Method for reducing residual monomer content in polymer composition, polymer composition, composition capable of free radical polymerization, polymer preparation method, polymer and application

Abstract

The invention relates to a method for reducing the content of residual monomers in a polymer composition, the polymer composition, a composition capable of free radical polymerization, a polymer preparation method, a polymer and application.

Description

Technical Field

[0001] The present invention relates to the field of polymers, in particular to the field of medical polymers. Specifically, the present invention relates to a method for reducing the residual monomer content in a polymer composition, a polymer composition prepared by the method, 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 use of the composition capable of free radical polymerization in preparing a polymer. Background Art

[0002] Medical polymer materials, also known as medical high polymer materials, are a type of synthetic polymer materials with special functions used to manufacture human internal organs, external organs, drug dosage forms and medical devices. They are one of the important components of biomedical materials. Medical polymer materials can have different physical and chemical properties through the control of composition and structure to meet the needs of different application scenarios. Because they act on the human body, the basic properties of medical polymer materials have higher requirements than ordinary polymer materials; for example, medical polymer materials require good biocompatibility, strong chemical stability, excellent physical and mechanical properties, and easy molding and processing of materials. The most critical of these is biocompatibility, and chemical residues, extractables and leachables are key factors affecting the biocompatibility of materials.

[0003] Corneal contact lenses are a type of commonly used medical polymer material. They are optical instruments attached to the surface of the cornea for correcting refractive errors; they include soft corneal contact lenses and hard corneal contact lenses. As a special biomaterial, corneal contact lenses must be compatible with various tissues on the ocular surface. Because they cover the human cornea, they reduce the oxygen supply level of the cornea. The oxygen permeability coefficient (DK) is the main parameter to measure the performance of a material in allowing oxygen to pass through. Since there are no blood vessels in the cornea, it must obtain nutrition and material metabolism from tears, aqueous humor, and oxygen dissolved in tears. Corneal hypoxia can cause edema of the corneal epithelium and stroma. As a result, rigid gas permeable corneal contact lenses (RGP, Rigid Gas Permeable) materials came into being.

[0004] Medical RGP materials are usually made of siloxane methacrylate, methacrylate or fluorine-substituted methacrylate as the main component, through free radical copolymerization or other polymerization methods. In clinical applications, in order to give the material resistance to protein deposition, specific toughness and strength, and hydrophilicity, some functional olefin-terminated polymerization monomers are often added to improve wearing comfort and safety.

[0005] For RGP materials that are in long-term contact with the cornea, it is important to improve oxygen permeability and reduce the chance of corneal edema. However, as a material that is in direct contact with the cornea, the lens material will be in full contact with eye tissues such as the cornea and conjunctiva during wear. The monomer components in the RGP material that are not fully involved in polymerization, as well as extractables and leachables will be absorbed by the ocular surface through tear exchange or passive diffusion, causing biological safety issues such as irritation and damage to the cornea and other eye tissues.

[0006] RGP materials are made of copolymerization and cross-linking of multiple functional monomers. Due to the different structures and chemical environments of the polymerization sites of each monomer participating in the polymerization reaction, it is difficult for different monomers to copolymerize ideally, and some or even a large amount of unpolymerized monomers will remain in the system. Moreover, after the RGP copolymer is formed in the polymerization process, it is difficult to purify it by conventional chemical means due to the particularity of its macromolecular structure. It is difficult to achieve the purpose of removing residual monomers and unknown impurities that have not fully participated in the reaction by post-treatment.

[0007] In order to reduce the residual RGP monomer, the art often needs to repeatedly and finely adjust the control prescription, increase the complex process control, use a longer polymerization reaction time, etc., which increases the complexity of the process and the production cost.

[0008] Therefore, if an excellent RGP material is evaluated from the perspective of clinical application, it must be a material with less extractables and leachables (chemical residues) and high oxygen permeability. But usually these two points are contradictory; to improve oxygen permeability, it is necessary to add one or more monomers that are conducive to oxygen permeation to the composition, such as siloxane oligomers, and highly sterically hindered silicon-containing and fluorinated monomers. However, the increase in the types of monomers, especially the presence of oligomers and monomers with large steric hindrance, increases the complexity of the copolymerization process, which will lead to further aggravation of monomer residues. This is also the reason why only a few materials have been approved for clinical use in the decades since the advent of hard contact lenses. The RGP materials currently used in Class 3 medical devices on the market in China are: Ⅱ(DK 85), Boston (DK 100) 、 Boston (DK 141), Paragon HDS (DK 100), Menicon (DK 163), Optimum (DK125), used in contact lenses abroad Optimum (DK 180), Acuity 200 TM (DK 200) and so on.

[0009] In short, the development of high oxygen permeability materials is inherently difficult; in addition to considering the DK parameter, physical parameters such as toughness, strength, and water wettability must also be taken into account. Under the premise of maintaining high oxygen permeability and other physical properties, it becomes extremely difficult to further reduce monomer residues and reduce the risk of biosafety assessment.

[0010] CN112513114A discloses a method for producing ultra-high Dk materials, which requires polymerizing fluoroalkyl methacrylate; alkyl glycol dimethacrylate; hydrophilic agent, such as methacrylic acid; hydroxyalkyl tris(trimethylsiloxy)silane; hydroxyalkyl-terminated polydimethylsiloxane; and styrylethyl tris(trimethylsiloxy)silane at a specific temperature in an inert atmosphere at a pressure of at least 25 pounds per square inch (PSI) to prepare an RGP material with a DK greater than 175. Polymerization under high pressure in an inert gas poses a huge challenge to the production process, molds, and operational safety. In this technical solution, the copolymerization process under high pressure is not analyzed, and no qualitative or quantitative analysis data on chemical residues are provided.

[0011] CN116515300A discloses a composition of a highly oxygen permeable material. The composition is cured by a special cross-linking process of non-radical curing to prepare a contact lens with a Shore D hardness ≥ 60 and a DK ≥ 200. The composition comprises the following components: a) a hydrogenated silicone resin containing SiH groups; (b) a vinyl 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 hydrogenated silicone resin and the vinyl silicone resin is limited. The data disclosed by this method show that materials with a KD greater than 200 can be prepared, but compared with the commercially available product Boston (Shore D=81), the hardness of the material is obviously too small, the material is too soft, and the material has poor processability. The technical solution also does not provide the residual data of the relevant monomers after polymerization.

[0012] CN106749877A discloses a high oxygen permeability optical lens material composition and its preparation method, the material composition: 1-30% methacryloyl T-structure siloxane, 30-60% fluorine-containing methyl acrylate monomer, 20-40% methacryloyl (trimethylsiloxy) silane, 3-15% hydrophilic monomer, 5-30% methacryloyl terminal siloxane, 1-10% crosslinking agent, 0.01-0.5% free radical initiator, 0.1-5% ultraviolet absorber. The above-disclosed optical lens material has a certain oxygen permeability (105-171), and has good wettability and anti-protein deposition. CN113698552A adds hydrophobic agent and fluorine-containing silicon methyl acrylate monomer to the prescription composition disclosed in CN106749877A, which comprehensively improves the oxygen permeability, spectral transmittance and mechanical properties of polyacrylate materials. However, these two patents also only disclose methods for improving the oxygen permeability of materials, but do not analyze and confirm the residual monomers after copolymerization by this method.

[0013] Menicon Company provides a method for reducing the monomer residue in the copolymer used for contact lens materials in patent CN1894620A, but this method is achieved at the cost of removing the hydrophilic monomer in the formula for preparing the copolymer. The obtained copolymer is obtained by polymerization using a monomer containing a polysiloxane with a special structure. The residual amount of the unpolymerized monomer component in the copolymer is ≤3%, DK≥130, and the water absorption rate of the copolymer is ≤0.3%. The material has almost no water wettability, and the wearing comfort of the purely hydrophobic material is very poor. At the same time, there is also a risk of corneal epithelial cell adhesion. Although the surface of the hydrophobic material can be modified to be hydrophilic by surface treatment technology, the validity period of the existing surface modification technology (generally 1-2 months) is much shorter than the validity period of RGP contact lenses (1 year). When the surface modification fails, the problem of the hydrophobic material is exposed again. Therefore, this technical solution cannot be used in clinical practice for the time being.

[0014] As mentioned above, medical polymer materials for hard contact lenses must take into account high oxygen permeability and low chemical residues (extractables and leachables) in their development and application, which together determine the safety and effectiveness of RGP materials. Existing technologies focus more on simply improving the oxygen permeability of materials, or improving monomer residues at the expense of the safety and comfort of wearing materials.

[0015] Therefore, there is still a need in the art to provide a polymer material such as a medical polymer material that can achieve low chemical residues and thus have high biocompatibility, in particular, a method for providing an RGP material that can achieve low chemical residues and at the same time have excellent oxygen permeability, and can also retain excellent comprehensive properties such as water wettability and processability. Summary of the invention

[0016] The present invention is made just for the above-mentioned 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), wherein the polymer composition is a polymer composition prepared by free radical polymerization using a first composition capable of free radical polymerization comprising an ethylenically unsaturated monomer in which the olefinic bond is derived from an isopropenyl group (CH2=C(CH3)-). The polymer composition (or polymer) obtained by the method of the present invention has low chemical residues and therefore has high biocompatibility, thereby being suitable for use as a medical polymer material. And the 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 a process according to the first aspect of the present invention.

[0019] In a third aspect, the present invention provides a composition capable of free radical polymerization, the composition comprising a monoalkenyl functional hydrophobic fluorine-containing monomer component, a monoalkenyl functional hydrophobic silicon-containing monomer component, and a monoalkenyl functional hydrophilic monomer component, wherein the polymer (or polymer composition) obtained by free radical polymerization has low chemical residues and thus has high biocompatibility, thereby being suitable for use as a medical polymer material. Moreover, the free radical polymerization does not require complicated process control.

[0020] Furthermore, the present invention provides a composition capable of free radical polymerization, the composition comprising a monoolefinic functional hydrophobic fluorine-containing monomer component, a monoolefinic functional hydrophobic silicon-containing monomer component, and a monoolefinic functional hydrophilic monomer component, wherein the polymer obtained by free radical polymerization has low chemical residues and does not require complicated process control for polymerization, and also has good hardness, oxygen permeability, water wettability and processability; and therefore, can be used, for example, to prepare corneal contact lenses such as hard oxygen permeable corneal contact lenses.

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

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

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

[0024] In particular, the present invention is achieved by:

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

[0026] a first ethylenically unsaturated monomer component based on a first ethylenically unsaturated monomer, wherein the olefinic bond in the first ethylenically unsaturated monomer is derived from an isopropenyl group (CH2=C(CH3)-),

[0027] Free radical initiators,

[0028] Optionally, a UV absorber, and

[0029] Optionally, a coloring agent;

[0030] The method comprises: providing a second free radical polymerizable composition by replacing a portion of the first ethylenically unsaturated monomer component with a second ethylenically unsaturated monomer component based on a second ethylenically unsaturated monomer as follows: wherein the olefinic bond of the second ethylenically unsaturated monomer is derived from a vinyl group (CH2=CH-);

[0031] The second free radical polymerizable composition is then free radically polymerized.

[0032] 2. The method according to item 1, wherein the olefinic bond in the first ethylenically unsaturated monomer is derived from a methacryloxy group, and the olefinic bond in the second ethylenically unsaturated monomer is derived from one or more of the following: acryloxy, acrylamido, N-vinylamido, vinylphenyl.

