.

118. The composition according to claim 117, wherein L1 is a C3-C6 dialkylene group optionally comprising one or more groups selected from ether-O-atom groups and -OH groups.

119. The composition according to claim 117, wherein each of R1 is independently methyl.

120. The composition according to claim 117, wherein each of R2 is independently methyl or -Si(R3)3.

121. The composition according to claim 117, wherein each of R3 is independently methyl.

122. The composition according to claim 117, wherein m is 0 or 1.

123. The composition according to claim 98 or 116, wherein the first hydrophobic silicon-containing monomer is selected from one or more of methacryloyloxypropyltris(trimethylsiloxane)silane and (3-methacryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane.

124. The composition according to claim 117, wherein the second hydrophobic silicon-containing monomer is CH2=CH-C(O)-O-L2-Si(R4). n (OR5) 3-n L2 may be the same as or different from L1 and is a C1-C10 divalent alkylene group that optionally includes one or more groups of ether-O-atom group or -OH group; R4 may be the same as or different from each other and the same as or different from R1 and each independently is a C1-C6 alkyl; R5 may be the same as or different from each other and the same as or different from R2 and each independently is a C1-C6 alkyl or -Si(R6)3, wherein R6 may be the same as or different from each other and the same as or different from R3 and each independently is a C1-C6 alkyl; n may be the same as or different from m and is 0, 1, 2 or 3.

125. The composition according to claim 124, wherein L2 is a C3-C6 dialkylene group optionally comprising one or more groups selected from ether-O-atom groups and -OH groups.

126. The composition according to claim 124, wherein each of R4 is independently methyl.

127. The composition according to claim 124, wherein each of R5 is independently methyl or -Si(R6)3.

128. The composition according to claim 124, wherein each of R6 is independently methyl.

129. The composition according to claim 124, wherein n is 0 or 1.

130. The composition according to claim 124, wherein -Si(R4) n (OR5) 3-n Partially related to -Si(R1)m(OR2) 3-m Some parts are the same or different.

131. The composition according to claim 124, wherein -L2-Si(R4) n (OR5) 3-n Partially related to -L1-Si(R1)m(OR2) 3-m Some parts are the same or different.

132. The composition according to claim 98, wherein the second hydrophobic silicon-containing monomer is selected from one or more of acryloyloxypropyltris(trimethylsiloxane)silane and (3-acryloyloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane.

133. The composition according to claim 98, wherein the first hydrophobic silicon-containing monomer is selected from methacryloyloxypropyltris(trimethylsiloxane)silane, and the second hydrophobic silicon-containing monomer is selected from acryloyloxypropyltris(trimethylsiloxane)silane.

134. The composition according to claim 98, wherein the monoalkenyl-functional hydrophilic monomer component comprises: (3-1) A first hydrophilic monomer component based on a first hydrophilic monomer containing a methacryloyl group; and / or (3-2) A second hydrophilic monomer component based on a second hydrophilic monomer containing an acryloxy group.

135. The composition according to claim 98 or 134, wherein the first hydrophilic monomer is selected from one or more of methacrylic acid, hydroxyethyl methacrylate, methacrylamide, and N,N-dimethylmethacrylamide.

136. The composition according to claim 98 or 134, wherein the second hydrophilic monomer differs from the first hydrophilic monomer only in that an acryloyl group is used in the second hydrophilic monomer instead of a methacryloyl group in the first hydrophilic monomer.

137. The composition according to claim 98 or 134, wherein the second hydrophilic monomer is selected from one or more of acrylic acid and hydroxyethyl acrylate.

138. The composition according to claim 98 or 134, wherein the first hydrophilic monomer is selected from methacrylic acid, and the second hydrophilic monomer is selected from acrylic acid.

139. The composition according to claim 98, wherein the crosslinking agent with a diene or higher functional group is selected from: alkyl diol dimethacrylate; siloxane-containing oligomers; or any combination thereof.

140. The composition according to claim 139, wherein the alkyl diol dimethacrylate is selected from neopentyl glycol dimethacrylate.

141. The composition according to claim 139, wherein the siloxane-containing oligomer is selected from 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane.

142. The composition according to claim 98, wherein the crosslinking agent with a diene function or above is a mixture of neopentyl glycol dimethacrylate and 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane.

143. The composition according to claim 142, wherein neopentyl glycol dimethacrylate and 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane are present in a mass ratio of 10:90 to 90:

10.

144. The composition according to claim 142, wherein neopentyl glycol dimethacrylate and 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane are present in a mass ratio of 30:70 to 70:

30.

145. The composition according to claim 142, wherein neopentyl glycol dimethacrylate and 1,3-bis(methacryloyloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane are present in a mass ratio of 50:50 to 60:

40.

146. The composition according to claim 98, wherein the free radical initiator is azobisisobutyronitrile or azobisisoheptanenitrile.

147. The composition according to claim 98, wherein the ultraviolet absorber is 2-hydroxy-4-(methacryloyloxy)benzophenone.

148. The composition according to claim 98, wherein, The composition comprises, based on the total mass of the composition: (1) 30-60% by mass of monoalkenyl-functional hydrophobic fluorinated monomer components; (2) 20-45% by mass of monoalkenyl-functional hydrophobic silicon-containing monomer components; (3) 3-20% by mass of monoalkenyl-functional hydrophilic monomer components; (4) Optionally, 1-20% by mass of a crosslinking agent component based on a diene-functionalized or higher crosslinking agent; (5) 0.1-2.0% by mass of a free radical initiator; and (6) Optionally, 0.1-5.0% by mass of a UV absorber.

149. The composition according to claim 148, wherein, The composition comprises, based on the total mass of the composition, 40-50% by mass of a monoalkenyl-functional hydrophobic fluorinated monomer component.