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

[0034] Preferably the first ethylenically unsaturated monomer is a monoethylenically functional ethylenically unsaturated monomer and the second ethylenically unsaturated monomer is a monoethylenically functional ethylenically unsaturated monomer.

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

[0036] The first ethylenically 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 ethylenically 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 ethylenically 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 by an acryloxy group, a 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 by an acryloxy group in the second hydrophilic monomer;

[0037] Preferably, the first ethylenically unsaturated monomer includes or is a first hydrophobic fluorine-containing monomer containing methacryloyl, such as a hydrophobic fluorine-containing alkyl methacrylate monomer, a first hydrophobic silicon-containing monomer containing methacryloyl, such as a silicon-containing hydrophobic methacrylate monomer, a first hydrophilic monomer containing methacryloyl, or any combination thereof; preferably, the first ethylenically unsaturated monomer includes or is a first hydrophobic fluorine-containing monomer containing methacryloyl, such as a hydrophobic fluorine-containing alkyl methacrylate monomer, a first hydrophobic silicon-containing monomer containing methacryloyl, such as a silicon-containing hydrophobic methacrylate monomer, and a first hydrophilic monomer containing methacryloyl, and the second ethylenically unsaturated monomer includes or is a second hydrophobic fluorine-containing monomer, such as a hydrophobic fluorine-containing alkyl acrylate. Monomer, a second hydrophobic silicon-containing monomer such as a silicon-containing hydrophobic acrylate monomer and / or a vinylphenyl-containing silane, a second hydrophilic monomer, or a combination thereof; preferably, the first hydrophobic fluorine-containing monomer differs from the second hydrophobic fluorine-containing monomer only in that the methacryloxy group in the first hydrophobic fluorine-containing monomer is replaced by an acryloxy group in the second hydrophobic fluorine-containing monomer; preferably, the first hydrophobic silicon-containing monomer differs from the second hydrophobic silicon-containing monomer only in that the methacryloxy group in the first hydrophobic silicon-containing monomer is replaced by an acryloxy group, vinylphenyl or a combination thereof in the second hydrophobic silicon-containing monomer; preferably, the first hydrophilic monomer differs from the second hydrophilic monomer only in that the methacryloxy group in the first hydrophilic monomer is replaced by an acryloxy group in the second hydrophilic monomer;

[0038] Preferably, the first ethylenically unsaturated monomer includes or is a monoolefinic first hydrophobic fluorinated monomer containing methacryloyl, such as a hydrophobic fluorinated alkyl methacrylate monomer, a monoolefinic first hydrophobic silicon-containing monomer containing methacryloyl, such as a silicon-containing hydrophobic methacrylate monomer, a monoolefinic first hydrophilic monomer containing methacryloyl, or any combination thereof; preferably, the first ethylenically unsaturated monomer includes or is a monoolefinic first hydrophobic fluorinated monomer containing methacryloyl, such as a hydrophobic fluorinated alkyl methacrylate monomer, a monoolefinic first hydrophobic silicon-containing monomer containing methacryloyl, such as a silicon-containing hydrophobic methacrylate monomer, and a monoolefinic first hydrophilic monomer containing methacryloyl, and the second ethylenically unsaturated monomer includes or is a monoolefinic second hydrophobic fluorinated monomer Preferably, the first hydrophobic fluorine-containing monomer and the second hydrophobic fluorine-containing monomer differ only in that the methacryloxy group in the first hydrophobic fluorine-containing monomer is replaced by the acryloxy group in the second hydrophobic fluorine-containing monomer; preferably, the first hydrophobic silicon-containing monomer and the second hydrophobic silicon-containing monomer differ only in that the methacryloxy group in the first hydrophobic silicon-containing monomer is replaced by the acryloxy group, vinylphenyl group or a combination thereof in the second hydrophobic silicon-containing monomer; preferably, the first hydrophilic monomer and the second hydrophilic monomer differ only in that the methacryloxy group in the first hydrophobic silicon-containing monomer is replaced by the acryloxy group in the second hydrophobic silicon-containing monomer.

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

[0040] (1) A monoethylenically functional hydrophobic fluorinated monomer component comprising or consisting of:

[0041] (1-1) a first hydrophobic fluorine-containing monomer component based on a fluoroalkyl methacrylate as a first hydrophobic fluorine-containing monomer;

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

[0043] and

[0044] (1-2) an optional second hydrophobic fluorine-containing monomer component based on a fluorine-containing alkyl acrylate as a second hydrophobic fluorine-containing 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, preferably the same;

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

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

[0048] (2) a monoolefin-functional hydrophobic silicon-containing monomer component comprising or consisting of:

[0049] (2-1) a first hydrophobic silicon-containing monomer component based on a silicon-containing methacrylate as a first hydrophobic silicon-containing monomer,

[0050] Preferably, the first hydrophobic silicon-containing monomer is a silicon-containing methacrylate of the following formula:

[0051] CH2=C(CH3)-C(O)-O-L1-Si(R1)m(OR2) 3-m , wherein L1 is a C1-C10, preferably C3-C6 divalent alkylene group, which optionally includes one or more of an ether -O-atom group and an -OH group, R1 is the same as or different from each other and is independently a C1-C6 alkyl group, preferably a methyl group, R2 is the same as or different from each other and is independently a C1-C6 alkyl group, preferably a methyl group, or -Si(R3)3, wherein R3 is the same as or different from each other and is independently a C1-C6 alkyl group, preferably a methyl group, and m is 0, 1, 2, or 3, preferably 0 or 1;

[0052] Preferably, the first hydrophobic silicon-containing monomer is selected from one or more of methacryloxypropyl tris(trimethylsiloxy)silane and (3-methacryloxy-2-hydroxypropoxy)propyl bis(trimethylsiloxy)methylsilane;

[0053] and

[0054] (2-2) an optional second hydrophobic silicon-containing monomer component based on a silicon-containing acrylate or a vinylphenyl-containing silane as the second hydrophobic silicon-containing monomer,

[0055] 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 , wherein Ph is a phenylene group such as a 1,4-phenylene group, L2 is the same as or different from L1 and is a C1-C10, preferably a C3-C6 divalent alkylene group which optionally includes one or more of an ether -O-atom group and a -OH group; R4 is the same as or different from each other and is the same as or different from R1 and is each independently a C1-C6 alkyl group, preferably a methyl group, R5 is the same as or different from each other and is the same as or different from R2 and is each independently a C1-C6 alkyl group, preferably a methyl group or -Si(R6)3, wherein R6 is the same as or different from each other and is the same as or different from R3 and is each independently a C1-C6 alkyl group, preferably a methyl group, and n is the same as or different from m and is 0, 1, 2 or 3, preferably 0 or 1;

[0056] Preferably, -Si(R4) n (OR5) 3-n Partially with -Si(R1)m(OR2) 3-m The parts are identical or different, preferably identical;

[0057] Preferably, -L2-Si(R4) n (OR5) 3-nPartially with -L1-Si(R1)m(OR2) 3-m The parts are identical or different, preferably identical;

[0058] Preferably, the second hydrophobic silicon-containing monomer is selected from one or more of acryloxypropyl tris(trimethylsiloxy)silane, (3-acryloxy-2-hydroxypropoxy)propyl bis(trimethylsiloxy)methylsilane and p-vinylphenyl tris(trimethylsiloxy)silane;

[0059] Preferably, the first hydrophobic silicon-containing monomer is selected from methacryloxypropyl tris(trimethylsiloxy)silane, and the second hydrophobic silicon-containing monomer is selected from one or more of acryloxypropyl tris(trimethylsiloxy)silane and p-vinylphenyl tris(trimethylsiloxy)silane, preferably acryloxypropyl tris(trimethylsiloxy)silane;

[0060] (3) a monoolefin-functional hydrophilic monomer component comprising or consisting of:

[0061] (3-1) a first hydrophilic monomer component based on a first hydrophilic monomer containing a methacryloyl group;

[0062] Preferably, the first hydrophilic monomer is selected from one or more of methacrylic acid, hydroxyethyl methacrylate, methacrylamide, and N,N-dimethylmethacrylamide;

[0063] and / or

[0064] (3-2) a second hydrophilic monomer component based on a second hydrophilic monomer containing an acryloxy group, an acrylamido group and / or an N-vinylamido group;

[0065] Preferably, 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;

[0066] Preferably, the second hydrophilic monomer is selected from acrylic acid, hydroxyethyl acrylate, acrylamide,

[0067] One or more of N,N-dimethylacrylamide, N-vinylpyrrolidone, and N-methyl-N-vinylacetamide;

[0068] 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-vinyl pyrrolidone (NVP) and N,N-dimethylacrylamide, preferably acrylic acid;

[0069] (4) optionally, a crosslinker component based on a diene-functional or higher crosslinker;

[0070] Preferably, the crosslinking agent with more than bis-alkenyl functionality is selected from: alkyl glycol dimethacrylate, preferably neopentyl glycol dimethacrylate; a siloxane-containing oligomer, preferably 1,3-bis(methacryloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, bis(methylpropoxy)butylpolydimethylsiloxane; or any combination thereof; for example, neopentyl glycol dimethacrylate and 1,3-bis(methacryloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, which are present in a mass ratio of, for example, 10:90-90:10, for example, 30:70-70:30, for example, 50:50-60:40;

[0071] (5) free radical initiators, such as azobisisobutyronitrile or azobisisoheptanenitrile;

[0072] (6) optionally, a UV absorber, such as 2-hydroxy-4-(methacryloyloxy)benzophenone;

[0073] When the first hydrophilic monomer is present, one, two or three of the second hydrophobic fluorine-containing monomer, the second hydrophobic silicon-containing monomer, and the second hydrophilic monomer are present.

[0074] 6. The method according to any one of items 1 to 5, wherein the second free radical polymerizable composition comprises, based on the total mass of the second free radical polymerizable composition:

[0075] (1) 30-60 mass %, for example 40-50 mass %, of a monoethylenically functional hydrophobic fluorinated monomer component;

[0076] (2) 20-45 mass %, for example 30-40 mass %, of a monoethylenic functional hydrophobic silicon-containing monomer component;

[0077] (3) 3-20 mass %, for example 5-10 mass %, of a monoethylenic functional hydrophilic monomer component;

[0078] (4) optionally, 1-20 mass %, e.g., 5-15 mass %, of a crosslinker component based on a diene-functional or higher crosslinker; and

[0079] (5) 0.1-2.0 mass %, for example 0.5-1.0 mass % of a free radical initiator; and

[0080] (6) Optionally, 0.1-5.0 mass %, such as 0.2-1.0 mass %, such as 0.4-0.6 mass % of an ultraviolet absorber.

[0081] 7. The method according to any one of items 4 to 6, wherein in the second free-radically polymerizable composition:

[0082] A second hydrophobic fluorinated monomer is present, preferably the first hydrophobic fluorinated monomer and the second hydrophobic fluorinated monomer are present in a mass ratio of 30:70-80:20, such as 50:50-80:20, such as 70:30-80:20; and / or

[0083] A second hydrophobic silicon-containing monomer is present, 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, such as 50:50-75:25; and / or

[0084] The first hydrophilic monomer and the second hydrophilic monomer are present, preferably the first hydrophilic monomer and the second hydrophilic monomer are present in a mass ratio of 0:100-85:15, such as 25:75-80:20, such as 40:60-75:25.

[0085] 8. The method according to any one of items 4 to 7, wherein a second hydrophobic fluorine-containing monomer, a second hydrophobic silicon-containing monomer, a first hydrophilic monomer and a second hydrophilic monomer are present in the second free-radically polymerizable composition.

[0086] 9. The method according to any one of items 1 to 8, wherein the method comprises, before polymerization, performing the following purification step before providing the second free radical polymerizable composition:

[0087] Purifying the first ethylenically unsaturated monomer component to increase the content of the first ethylenically unsaturated monomer and / or reduce the content of the polymerization inhibitor therein, for example, to make the content of the first ethylenically unsaturated monomer therein 98 mass % or more, preferably 99 mass % or more and / or the content of the polymerization inhibitor therein is 50 ppm by mass or less; and / or

[0088] The second ethylenically unsaturated monomer component is purified to increase the second ethylenically unsaturated monomer content and / or reduce the polymerization inhibitor content therein, for example, so that the second ethylenically unsaturated monomer content therein is 98% by mass or more, preferably 99% by mass or more and / or the polymerization inhibitor content therein is 50 ppm by mass or less.

[0089] 10. The method according to any one of items 4 to 9, wherein the method comprises, before polymerization and before providing the second free radical polymerizable composition, performing the following purification step:

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

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

[0092] Purifying the first hydrophobic silicon-containing monomer component to increase the content of the first hydrophobic silicon-containing monomer and / or reduce the content of the polymerization inhibitor, for example, to make the content of the first hydrophobic silicon-containing monomer greater than 98 mass %, preferably greater than 99 mass % and / or the content of the polymerization inhibitor less than 50 ppm by mass; and / or

[0093] Purifying the second hydrophobic silicon-containing monomer component to increase the content of the second hydrophobic silicon-containing monomer and / or reduce the content of the polymerization inhibitor, for example, to make the content of the second hydrophobic silicon-containing monomer greater than 98 mass %, preferably greater than 99 mass % and / or the content of the polymerization inhibitor less than 50 ppm by mass; and / or

[0094] Purifying the first hydrophilic monomer component to increase the content of the first hydrophilic monomer and / or reduce the content of the polymerization inhibitor therein, for example, to make the content of the first hydrophilic monomer therein 98 mass % or more, preferably 99 mass % or more and / or the content of the polymerization inhibitor therein be 50 ppm by mass or less; and / or

[0095] Purifying the second hydrophilic monomer component to increase the content of the second hydrophilic monomer and / or reduce the content of the polymerization inhibitor therein, for example, to make the content of the second hydrophilic monomer therein 98 mass % or more, preferably 99 mass % or more and / or the content of the polymerization inhibitor therein 50 ppm by mass or less; and / or

[0096] The crosslinker component based on a diene-functional or higher crosslinker is purified to increase the crosslinker content and / or reduce the polymerization inhibitor content therein, for example, so that the crosslinker content therein 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.

[0097] 11. The method according to any one of items 1 to 10, wherein the first free radical polymerizable composition comprises a non-reactive dye, for example, in an amount of 0.001-0.5 mass %, for example, 0.005-0.01 mass %, and the method further comprises partially or completely replacing the non-reactive dye in the first free radical polymerizable composition with a reactive dye, for example, containing an alkenyl group, for example, containing a methacryloyl group, the reactive dye being selected from, for example, one or more of 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone, 1,4-bis((2-hydroxyethyl)amino)-9,10-anthracenedione bis(2-propylene OIC) ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenethyl)methacrylamide.

[0098] 12. The method according to any one of items 1 to 11, wherein the polymer is a medical polymer, preferably a polymer for preparing corneal contact lenses, preferably a polymer for preparing hard oxygen permeable corneal contact lenses.

[0099] 13. A method for reducing the residual monomer content in a polymer composition, the polymer composition being a polymer composition prepared by free radical polymerization using a first free radical polymerizable composition, the first free radical polymerizable composition comprising a mixture of:

[0100] a first ethylenically unsaturated monomer component based on a first ethylenically unsaturated monomer, wherein the olefinic bond in the first ethylenically unsaturated monomer is derived from an isopropenyl group (CH2=C(CH3)-),

[0101] Free radical initiators,

[0102] Optionally, a UV absorber, and

[0103] Optionally, a coloring agent;

[0104] The method comprises the following purification step before the polymerization and before the components are combined to form the first free radical polymerizable composition: purifying the first ethylenically unsaturated monomer component to increase the content of the first ethylenically unsaturated monomer and / or reduce the content of the polymerization inhibitor therein, for example, to make the content of the first ethylenically unsaturated monomer therein 98 mass % or more, preferably 99 mass % or more and / or the content of the polymerization inhibitor therein be 50 ppm by mass or less;

[0105] Free radical polymerization is then carried out.

[0106] 14. The method according to item 13, wherein the method comprises: providing a second free radical polymerizable composition by replacing a portion of the first ethylenically unsaturated monomer component with a second ethylenically unsaturated monomer component based on a second ethylenically unsaturated monomer as follows: wherein the olefinic bond of the second ethylenically unsaturated monomer is derived from a vinyl group (CH2=CH-);

[0107] The second free radical polymerizable composition is then free radically polymerized.

[0108] 15. The method according to item 14, wherein the first free radically polymerizable composition and the second free radically polymerizable composition are as defined in any one of items 2-12.

[0109] 16. A method for reducing the residual monomer content in a polymer composition, the polymer composition being a polymer composition prepared by free radical polymerization using a first free radical polymerizable composition, the first free radical polymerizable composition comprising a mixture of:

[0110] a first ethylenically unsaturated monomer component based on a first ethylenically unsaturated monomer, wherein the olefinic bond in the first ethylenically unsaturated monomer is derived from an isopropenyl group (CH2=C(CH3)-),

[0111] Free radical initiators,

[0112] Optionally, a UV absorber, and

[0113] Non-reactive stains;

[0114] The method comprises: partially or completely replacing the non-reactive dye in the first composition capable of free radical polymerization with a reactive dye containing, for example, an alkenyl group, for example, a methacryloyl group, to provide a second composition capable of free radical polymerization, wherein the reactive dye is, for example, one or more selected from 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone, 1,4-bis((2-hydroxyethyl)amino)-9,10-anthracenedione bis(2-propylene OIC)ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenethyl)methacrylamide;

[0115] Free radical polymerization is then carried out.

[0116] 17. The method according to item 16, wherein the amount of the dye in the first free-radically polymerizable composition and the amount of the reactive dye in the second free-radically polymerizable composition are each independently 0.001-0.5 mass %, such as 0.005-0.01 mass %.

[0117] 18. The method according to any one of items 16-17, wherein the method further comprises: providing the second free radical polymerizable composition by replacing a portion of the first ethylenically unsaturated monomer component with a second ethylenically unsaturated monomer component based on a second ethylenically unsaturated monomer as follows: wherein the olefinic bond of the second ethylenically unsaturated monomer is derived from a vinyl group (CH2=CH-);

[0118] The second free radical polymerizable composition is then free radically polymerized.

[0119] 19. The method according to item 18, wherein the first free radical polymerizable composition and the second free radical polymerizable composition are as defined in any one of items 2-10 and 12.

[0120] 20. A polymer composition obtained by the process according to any one of items 1 to 19.

[0121] 21. A free radical polymerizable composition comprising:

[0122] (1) A monoethylenically functional hydrophobic fluorinated monomer component comprising or consisting of:

[0123] (1-1) a first hydrophobic fluorine-containing monomer component based on a fluoroalkyl methacrylate as a first hydrophobic fluorine-containing monomer;

[0124] Preferably, the first hydrophobic fluorine-containing monomer is C1-C10 fluorine-containing alkyl methacrylate, preferably C1-C6 fluorine-containing alkyl methacrylate, preferably C2-C5 fluorine-containing alkyl methacrylate, more preferably C2-C3 fluorine-containing alkyl methacrylate; preferably, the first hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate; more preferably, the first hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl methacrylate and hexafluoroisopropyl methacrylate;

[0125] and

[0126] (1-2) an optional second hydrophobic fluorine-containing monomer component based on a fluorine-containing alkyl acrylate as a second hydrophobic fluorine-containing monomer;

[0127] 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, preferably the same;

[0128] Preferably, the second hydrophobic fluorine-containing monomer is C1-C10 fluorine-containing alkyl acrylate, preferably C1-C6 fluorine-containing alkyl acrylate, preferably C2-C5 fluorine-containing alkyl acrylate, more preferably C2-C3 fluorine-containing alkyl acrylate; preferably, the second hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl acrylate, hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate; more preferably, the second hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl acrylate and hexafluoroisopropyl acrylate;

[0129] Preferably, the first hydrophobic fluorine-containing monomer is selected from one or more of hexafluoroisopropyl methacrylate and trifluoroethyl methacrylate, and the second hydrophobic fluorine-containing monomer is selected from one or more of hexafluoroisopropyl acrylate and trifluoroethyl acrylate; preferably, the first hydrophobic fluorine-containing monomer is hexafluoroisopropyl methacrylate and the second hydrophobic fluorine-containing monomer is hexafluoroisopropyl acrylate, or the first hydrophobic fluorine-containing monomer is trifluoroethyl methacrylate and the second hydrophobic fluorine-containing monomer is trifluoroethyl acrylate;

[0130] (2) a monoolefin-functional hydrophobic silicon-containing monomer component comprising or consisting of:

[0131] (2-1) a first hydrophobic silicon-containing monomer component based on a silicon-containing methacrylate as a first hydrophobic silicon-containing monomer,

[0132] Preferably, the first hydrophobic silicon-containing monomer is a silicon-containing methacrylate of the following formula:

[0133] CH2=C(CH3)-C(O)-O-L1-Si(R1)m(OR2) 3-m , wherein L1 is a C1-C10, preferably C3-C6 divalent alkylene group, which optionally includes one or more of an ether -O-atom group and an -OH group, R1 is the same as or different from each other and is independently a C1-C6 alkyl group, preferably a methyl group, R2 is the same as or different from each other and is independently a C1-C6 alkyl group, preferably a methyl group, or -Si(R3)3, wherein R3 is the same as or different from each other and is independently a C1-C6 alkyl group, preferably a methyl group, and m is 0, 1, 2, or 3, preferably 0 or 1;

[0134] Preferably, the first hydrophobic silicon-containing monomer is selected from one or more of methacryloxypropyl tris(trimethylsiloxy)silane and (3-methacryloxy-2-hydroxypropoxy)propyl bis(trimethylsiloxy)methylsilane;

[0135] and

[0136] (2-2) an optional second hydrophobic silicon-containing monomer component based on a silicon-containing acrylate or a vinylphenyl-containing silane as the second hydrophobic silicon-containing monomer,

[0137] 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 , wherein Ph is a phenylene group such as a 1,4-phenylene group, L2 is the same as or different from L1 and is a C1-C10, preferably a C3-C6 divalent alkylene group which optionally includes one or more of an ether -O-atom group and a -OH group; R4 is the same as or different from each other and is the same as or different from R1 and is each independently a C1-C6 alkyl group, preferably a methyl group, R5 is the same as or different from each other and is the same as or different from R2 and is each independently a C1-C6 alkyl group, preferably a methyl group or -Si(R6)3, wherein R6 is the same as or different from each other and is the same as or different from R3 and is each independently a C1-C6 alkyl group, preferably a methyl group, and n is the same as or different from m and is 0, 1, 2 or 3, preferably 0 or 1;