150. The composition according to claim 148, wherein, The composition comprises, based on the total mass of the composition, 30-40% by mass of a monoalkenyl-functional hydrophobic silicon-containing monomer component.

151. The composition according to claim 148, wherein, The composition comprises, based on the total mass of the composition, 5-10% by mass of a monoalkenyl-functional hydrophilic monomer component.

152. The composition according to claim 148, wherein, The composition comprises, based on the total mass of the composition, 5-15% by mass of a crosslinking agent component based on a diene-functionalized or higher crosslinking agent.

153. The composition according to claim 148, wherein, The composition comprises, based on the total mass of the composition, 0.5-1.0% by mass of a free radical initiator.

154. The composition according to claim 148, wherein, The composition comprises, based on the total mass of the composition, 0.2-1.0% by mass of a UV absorber.

155. The composition according to claim 148, wherein, The composition comprises, based on the total mass of the composition, 0.4-0.6% by mass of a UV absorber.

156. The composition according to claim 98, wherein a second hydrophobic fluorinated monomer is present in the composition.

157. The composition according to claim 98, wherein a second hydrophilic monomer is present in the composition and optionally a first hydrophilic monomer is present.

158. The composition according to claim 98, wherein a second hydrophobic fluorinated monomer, a second hydrophobic silicon-containing monomer, a first hydrophilic monomer, and a second hydrophilic monomer are present.

159. The composition according to claim 98, wherein The content of the first hydrophobic fluorinated monomer in the first hydrophobic fluorinated monomer component, and / or the content of the second hydrophobic fluorinated monomer in the second hydrophobic fluorinated monomer component, and / or the content of the first hydrophobic silicon-containing monomer in the first hydrophobic silicon-containing monomer component, and / or the content of the second hydrophobic silicon-containing monomer in the second hydrophobic silicon-containing monomer component, and / or the content of the first hydrophilic monomer in the first hydrophilic monomer component, and / or the content of the second hydrophilic monomer in the second hydrophilic monomer component, and / or the content of the crosslinking agent in the crosslinking agent component based on a diene-functionalized or higher crosslinking agent, each independently comprises 98% by mass or more; and / or The content of the polymerization inhibitor in each of the first hydrophobic fluorinated monomer component, and / or the second hydrophobic fluorinated monomer component, and / or the first hydrophobic silicon-containing monomer component, and / or the second hydrophobic silicon-containing monomer component, and / or the first hydrophilic monomer component, and / or the second hydrophilic monomer component, and / or the crosslinking agent component is independently less than 50 ppm by mass.

160. The composition according to claim 98, wherein The content of the first hydrophobic fluorinated monomer in the first hydrophobic fluorinated monomer component, and / or the content of the second hydrophobic fluorinated monomer in the second hydrophobic fluorinated monomer component, and / or the content of the first hydrophobic silicon-containing monomer in the first hydrophobic silicon-containing monomer component, and / or the content of the second hydrophobic silicon-containing monomer in the second hydrophobic silicon-containing monomer component, and / or the content of the first hydrophilic monomer in the first hydrophilic monomer component, and / or the content of the second hydrophilic monomer in the second hydrophilic monomer component, and / or the content of the crosslinking agent in the crosslinking agent component based on a diene-functionalized or higher crosslinking agent, each independently comprises 99% by mass or more.

161. The composition according to claim 98, wherein the composition further comprises a dyeing agent.

162. The composition according to claim 161, wherein the composition comprises 0.001-0.5% by mass of a dye.

163. The composition according to claim 161, wherein the composition comprises 0.005-0.01% by mass of a dye.

164. The composition according to claim 161, wherein the dye is selected from reactive dyes containing an alkenyl group.

165. The composition according to claim 161, wherein the reactive staining agent is a reactive staining agent containing a methacryloyl group.

166. The composition according to claim 165, wherein the reactive dye is selected from one or more of 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone, 1,4-bis((2-hydroxyethyl)amino)-9,10-anthradinone bis(2-propeneOIC) ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenylethyl)methacrylamide.

167. The composition according to claim 98, wherein the composition is a composition for preparing a medical polymer.

168. The composition of claim 167, wherein the composition is a composition for preparing a corneal contact lens.

169. The composition of claim 167, wherein the composition is a composition for preparing rigid gas permeable contact lenses.

170. The composition according to claim 98, wherein the mass ratio of the second hydrophobic silicon-containing monomer to (the first hydrophobic silicon-containing monomer + the second hydrophobic silicon-containing monomer) is 30-50 by mass.

171. The composition according to claim 98, wherein when a second hydrophobic fluorinated monomer is present, the mass ratio of the second hydrophobic fluorinated monomer to (the first hydrophobic fluorinated monomer + the second hydrophobic fluorinated monomer) is 30-50 by mass.

172. The composition according to claim 98, wherein when a second hydrophilic monomer is present, the mass ratio of the second hydrophilic monomer to (the first hydrophilic monomer + the second hydrophilic monomer) is 40-60 by mass.

173. A method for preparing a polymer, comprising: Provide a composition according to any one of claims 98-172, and subject the composition to free radical polymerization.

174. A polymer obtained by the method of claim 173.

175. The polymer of claim 174, wherein the polymer is a medical polymer.

176. The polymer of claim 174, wherein the polymer is a polymer for use in corneal contact lenses.

177. The polymer of claim 174, wherein the polymer is a polymer for use in rigid gas permeable contact lenses.

178. Use of the composition according to any one of claims 98-172 in the preparation of polymers.

179. The use according to claim 178, wherein the polymer is a medical polymer.

180. The use according to claim 179, wherein the medical polymer is a polymer for use in corneal contact lenses.

181. The use according to claim 180, wherein the corneal contact lens is a rigid gas permeable corneal contact lens.

Images