[0138] Preferably, -Si(R4) n (OR5) 3-n Partially with -Si(R1)m(OR2) 3-m The parts are identical or different, preferably identical;

[0139] Preferably, -L2-Si(R4) n (OR5) 3-n Partially with -L1-Si(R1)m(OR2) 3-m The parts are identical or different, preferably identical;

[0140] Preferably, the second hydrophobic silicon-containing monomer is selected from one or more of acryloxypropyl tris(trimethylsiloxy)silane, (3-acryloxy-2-hydroxypropoxy)propyl bis(trimethylsiloxy)methylsilane and p-vinylphenyl tris(trimethylsiloxy)silane;

[0141] Preferably, the first hydrophobic silicon-containing monomer is selected from methacryloxypropyl tris(trimethylsiloxy)silane, and the second hydrophobic silicon-containing monomer is selected from one or more of acryloxypropyl tris(trimethylsiloxy)silane and p-vinylphenyl tris(trimethylsiloxy)silane, preferably acryloxypropyl tris(trimethylsiloxy)silane;

[0142] (3) a monoolefin-functional hydrophilic monomer component comprising or consisting of:

[0143] (3-1) a first hydrophilic monomer component based on a first hydrophilic monomer containing a methacryloyl group;

[0144] Preferably, the first hydrophilic monomer is selected from one or more of methacrylic acid, hydroxyethyl methacrylate, methacrylamide, and N,N-dimethylmethacrylamide;

[0145] and / or

[0146] (3-2) a second hydrophilic monomer component based on a second hydrophilic monomer containing an acryloxy group, an acrylamido group and / or an N-vinylamido group;

[0147] Preferably, 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;

[0148] Preferably, the second hydrophilic monomer is selected from one or more of acrylic acid, hydroxyethyl acrylate, acrylamide, N,N-dimethylacrylamide, N-vinyl pyrrolidone, and N-methyl-N-vinylacetamide;

[0149] 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-vinyl pyrrolidone (NVP) and N,N-dimethylacrylamide, preferably acrylic acid;

[0150] (4) optionally, a crosslinker component based on a diene-functional or higher crosslinker;

[0151] Preferably, the crosslinking agent with more than bis-alkenyl functionality is selected from: alkyl glycol dimethacrylate, preferably neopentyl glycol dimethacrylate; a siloxane-containing oligomer, preferably 1,3-bis(methacryloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, bis(methylpropoxy)butylpolydimethylsiloxane; or any combination thereof; for example, neopentyl glycol dimethacrylate and 1,3-bis(methacryloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, which are present in a mass ratio of, for example, 10:90-90:10, for example, 30:70-70:30, for example, 50:50-60:40;

[0152] (5) free radical initiators, such as azobisisobutyronitrile or azobisisoheptanenitrile;

[0153] (6) optionally, a UV absorber, such as 2-hydroxy-4-(methacryloyloxy)benzophenone;

[0154] The composition satisfies one, two or three of the following conditions (1)-(3):

[0155] (1) when the first hydrophilic monomer is present, one, two or three of a second hydrophobic fluorine-containing monomer, a second hydrophobic silicon-containing monomer, and a second hydrophilic monomer are present; and / or

[0156] (2) the content of the first hydrophobic fluorine-containing monomer in the first hydrophobic fluorine-containing monomer component, and / or the content of the second hydrophobic fluorine-containing monomer in the second hydrophobic fluorine-containing 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 crosslinker based on a diene-functional or higher crosslinker in the crosslinker component are each independently 98% by mass or more, preferably 99% by mass or more; and / or

[0157] The content of the polymerization inhibitor in the first hydrophobic fluorine-containing monomer component, and / or the second hydrophobic fluorine-containing 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 cross-linking agent component is independently 50 ppm by mass or less; and / or

[0158] (3) The composition includes a dye, and part or all of the dye is a reactive dye containing an alkenyl group, such as a methacryloyl group, which is, for example, one or more reactive dyes selected from 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone, 1,4-bis((2-hydroxyethyl)amino)-9,10-anthracenedione bis(2-propylene OIC)ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenethyl)methacrylamide.

[0159] 22. The composition according to item 21, wherein the composition comprises, based on the total mass of the composition:

[0160] (1) 30-60 mass %, for example 40-50 mass %, of a monoethylenically functional hydrophobic fluorinated monomer component;

[0161] (2) 20-45 mass %, for example 30-40 mass %, of a monoethylenic functional hydrophobic silicon-containing monomer component;

[0162] (3) 3-20 mass %, for example 5-10 mass %, of a monoethylenic functional hydrophilic monomer component;

[0163] (4) optionally, 1-20 mass %, e.g., 5-15 mass %, of a crosslinker component based on a diene-functional or higher crosslinker; and

[0164] (5) 0.1-2.0 mass %, for example 0.5-1.0 mass % of a free radical initiator;

[0165] (6) optionally, 0.1-5.0 mass %, such as 0.2-1.0 mass %, such as 0.4-0.6 mass % of an ultraviolet absorber; and

[0166] (7) Optionally, 0.001-0.5 mass %, for example 0.005-0.01 mass %, of a coloring agent.

[0167] 23. The composition according to any one of items 21-22, wherein in the composition:

[0168] A second hydrophobic fluorinated monomer is present, preferably the first hydrophobic fluorinated monomer and the second hydrophobic fluorinated monomer are present in a mass ratio of 30:70-80:20, such as 50:50-80:20, such as 70:30-80:20; and / or

[0169] A second hydrophobic silicon-containing monomer is present, 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, such as 50:50-75:25; and / or

[0170] The first hydrophilic monomer and the second hydrophilic monomer are present, preferably the first hydrophilic monomer and the second hydrophilic monomer are present in a mass ratio of 0:100-85:15, such as 25:75-80:20, such as 40:60-75:25.

[0171] 24. The composition of any one of items 21-23, wherein a second hydrophobic fluorine-containing monomer, a second hydrophobic silicon-containing monomer, a first hydrophilic monomer, and a second hydrophilic monomer are present.

[0172] 25. The composition according to any one of items 21 to 24, wherein the composition is a composition for preparing a medical polymer, preferably a composition for preparing a corneal contact lens, preferably a hard oxygen permeable corneal contact lens.

[0173] 26. A method for preparing a polymer, comprising: providing a composition according to any one of items 21 to 24, and subjecting the composition to free radical polymerization.

[0174] 27. A polymer obtained by the method of item 26, preferably the polymer is a medical polymer, preferably a polymer for corneal contact lenses, preferably the corneal contact lenses are hard oxygen permeable corneal contact lenses.

[0175] 28. Use of the composition according to any one of items 21 to 25 in the preparation of a polymer, preferably the polymer is a medical polymer, preferably a polymer for corneal contact lenses, preferably the corneal contact lenses are hard oxygen permeable corneal contact lenses.

[0176] The applicant has found that for a polymer (or polymer composition) prepared by free radical polymerization using an olefinic unsaturated monomer in which the olefinic bond is derived from an isopropenyl group, especially a methacryloyl group (e.g., a methacryloyloxy group), it has a high residual monomer content; by partially replacing the olefinic unsaturated monomer with an olefinic unsaturated monomer in which the olefinic bond is derived from a vinyl group, especially from one or more olefinic unsaturated monomers of acryloxy, acrylamido, N-vinylamido, and vinylphenyl, the residual monomer content in the prepared polymer (or polymer composition) can be significantly reduced, and the prepared polymer therefore has high biocompatibility, so that it is suitable for use as a medical polymer material. And the free radical polymerization does not require complex process control. By further regulating the composition of the composition, the prepared polymer can also simultaneously achieve the desired hardness, oxygen permeability, water wettability, and processability.

[0177] In particular, when a polymer is prepared by free radical polymerization using a fluoroalkyl methacrylate as a monoalkenyl-functional hydrophobic fluorine-containing monomer component, a methacrylate-type silicon-containing monomer as a monoalkenyl-functional hydrophobic silicon-containing monomer component, and a methacryloyl-containing compound as a monoalkenyl-functional hydrophilic monomer component, the monoalkenyl-functional hydrophobic fluorine-containing monomer component can be partially replaced by a fluoroalkyl acrylate (e.g., a fluoroalkyl acrylate having the same fluorine-containing alkyl moiety) for the monoalkenyl-functional hydrophobic silicon-containing monomer component, and / or by partially replacing the methacrylate-type silicon-containing monomer with an acrylate-type or other vinyl-type silicon-containing monomer (e.g., a vinylbenzene-type silicon-containing monomer). The invention relates to a method for preparing a monoolefin functional hydrophilic monomer component comprising a methacrylic acid fluorinated alkyl ester (especially an acrylate or other vinyl silicon-containing monomer having the same silicon-containing functional part), and / or for a monoolefin functional hydrophilic monomer component, a methacrylic acid fluorinated alkyl ester is partially replaced by a methacrylic acid fluorinated alkyl ester, a monoolefin functional hydrophobic silicon-containing monomer component is only a methacrylate type silicon-containing monomer, and a monoolefin functional hydrophilic monomer component is only a methacrylic acid methacrylic acid fluorinated alkyl ester. Compared with the monoolefin functional hydrophobic fluorinated monomer component, the monoolefin functional hydrophobic silicon-containing monomer component is only a methacrylate type silicon-containing monomer, and the monoolefin functional hydrophilic monomer component is only a methacrylic acid ... Alternatively or additionally, the chemical residues of the produced polymers can be further reduced by using reactive monomers with higher purity and lower inhibitor content and / or by using reactive dyes (eg instead of conventional dyes). DETAILED DESCRIPTION

[0178] In the present application, unless otherwise specified, the temperature refers to room temperature (25° C.) and the pressure refers to atmospheric pressure.

[0179] In the present application, unless otherwise specified, the expression "%" used when referring to the content or concentration of a component in a composition means "mass %".

[0180] In the present application, unless otherwise specified, when referring to the content or concentration of a component in a composition, it is calculated based on the composition.

[0181] In the present application, unless otherwise specified, even if the term “about” is not used to modify a numerical value, the numerical value should be understood to be modified by “about”; the term “about” includes a deviation of ±5% of the stated numerical value, that is, for a numerical value a, whether or not it is modified by “about”, it should be understood to represent a range of a±5%a, that is, 0.95a to 1.05a.

[0182] In the present 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 "acrylamido" refers to "N-vinylamido" refers to "Vinylphenyl" refers to CH2=CH-Ph-, where Ph is phenylene such as 1,4-phenylene.

[0183] In the present application, the terms "first" and "second" are not intended to be restrictive, and they are not intended to indicate that other elements (such as compounds) must exist in the target object in addition to the stated elements (such as compounds). In other words, they may indicate the presence or absence of other elements in addition to the stated elements; they are only used to distinguish one compound, monomer, component or composition from another compound, monomer, component or composition.

[0184] In the present application, the term "fluorine-containing" or "silicon-containing" means that the stated compound includes fluorine or silicon, respectively, 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 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.

[0185] The present 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 use of the composition capable of free radical polymerization in preparing a polymer.

[0186] The present invention will be described in detail below.

[0187] Method for reducing residual monomer content in polymer compositions

[0188] In a first aspect, the present invention relates to a method for reducing the residual monomer content in a polymer composition (or polymer), wherein the polymer composition (or polymer) is a polymer composition (or polymer) prepared by free radical polymerization using a first free radical polymerizable composition, wherein the first free radical polymerizable composition may include a mixture of:

[0189] a first ethylenically unsaturated monomer component based on a first ethylenically unsaturated monomer, wherein the olefinic bond in the first ethylenically unsaturated monomer is derived from an isopropenyl group (CH2=C(CH3)-),

[0190] Free radical initiators,

[0191] Optionally, a UV absorber, and

[0192] Optionally, a coloring agent;

[0193] The method comprises:

[0194] (1) providing a second free radical polymerizable composition by replacing a portion of the first ethylenically unsaturated monomer component with a second ethylenically unsaturated monomer component based on a second ethylenically unsaturated monomer wherein the olefinic bond of the second ethylenically unsaturated monomer is derived from a vinyl group (CH2=CH-); and then subjecting the second free radical polymerizable composition to free radical polymerization; and / or

[0195] (2) before polymerization, before combining the components to form the first free radical polymerizable composition, the following purification step is performed: the first ethylenically unsaturated monomer component is purified to increase the content of the first ethylenically unsaturated monomer and / or reduce the content of the polymerization inhibitor, for example, to make the content of the first ethylenically unsaturated monomer therein 98 mass % or more, preferably 99 mass % or more and / or the content of the polymerization inhibitor is 50 ppm by mass or less; then free radical polymerization is performed; and / or

[0196] (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 containing an olefinic group, such as a methacryloyl group, to provide a second composition capable of free radical polymerization, 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-anthracenedione bis(2-propylene OIC) ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenethyl)methacrylamide.

[0197] 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 bulk. The polymerization can be carried out under an inert atmosphere (such as 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, so it is not repeated here.

[0198] The first to third embodiments (1) to (3) of the method will be described below.

[0199] First embodiment

[0200] In a first embodiment of the 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), wherein the polymer composition (or polymer) is a polymer composition (or polymer) prepared by free radical polymerization using a first free radical polymerizable composition, wherein the first free radical polymerizable composition may include a mixture of:

[0201] a first ethylenically unsaturated monomer component based on a first ethylenically unsaturated monomer, wherein the olefinic bond in the first ethylenically unsaturated monomer is derived from an isopropenyl group (CH2=C(CH3)-),

[0202] Free radical initiators,

[0203] Optionally, a UV absorber, and

[0204] Optionally, a coloring agent;

[0205] The method comprises:

[0206] (1) providing a second free radical polymerizable composition by replacing a portion of a first ethylenically unsaturated monomer component with a second ethylenically unsaturated monomer component based on a second ethylenically unsaturated monomer wherein the olefinic bond of the second ethylenically unsaturated monomer is derived from a vinyl group (CH2=CH-); and then subjecting the second free radical polymerizable composition to free radical polymerization.

[0207] In the present application, unless otherwise specified, the term "Xth monomer component based on ...Xth monomer" means that the monomer component mainly includes the mentioned monomer compound, for example, at least 90% by mass based on the total weight of the monomer component, for example, the following amounts of the mentioned monomer compound: 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, by-products generated during the preparation, storage, and transportation of the compound, and inhibitors added for stability (avoiding polymerization) during storage and transportation. This definition also applies to other monomer components capable of free radical polymerization, including crosslinking agent components and reactive dye components.

[0208] The method includes replacing a portion of the first ethylenically unsaturated monomer component with a second ethylenically unsaturated monomer component, so as to replace a portion of the first ethylenically unsaturated monomer with the second ethylenically unsaturated monomer. The replacement ratio of the first ethylenically unsaturated monomer component and the first ethylenically unsaturated monomer (i.e., the sum of the mass of the second ethylenically unsaturated monomer component relative to the mixture of the first ethylenically unsaturated monomer component and the second ethylenically unsaturated monomer component after replacement, and the sum of the mass of the second ethylenically unsaturated monomer relative to the mixture of the first ethylenically unsaturated monomer and the second ethylenically unsaturated monomer) is not particularly limited, and can be appropriately selected according to the properties of the polymer (or polymer composition) to be prepared, for example, each 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, 68 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 mass %, or a range limited by any two thereof.

[0209] The applicant has found that when monomers in which the olefinic bonds are derived from isopropenyl CH2=C(CH3)- are partially replaced by monomers in which the olefinic bonds are derived from vinyl (CH2=CH-), for example, when monomers in which the olefinic bonds are derived from methacryloyl groups such as methacryloyloxy groups are partially replaced by monomers in which the olefinic bonds are derived from acryloyloxy groups, acrylamido groups, N-vinylamido groups and / or vinylphenyl groups, the residual monomer content in the prepared polymer (or polymer composition) can be significantly reduced.

[0210] Preferably, the olefinic bond in the first ethylenically unsaturated monomer may be derived from a methacryloxy group, and the olefinic bond in the second ethylenically unsaturated monomer may be derived from one or more of the following: acryloxy, acrylamido, N-vinylamido, vinylphenyl.

[0211] Preferably, the first ethylenically unsaturated monomer and the second ethylenically unsaturated monomer may have the same or different, preferably the same, ethylenic functionality; for example, the first ethylenically unsaturated monomer and the second ethylenically unsaturated monomer may both be monoethylenically functional ethylenically unsaturated monomers.

[0212] Preferably, the first ethylenically 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.

[0213] For example, the first ethylenically 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 ethylenically 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.

[0214] Preferably, the first hydrophobic monomer differs from the second hydrophobic monomer only in that the methacryloxy group in the first hydrophobic monomer is replaced by an acryloxy group, a vinylphenyl group or a combination thereof in the second hydrophobic monomer.

[0215] Preferably, the first hydrophilic monomer differs from the second hydrophilic monomer only in that the methacryloxy group in the first hydrophilic monomer is replaced by the acryloxy group in the second hydrophilic monomer.

[0216] Preferably, the first ethylenically unsaturated monomer may include or be a first hydrophobic fluorine-containing monomer containing a methacryloyl group, such as a hydrophobic methacrylate fluoroalkyl ester 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.

[0217] For example, the first ethylenically unsaturated monomer may include or be a first hydrophobic fluorine-containing monomer containing a methacryloyl group, such as a hydrophobic methacrylate fluorine-containing alkyl ester 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 ethylenically unsaturated monomer may include or be a second hydrophobic fluorine-containing monomer, such as a hydrophobic methacrylate fluorine-containing alkyl ester monomer, a second hydrophobic silicon-containing 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.

[0218] Preferably, the first hydrophobic fluorine-containing monomer differs from the second hydrophobic fluorine-containing monomer only in that the methacryloyloxy group in the first hydrophobic fluorine-containing monomer is replaced by the acryloyloxy group in the second hydrophobic fluorine-containing monomer.

[0219] Preferably, the first hydrophobic silicon-containing monomer differs from the second hydrophobic silicon-containing monomer only in that the methacryloxy group in the first hydrophobic silicon-containing monomer is replaced by an acryloxy group, a vinylphenyl group or a combination thereof in the second hydrophobic silicon-containing monomer.

[0220] Preferably, the first hydrophilic monomer differs from the second hydrophilic monomer only in that the methacryloxy group in the first hydrophilic monomer is replaced by the acryloxy group in the second hydrophilic monomer.

[0221] Preferably, the first ethylenically unsaturated monomer may include or be a monoolefinic functional first hydrophobic fluorine-containing monomer containing a methacryloyl group, such as a hydrophobic fluoroalkyl methacrylate monomer, a monoolefinic functional first hydrophobic silicon-containing monomer containing a methacryloyl group, such as a silicon-containing hydrophobic methacrylate monomer, a monoolefinic functional first hydrophilic monomer containing a methacryloyl group, or any combination thereof.

[0222] For example, the first ethylenically unsaturated monomer may include or be a monoolefinic functional first hydrophobic fluorine-containing monomer containing methacryloyl, such as a hydrophobic fluorine-containing alkyl methacrylate monomer, a monoolefinic functional first hydrophobic silicon-containing monomer containing methacryloyl, such as a silicon-containing hydrophobic methacrylate monomer, and a monoolefinic functional first hydrophilic monomer containing methacryloyl, and the second ethylenically unsaturated monomer may include or be a monoolefinic functional second hydrophobic fluorine-containing monomer, such as a hydrophobic fluorine-containing alkyl acrylate monomer, a monoolefinic functional second hydrophobic silicon-containing monomer, such as a silicon-containing hydrophobic acrylate monomer, a vinylphenyl-containing silane or a combination thereof, a monoolefinic functional second hydrophilic monomer, or a combination thereof, preferably a combination thereof.

[0223] Preferably, the first hydrophobic fluorine-containing monomer differs from the second hydrophobic fluorine-containing monomer only in that the methacryloyloxy group in the first hydrophobic fluorine-containing monomer is replaced by the acryloyloxy group in the second hydrophobic fluorine-containing monomer.

[0224] Preferably, the first hydrophobic silicon-containing monomer differs from the second hydrophobic silicon-containing monomer only in that the methacryloxy group in the first hydrophobic silicon-containing monomer is replaced by an acryloxy group, a vinylphenyl group or a combination thereof in the second hydrophobic silicon-containing monomer.

[0225] Preferably, the first hydrophilic monomer differs from the second hydrophilic monomer only in that the methacryloxy group in the first hydrophilic monomer is replaced by the acryloxy group in the second hydrophilic monomer.

[0226] Preferably, when the first ethylenically 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 / (first hydrophobic monomer+first hydrophilic monomer) in the first composition or the first ethylenically unsaturated monomer, the mass ratio of the second hydrophobic monomer / (first hydrophobic monomer+second hydrophilic monomer) in the second composition, and the mass ratio of the second hydrophilic monomer / (first hydrophilic monomer+second hydrophilic monomer) are not particularly limited and may be appropriately selected according to the intended purpose, for example, each 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, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35 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 limited by any two of them.

[0227] Preferably, the mass ratio of the second hydrophobic monomer / (the first hydrophobic monomer+the second hydrophobic monomer) may 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 mass %, or a range limited by any two of them. Preferably, the mass ratio of the second hydrophilic monomer / (the first hydrophilic monomer+the second hydrophilic monomer) may 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, 58 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 them. 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 performance balance.

[0228] Preferably, when the first ethylenically unsaturated monomer includes or is a first hydrophobic fluorinated monomer containing a methacryloyl group, such as a hydrophobic methacrylate fluorinated alkyl ester monomer, a first hydrophobic silicon-containing 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 / (the first hydrophobic fluorinated monomer+the first hydrophobic silicon-containing monomer+the first hydrophilic monomer) in the first composition or the first ethylenically unsaturated monomer, the mass ratio of the first hydrophobic silicon-containing monomer / (the first hydrophobic fluorinated monomer+the first hydrophobic fluorinated monomer) in the first composition or the first ethylenically unsaturated monomer, the mass ratio of the first hydrophobic silicon-containing monomer / (the first hydrophobic fluorinated ...philic monomer) in the first composition or the first ethylenically unsaturated monomer, the mass ratio of the first hydrophobic silicon-containing monomer / (the first hydrophobic The mass ratio of the first hydrophilic monomer / (the first hydrophobic fluorinated monomer+the first hydrophobic silicon-containing monomer+the first hydrophilic monomer) in the first composition, the mass ratio of the second hydrophobic fluorinated monomer / (the first hydrophobic fluorinated monomer+the second hydrophobic fluorinated monomer) in the second composition, the mass ratio of the second hydrophobic silicon-containing monomer / (the first hydrophobic silicon-containing monomer+the second hydrophobic silicon-containing monomer), the mass ratio of the second hydrophobic fluorinated monomer / (the first hydrophobic silicon-containing monomer+the second hydrophobic silicon-containing monomer), the mass ratio of the second hydrophobic fluorinated monomer+the second hydrophobic silicon-containing monomer) / (the first hydrophobic fluorinated monomer+the second hydrophobic fluorinated monomer+the first hydrophobic silicon-containing monomer+the second hydrophobic silicon-containing monomer) The mass ratio of the first hydrophilic monomer / (the first hydrophilic monomer+the second hydrophilic monomer) can 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, 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, 99, 99.5, 99.8, 99.9, 100% by mass, or a range defined by any two of them.

[0229] Preferably, the mass ratio of the second hydrophobic fluorine-containing monomer / (the first hydrophobic fluorine-containing monomer+the second hydrophobic fluorine-containing monomer) and the mass ratio of the second hydrophobic silicon-containing monomer / (the first hydrophobic silicon-containing monomer+the second hydrophobic silicon-containing monomer) in the second composition may be independently 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 mass %, or the range limited by any two thereof. Preferably, the mass ratio of (second hydrophobic fluorine-containing monomer + second hydrophobic silicon-containing monomer) / (first hydrophobic fluorine-containing monomer + second hydrophobic fluorine-containing monomer + first hydrophobic silicon-containing monomer + second hydrophobic silicon-containing monomer) may 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 limited by any two of them. Preferably, the mass ratio of the second hydrophilic monomer / (the first hydrophilic monomer+the second hydrophilic monomer) may 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, 60 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 them. 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 performance balance.

[0230] Preferably, the second free radical polymerizable composition may include:

[0231] (1) A monoethylenically functional hydrophobic fluorinated monomer component which may include or consist of:

[0232] (1-1) a first hydrophobic fluorine-containing monomer component based on a fluoroalkyl methacrylate as a first hydrophobic fluorine-containing monomer;

[0233] and

[0234] (1-2) an optional second hydrophobic fluorine-containing monomer component based on a fluorine-containing alkyl acrylate as a second hydrophobic fluorine-containing monomer;

[0235] (2) a monoolefin-functional hydrophobic silicon-containing monomer component, which may include or consist of:

[0236] (2-1) a first hydrophobic silicon-containing monomer component based on a silicon-containing methacrylate as a first hydrophobic silicon-containing monomer;

[0237] and

[0238] (2-2) an optional second hydrophobic silicon-containing monomer component based on a silicon-containing acrylate or a vinylphenyl-containing silane as the second hydrophobic silicon-containing monomer;

[0239] (3) A monoethylenic functional hydrophilic monomer component which may include, or consist of:

[0240] (3-1) a first hydrophilic monomer component based on a first hydrophilic monomer containing a methacryloyl group;

[0241] and / or

[0242] (3-2) a second hydrophilic monomer component based on a second hydrophilic monomer containing an acryloxy group, an acrylamido group and / or an N-vinylamido group;

[0243] (4) optionally, a crosslinker component based on a diene-functional or higher crosslinker;

[0244] (5) free radical initiator;

[0245] (6) optionally, a UV absorber;

[0246] When the first hydrophilic monomer is present, one, two or three of the second hydrophobic fluorine-containing monomer, the second hydrophobic silicon-containing monomer, and the second hydrophilic monomer are present.

[0247] The second composition may include a monoalkenyl functional hydrophobic fluorinated monomer component. The amount of the monoalkenyl functional 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 mass %, such as 40-50 mass %, such as the following amount of monoalkenyl functional hydrophobic fluorinated monomer component: 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 mass %, or a range limited by any two thereof.

[0248] The monoethylenically functional hydrophobic fluoromonomer component may comprise, or consist of, a first hydrophobic fluoromonomer component based on a fluoroalkyl methacrylate as a first hydrophobic fluoromonomer, and optionally, a second hydrophobic fluoromonomer component based on a fluoroalkyl acrylate as a second hydrophobic fluoromonomer.

[0249] The applicant has found that when the monoolefinic 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 monoolefinic functional hydrophobic fluorinated monomer component only uses the first hydrophobic fluorinated monomer.

[0250] The number of carbon atoms of the fluorinated alkyl group in the fluoroalkyl methacrylate as the first hydrophobic fluorinated monomer and the number of carbon atoms of the fluorinated alkyl group in the fluoroalkyl acrylate as the second hydrophobic fluorinated monomer are not particularly limited, and for example, they may each independently be 1-20, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or a range limited by any two of them.

[0251] Preferably, the first hydrophobic fluorine-containing monomer may be a C1-C10 fluorine-containing alkyl methacrylate. The first hydrophobic fluorine-containing monomer may be a single compound or a mixture of two or more compounds.

[0252] For example, the carbon number of the fluorinated alkyl group may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or a range limited by any two of them, that is, the alkyl group may 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, isoheptyl, sec-heptyl, tert-heptyl, neoheptyl), octyl (e.g., n-octyl, isooctyl, sec-octyl, tert-octyl, neo-octyl), nonyl (e.g., n-nonyl, isononyl, sec-nonyl, tert-nonyl, neononyl), decyl (e.g., n-decyl, isodecyl, sec-decyl, tert-decyl, neodecyl), or any combination thereof.

[0253] The number of fluorine substituents in the fluorine-containing alkyl group is not particularly limited, and for an alkyl group with a carbon number of n, the number of fluorine substituents may be, for example, in the range of 1 to 2n+1. That is, for a carbon number of 1, the number of fluorine substituents may be 1, 2, or 3; for a carbon number of 10, the number of fluorine substituents may 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 numbers, the number of fluorine substituents may be any value from 1 to the value corresponding to 2n+1 listed above for a carbon number of 10.

[0254] Preferably, the first hydrophobic fluorine-containing monomer is a C1-C6 fluorine-containing alkyl methacrylate, preferably a C2-C5 fluorine-containing alkyl methacrylate, and more preferably a C2-C3 fluorine-containing alkyl methacrylate. For example, the first hydrophobic fluorine-containing 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, for example, the first hydrophobic fluorine-containing monomer may be one or more selected from trifluoroethyl methacrylate and hexafluoroisopropyl methacrylate.

[0255] Preferably, there is a second hydrophobic fluorinated monomer component in the second composition. When present, the amount of the second hydrophobic fluorinated monomer relative to the total mass of the first hydrophobic fluorinated monomer and the second hydrophobic fluorinated monomer is not particularly limited and can be appropriately selected according to the intended purpose. For example, when the total mass of the first hydrophobic fluorinated monomer and the second hydrophobic fluorinated monomer 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, 94, 95, 96, 97, 98, 99 parts by mass, or a range defined by any two of them. Preferably, the first hydrophobic fluorinated monomer and the second hydrophobic fluorinated monomer may be present in a mass ratio of 30:70-80:20; within the preferred range, the prepared polymer has significantly reduced monomer residues; and in addition, it may have good hardness, oxygen permeability, static contact angle, water absorption, and may improve at least one of hardness and oxygen permeability. More preferably, the first hydrophobic fluorinated monomer and the second hydrophobic fluorinated monomer may be present in a mass ratio of 50:50-80:20, for example, 70:30-80:20, within the preferred range, the prepared polymer may have further improved hardness.

[0256] The second hydrophobic fluorine-containing monomer may be a fluorine-containing alkyl acrylate. The above description of the number of carbon atoms and the number of fluorine substituents in the fluorine-containing alkyl group of the first hydrophobic fluorine-containing monomer also applies here. No further description is given here. The second hydrophobic fluorine-containing monomer may be a single compound or a mixture of two or more compounds.

[0257] The fluoroalkyl group in the second hydrophobic fluorine-containing monomer may be the same as or different from the fluoroalkyl group in the first hydrophobic fluorine-containing monomer, preferably the same. When the fluoroalkyl group in the second hydrophobic fluorine-containing monomer is the same as the fluoroalkyl group in the first hydrophobic fluorine-containing monomer, it is more helpful to reduce the monomer residue in the prepared polymer.

[0258] Preferably, the second hydrophobic fluorine-containing monomer may be C1-C10 fluorine-containing alkyl acrylate, preferably C1-C6 fluorine-containing alkyl acrylate, preferably C2-C5 fluorine-containing alkyl acrylate, more preferably C2-C3 fluorine-containing alkyl acrylate, preferably the second hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl acrylate, hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, more preferably, the second hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl acrylate and hexafluoroisopropyl acrylate.

[0259] Preferably, the first hydrophobic fluorine-containing monomer is selected from one or more of hexafluoroisopropyl methacrylate and trifluoroethyl methacrylate; and the second hydrophobic fluorine-containing monomer is selected from one or more of hexafluoroisopropyl acrylate and trifluoroethyl acrylate; for example, the first hydrophobic fluorine-containing monomer is hexafluoroisopropyl methacrylate and the second hydrophobic fluorine-containing monomer is hexafluoroisopropyl acrylate, or the first hydrophobic fluorine-containing monomer is trifluoroethyl methacrylate and the second hydrophobic fluorine-containing monomer is trifluoroethyl acrylate.

[0260] The second composition may include a monoalkenyl-functional hydrophobic silicon-containing monomer component. The amount of the monoalkenyl-functional 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, such as the following amount of a monoalkenyl-functional 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 of them.

[0261] The mono-ethylenically functional hydrophobic silicon-containing monomer component may include or consist of 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.

[0262] The applicant has found 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, the chemical residue (residual monomer content) in the polymer prepared under the same polymerization conditions can be reduced compared to the case where the monoalkenyl-functional hydrophobic silicon-containing monomer component only uses the first hydrophobic silicon-containing monomer, and that replacing a portion of the first hydrophobic silicon-containing monomer with the second hydrophobic silicon-containing monomer in the same amount can more significantly reduce the chemical residue (residual monomer content) in the polymer prepared under the same polymerization conditions compared to the case where only a portion of the first hydrophobic fluorine-containing monomer is replaced with the second hydrophobic fluorine-containing monomer.

[0263] 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 , wherein L1 is a C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10), preferably a C3-C6 divalent alkylene group, optionally including one or more groups selected from an ether-O-atom group, a -OH group, such as a methylene group, an ethylene group, an n- or iso-propylene group, an n-, iso- or tert-butylene group, an n-, iso- or tert-pentylene group, an n-, iso- or tert-hexylene group, an n-, iso- or tert-hexylene group, an n-, iso- R1 is the same as or different from each other and is 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, isopentyl, sec-pentyl, tert-pentyl, neopentyl), R2 is the same as or different from each other and is each independently C1-C6 alkyl (for example, methyl, ethyl, propyl (for example, n-propyl, isopropyl), butyl (for example, n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (for example, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl), hexyl (for example, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, neohexyl)) or -Si(R3 )3, wherein R3 are the same as or different from each other and are each independently C1-C6 alkyl ((for example, methyl, ethyl, propyl (for example, n-propyl, isopropyl), butyl (for example, n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (for example, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl), hexyl (for example, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, neohexyl)), preferably methyl, and m is 0, 1, 2, or 3, preferably 0 or 1.

[0264] The first hydrophobic silicon-containing monomer may be a single compound or a mixture of two or more compounds.

[0265] Preferably, the first hydrophobic silicon-containing monomer is selected from one or more of methacryloxypropyl tris(trimethylsiloxy)silane and (3-methacryloxy-2-hydroxypropoxy)propyl bis(trimethylsiloxy)methylsilane.

[0266] Preferably, a second hydrophobic silicon-containing monomer component is present in the second composition. When present, the amount of the second hydrophobic silicon-containing monomer relative to the total mass of the first hydrophobic silicon-containing monomer and the second hydrophobic silicon-containing monomer is not particularly limited and can be appropriately selected according to the intended purpose. For example, when the total mass of the first hydrophobic silicon-containing monomer and the second hydrophobic silicon-containing monomer 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, 94, 95, 96, 97, 98, 99 parts by mass, or a range defined by any two of them. Preferably, the first hydrophobic silicon-containing monomer and the second hydrophobic silicon-containing monomer may be present in a mass ratio of 30:70-80:20; within the preferred range, the prepared polymer has significantly reduced monomer residues; and in addition, it may have good hardness, oxygen permeability, static contact angle, water absorption, and may 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, and within the preferred range, the prepared polymer may have further improved hardness.

[0267] 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-n, wherein Ph is a phenylene group such as a 1,4-phenylene group, L2 is 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 a C3-C6 divalent alkylene group (e.g., a methylene group, an ethylene group, a n- or i-propylene group, a n-, i- or t-butylene group, a n-, i- or t-pentylene group, a n-, i- or t-hexylene group) which optionally includes one or more of an ether-O-atom group and an -OH group. R4 is the same as or different from each other and is the same as or different from R1 and is each 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., R5 is the same or different from each other and is the same or different from R2 and is 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)) or -Si(R6) 3, wherein R6 are the same as or different from each other and are the same as or different from R3 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, n and m are the same as or different and are 0, 1, 2, or 3, preferably 0 or 1.

[0268] The second hydrophobic silicon-containing monomer may be a single compound or a mixture of two or more compounds.

[0269] Preferably, -Si(R4) n (OR5) 3-n Partially with -Si(R1) m (OR2) 3-m Preferably, at least a portion, for example, all, of the second hydrophobic silicon-containing monomers -Si(R4) n (OR5) 3-n Partially with -Si(R1) in the first hydrophobic silicon-containing monomer m (OR2) 3-m When -Si(R4) in the first hydrophobic silicon-containing monomer and the second hydrophobic silicon-containing monomern (OR5) 3-n Partially with -Si(R1) in the first hydrophobic silicon-containing monomer m (OR2) 3-m When the two parts are the same, it helps to reduce the monomer residue in the prepared polymer.

[0270] Preferably, -L2-Si(R4) n (OR5) 3-n Partially compatible with -L1-Si(R1) m (OR2) 3-m Preferably, at least a portion, for example, all, of the second hydrophobic silicon-containing monomers -L2-Si(R4) n (OR5) 3-n Partially with -L1-Si(R1) in the first hydrophobic silicon-containing monomer m (OR2) 3-m When -L2-Si(R4) in the second hydrophobic silicon-containing monomer n (OR5) 3-n Partially with -L1-Si(R1) in the first hydrophobic silicon-containing monomer m (OR2) 3-m When the two parts are the same, it is more helpful to reduce the monomer residue in the prepared polymer.

[0271] Preferably, the second hydrophobic silicon-containing monomer is selected from one or more of acryloxypropyl tris(trimethylsiloxy)silane, (3-acryloxy-2-hydroxypropoxy)propyl bis(trimethylsiloxy)methylsilane and p-vinylphenyl tris(trimethylsiloxy)silane.

[0272] Preferably, the first hydrophobic silicon-containing monomer is selected from methacryloxypropyl tris(trimethylsiloxy)silane, and the second hydrophobic silicon-containing monomer is selected from one or more of acryloxypropyl tris(trimethylsiloxy)silane and p-vinylphenyl tris(trimethylsiloxy)silane, preferably acryloxypropyl tris(trimethylsiloxy)silane.

[0273] 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 mass %, such as 5-10 mass %, such as the following amount of monoalkenyl functional hydrophilic monomer component: 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 mass %, or a range limited by any two thereof.

[0274] The monoolefin functional hydrophilic monomer component may include or consist of a first hydrophilic monomer component based on a first hydrophilic monomer containing a methacryloyl group and / or a second hydrophilic monomer component based on a second hydrophilic monomer containing an acryl group, an acrylamido group and / or an N-vinylamido group. The second hydrophilic monomer containing an acryl group, an acrylamido group and / or an N-vinylamido group may be a hydrophilic monomer containing an acryl group, a hydrophilic monomer containing an acrylamido group, a hydrophilic monomer containing an N-vinylamido group or any combination thereof.

[0275] The applicant has found that when part 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.

[0276] 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.

[0277] Preferably, the first hydrophilic monomer may be one or more selected from methacrylic acid, hydroxyethyl methacrylate, methacrylamide, and N,N-dimethylmethacrylamide.

[0278] In an embodiment, the second hydrophilic monomer is a hydrophilic compound containing an acryl group, an acrylamido group and / or an N-vinylamido group. The second hydrophilic monomer may be a single compound or a mixture of two or more compounds.

[0279] When the second hydrophilic monomer is present, the amount of the second hydrophilic monomer relative to the total mass of the first hydrophilic monomer and the second hydrophilic monomer is not particularly limited and can be appropriately selected according to the intended purpose. For example, when the total mass of the first hydrophilic monomer and the second hydrophilic monomer 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 94, 95, 96, 97, 98, 99, 100 parts by mass or a range limited by any two of them. 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 the preferred range, the prepared polymer has significantly reduced monomer residues; and can also have good hardness, oxygen permeability, static contact angle, 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, and within the preferred range, the prepared polymer can have improved hardness and processability.

[0280] Preferably, the second hydrophilic monomer has similar or identical functional groups to the first hydrophilic monomer except for the alkenyl moiety. For example, the second hydrophilic monomer is different from the first hydrophilic monomer only in that the second hydrophilic monomer uses an acryloyl group instead of the methacryloyl group in the first hydrophilic monomer. When the second hydrophilic monomer has similar or identical functional groups to the first hydrophilic monomer except for the alkenyl moiety, it is more helpful to reduce the monomer residue of the prepared polymer.

[0281] Preferably, the second hydrophilic monomer is selected from one or more of acrylic acid, hydroxyethyl acrylate, acrylamide, N,N-dimethylacrylamide, N-vinyl pyrrolidone, and N-methyl-N-vinylacetamide.

[0282] 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-vinyl pyrrolidone (NVP) and N,N-dimethylacrylamide, preferably acrylic acid.

[0283] In the second composition, when the first hydrophilic monomer is present, one, two or three, preferably three (i.e. all) of the second hydrophobic fluorine-containing monomer, the second hydrophobic silicon-containing monomer, and the second hydrophilic monomer are present; in this case, compared with the corresponding case where only the first hydrophobic fluorine-containing 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 (i.e. all) of the second hydrophobic fluorine-containing monomer, the second hydrophobic silicon-containing monomer, and the second hydrophilic monomer are present, the chemical residue (residual monomer content) in the polymer prepared under the same polymerization conditions can be further significantly reduced.

[0284] In the second composition, when the first hydrophilic monomer is absent and the second hydrophilic monomer is present, the second hydrophobic fluorine-containing monomer and / or the second hydrophobic silicon-containing monomer may not be present, or one or both of the second hydrophobic fluorine-containing 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 fluorine-containing monomer and the second hydrophobic silicon-containing monomer are present in addition to the first hydrophobic fluorine-containing 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 relative to the corresponding situation where only the first hydrophobic fluorine-containing monomer, the first hydrophobic silicon-containing monomer and the second hydrophilic monomer are present; when two (i.e., all) of the second hydrophobic fluorine-containing 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 further significantly reduced.

[0285] The first and second compositions may optionally include a crosslinker component based on a crosslinker having a diene functional group or more. When the first and second compositions further include a crosslinker, the mechanical properties of the prepared polymer can be improved. The amount of the crosslinker component is not particularly limited and may 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, the following amount of crosslinker component: 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 of them.

[0286] Preferably, the crosslinking agent is selected from alkyl glycol dimethacrylate, preferably neopentyl glycol dimethacrylate; a siloxane-containing oligomer, preferably 1,3-bis(methacryloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, bis(methylpropoxy)butylpolydimethylsiloxane; or any combination thereof; for example, neopentyl glycol dimethacrylate and 1,3-bis(methacryloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, wherein For example, in a mass ratio of 10:90-90:10, for example, 20:80-80:20, for example, 30:70-70:30, for example, 40:60-60:40, for example, 50:50-60:40, for example, 45:55-55:45, for example, 50:50, for example, when the total mass of neopentyl glycol dimethacrylate and 1,3-bis(methacryloxypropyl)-1,1,3,3-tetrakis(trimethylsiloxy)disiloxane is 100 parts by mass, 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, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105 94, 95, 96, 97, 98, 99, 100 parts by mass, or a range defined by any two of them.

[0287] 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 mass %, such as 0.5-1.0 mass %, such as the following amount of initiator: 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 mass %, or the range defined by any two thereof.

[0288] The initiator is not particularly limited and may be a free radical initiator commonly used in the art such as azobisisobutyronitrile or azobisisoheptanenitrile.

[0289] According to the intended use (for example, to improve anti-aging properties), the first and second compositions may each further include an ultraviolet absorber, for example, 0.1-5.0 mass %, for example, 0.2-1.0 mass %, for example, 0.4-0.6 mass %, for example, the following amount of ultraviolet absorber: 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 mass %, or the range defined by any two thereof. The ultraviolet absorber is not particularly limited, for example, the ultraviolet absorber is 2-hydroxy-4-(methacryloyloxy)benzophenone.

[0290] Preferably, the second composition may include, based on the total mass of the second composition:

[0291] (1) 30-60 mass %, for example 40-50 mass %, of a monoethylenically functional hydrophobic fluorinated monomer component;

[0292] (2) 20-45 mass %, for example 30-40 mass %, of a monoethylenic functional hydrophobic silicon-containing monomer component;

[0293] (3) 3-20 mass %, for example 5-10 mass %, of a monoethylenic functional hydrophilic monomer component;

[0294] (4) optionally, 1-20 mass %, e.g., 5-15 mass %, of a crosslinker component based on a diene-functional or higher crosslinker; and

[0295] (5) 0.1-2.0 mass %, for example 0.5-1.0 mass %, of a free radical initiator.

[0296] (6) optionally, 0.1-5.0 mass %, such as 0.2-1.0 mass %, such as 0.4-0.6 mass % of an ultraviolet absorber; and

[0297] (7) Optionally, 0.001-0.5 mass %, for example 0.005-0.01 mass %, of a coloring agent.

[0298] The applicant has found that by regulating the composition of the second composition within the above range, the prepared polymer can also simultaneously achieve good hardness, oxygen permeability, water wettability and processability; and therefore, can be used to prepare, for example, corneal contact lenses such as hard oxygen permeable corneal contact lenses.

[0299] During the storage or preparation and purification process, the monomers of free radical polymerization are often polymerized due to the effects of factors such as light and heat. Adding a small amount of polymerization inhibitor can avoid this destructive reaction. Considering the reasons of transportation and storage stability, monomer suppliers dare not easily reduce the amount of polymerization inhibitor added. Therefore, for the polymer prepared by free radical polymerization using ethylenically unsaturated monomers (including the first ethylenically unsaturated monomer and the second ethylenically unsaturated monomer described herein) (including the hydrophobic monomers described herein (including the first and second hydrophobic monomers, the first and second hydrophobic fluorine-containing monomers, and the first and second hydrophobic silicon-containing monomers) and hydrophilic monomers (including the first and second hydrophilic monomers)), the above-mentioned monomer components used will also have higher impurities (including oligomers and polymers that may be produced during storage and transportation due to monomer polymerization) and polymerization inhibitor content. These monomers usually have relatively high molecular weight and boiling point. Usually, even if they are purified by methods such as distillation, the final purified product will also contain a certain amount of impurities and polymerization inhibitors.

[0300] The applicant has further discovered that, alternatively or additionally, when each reactive monomer, including the first ethylenically unsaturated monomer and the second ethylenically unsaturated monomer described herein, the hydrophobic monomers (including the first and second hydrophobic monomers, the first and second hydrophobic fluorine-containing monomers, and the first and second hydrophobic silicon-containing monomers) and the hydrophilic monomers (including the first and second hydrophilic monomers) involved therein, and the possible presence of a cross-linking agent, have a higher purity and a lower inhibitor content (i.e., are provided in the form of a raw material with a higher purity and a lower inhibitor content), the chemical residue (residual monomer content) in the polymer prepared under the same polymerization conditions can be further reduced.

[0301] Therefore, preferably, the method may include a purification step prior to polymerization and prior to providing the second free-radically polymerizable composition as follows:

[0302] (1) purifying the first ethylenically unsaturated monomer component to increase the content of the first ethylenically unsaturated monomer and / or reduce the content of the polymerization inhibitor therein, for example, to make the content of the first ethylenically unsaturated monomer therein 98 mass % or more, preferably 99 mass % or more and / or the content of the polymerization inhibitor therein be 50 ppm by mass or less; and / or

[0303] (2) Purifying the second ethylenically unsaturated monomer component to increase the content of the second ethylenically unsaturated monomer and / or reduce the content of the polymerization inhibitor therein, for example, to make the content of the second ethylenically unsaturated monomer therein 98% by mass or more, preferably 99% by mass or more and / or the content of the polymerization inhibitor therein be 50 ppm by mass or less.

[0304] Further preferably, the method may include the following purification step before providing the second free radical polymerizable composition prior to polymerization:

[0305] a) purifying the first hydrophobic fluorinated monomer component to increase the content of the first hydrophobic fluorinated monomer and / or reduce the content of the polymerization inhibitor therein, for example, to make the content of the first hydrophobic fluorinated monomer therein be 98 mass % or more, preferably 99 mass % or more and / or the content of the polymerization inhibitor be 50 ppm by mass or less; and / or

[0306] b) purifying the second hydrophobic fluorinated monomer component to increase the content of the second hydrophobic fluorinated monomer and / or reduce the content of the polymerization inhibitor therein, for example, to make the content of the second hydrophobic fluorinated monomer therein 98 mass % or more, preferably 99 mass % or more and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or

[0307] c) purifying the first hydrophobic silicon-containing monomer component to increase the content of the first hydrophobic silicon-containing monomer and / or reduce the content of the polymerization inhibitor therein, for example, to make the content of the first hydrophobic silicon-containing monomer therein be 98% by mass or more, preferably 99% by mass or more and / or the content of the polymerization inhibitor be 50 ppm by mass or less; and / or

[0308] d) purifying the second hydrophobic silicon-containing monomer component to increase the content of the second hydrophobic silicon-containing monomer and / or reduce the content of the polymerization inhibitor, for example, to make the content of the second hydrophobic silicon-containing monomer greater than 98% by mass, preferably greater than 99% by mass and / or the content of the polymerization inhibitor less than 50 ppm by mass; and / or

[0309] e) purifying the first hydrophilic monomer component to increase the content of the first hydrophilic monomer and / or reduce the content of the polymerization inhibitor therein, for example, to make the content of the first hydrophilic monomer therein 98 mass % or more, preferably 99 mass % or more and / or the content of the polymerization inhibitor therein is 50 ppm by mass or less; and / or

[0310] f) purifying the second hydrophilic monomer component to increase the content of the second hydrophilic monomer and / or reduce the content of the polymerization inhibitor therein, for example, to make the content of the second hydrophilic monomer therein 98 mass % or more, preferably 99 mass % or more and / or the content of the polymerization inhibitor therein 50 ppm by mass or less; and / or

[0311] g) purifying the crosslinker component based on a diene-functional or higher crosslinker to increase the crosslinker content and / or reduce the polymerization inhibitor content therein, for example, to make the crosslinker content therein 98 mass % or more, preferably 99 mass % or more and / or the polymerization inhibitor content therein 50 ppm by mass or less.

[0312] More preferably, the method comprises performing any one, two, three, four, five, six, or seven, i.e. all, of the above-mentioned purification steps a) to h), preferably all to reduce the monomer content of the corresponding monomer component and / or cross-linking agent component (for example, any one, two, three, four, five, six, or seven, i.e. all, of the first hydrophobic fluorine-containing monomer component, the second hydrophobic fluorine-containing 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 cross-linking agent component). and / or the cross-linking agent content is each independently increased to 98% by mass or more, preferably 99% by mass or more; and / or the polymerization inhibitor content in the corresponding monomer components (for example, the polymerization inhibitor content in any one, two, three, four, five, six, or seven of the first hydrophobic fluorine-containing monomer component, the second hydrophobic fluorine-containing 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 cross-linking agent component, preferably in all) is each independently reduced to 50 ppm by mass or less.

[0313] According to the intended use (for example, in the field of RGP materials, in order to distinguish the RGP lenses used for the left and right eyes), the first composition may further include a dye such as a non-reactive dye, and its amount is, for example, 0.001-0.5% by mass, such as 0.005-0.01% by mass, such as 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 the range defined by any two thereof.

[0314] Herein, 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, such as a methacryloyl group.

[0315] Applicants have found that, alternatively or additionally, when a reactive dye is used to partially or completely replace the non-reactive dye, the residual monomer content in the polymer produced can be further reduced; although the extent of this reduction is relatively small due to the relatively low amount of dye in the composition.

[0316] Therefore, preferably, the dye is a reactive dye selected from, for example, an alkenyl group-containing dye, for example, a methacryloyl group-containing dye, for example, one or more selected from 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone, 1,4-bis((2-hydroxyethyl)amino)-9,10-anthracenedione bis(2-propylene OIC)ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenethyl)methacrylamide.

[0317] Second embodiment

[0318] 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), wherein the polymer composition (or polymer) is a polymer composition (or polymer) prepared by free radical polymerization using a first free radical polymerizable composition, wherein the first free radical polymerizable composition may include a mixture of:

[0319] a first ethylenically unsaturated monomer component based on a first ethylenically unsaturated monomer, wherein the olefinic bond in the first ethylenically unsaturated monomer is derived from an isopropenyl group (CH2=C(CH3)-),

[0320] Free radical initiators,

[0321] Optionally, a UV absorber, and

[0322] Optionally, a coloring agent;

[0323] The method comprises (2) before polymerization and before combining the components to form the first composition capable of free radical polymerization, performing the following purification step: purifying the first ethylenically unsaturated monomer component to increase the content of the first ethylenically unsaturated monomer and / or reduce the content of the polymerization inhibitor therein, for example, so that the content of the first ethylenically unsaturated monomer therein 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.

[0324] Preferably, the method may further comprise: providing a second free radical polymerizable composition by replacing a portion of the first ethylenically unsaturated monomer component with a second ethylenically unsaturated monomer component based on a second ethylenically unsaturated monomer as follows: wherein the olefinic bond of the second ethylenically unsaturated monomer is derived from a vinyl group (CH2=CH-);

[0325] The second free radical polymerizable composition is then free radically polymerized.

[0326] All the above descriptions of the first embodiment of the first aspect of the present invention (including the description of the composition of the first composition and the second composition, and the description of the purification steps of various components) are applicable here, can be combined with the above-mentioned method of the second embodiment and its preferred embodiment, and constitute a further preferred embodiment of the second embodiment, which will not be repeated here.

[0327] Third embodiment

[0328] 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, wherein the polymer composition is a polymer composition prepared by free radical polymerization using a first free radical polymerizable composition, wherein the first free radical polymerizable composition may include a mixture of:

[0329] a first ethylenically unsaturated monomer component based on a first ethylenically unsaturated monomer, wherein the olefinic bond in the first ethylenically unsaturated monomer is derived from an isopropenyl group (CH2=C(CH3)-),

[0330] Free radical initiators,

[0331] Optionally, a UV absorber, and

[0332] Non-reactive stains;

[0333] The method comprises: (3) partially or completely replacing the non-reactive dye in the first composition capable of free radical polymerization with a reactive dye containing, for example, an alkenyl group, for example, a methacryloyl group, to provide a second composition capable of free radical polymerization, wherein the reactive dye is selected from, for example, one or more of 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone, 1,4-bis((2-hydroxyethyl)amino)-9,10-anthracenedione bis(2-propylene OIC) ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenethyl)methacrylamide;

[0334] Free radical polymerization is then carried out.

[0335] The amount of the dye in the second radically polymerizable composition may be, for example, 0.001-0.5% by mass, such as 0.005-0.01% by mass.

[0336] Preferably, the method may further comprise: providing the second free radical polymerizable composition by replacing a portion of the first ethylenically unsaturated monomer component with a second ethylenically unsaturated monomer component based on a second ethylenically unsaturated monomer as follows: wherein the olefinic bond of the second ethylenically unsaturated monomer is derived from a vinyl group (CH2=CH-);

[0337] The second free radical polymerizable composition is then free radically polymerized.

[0338] All the above descriptions about the first embodiment of the first aspect of the present invention (including the description of the composition of the first composition and the second composition, and the description of the purification steps of various components) are applicable here, and can be combined with the above-mentioned method of the third embodiment and its preferred embodiment, and constitute a further preferred embodiment of the third embodiment, which will not be repeated here.

[0339] By using the method of the present invention, the olefinic unsaturated monomers in which the olefinic bonds are derived from isopropenyl, particularly methacryloyl (e.g. methacryloyloxy) are partially replaced by olefinic unsaturated monomers in which the olefinic bonds are derived from vinyl, particularly one or more olefinic unsaturated monomers derived from acryloxy, acrylamido, N-vinylamido and vinylphenyl, which can significantly reduce the residual monomer content in the prepared polymer (or polymer composition), and the prepared polymer therefore has high biocompatibility, thereby being suitable for use as a medical polymer material. And the free radical polymerization does not require complex process control. By further regulating the composition of the second composition, the prepared polymer can also simultaneously achieve the desired hardness, oxygen permeability, water wettability and processability and other properties.

[0340] Polymer composition

[0341] A second aspect of the present invention relates to a polymer composition (or polymer) obtainable by the process according to the first aspect of the present invention.

[0342] The polymer according to the second aspect of the present invention may be a medical polymer, in particular a polymer for contact lenses, such as a polymer for hard oxygen permeable contact lenses.

[0343] All the above descriptions about the first aspect of the present invention are applicable here.

[0344] Free radical polymerizable composition

[0345] A third aspect of the present invention relates to a composition capable of free radical polymerization, which composition may include:

[0346] (1) A monoethylenically functional hydrophobic fluorinated monomer component comprising or consisting of:

[0347] (1-1) a first hydrophobic fluorine-containing monomer component based on a fluoroalkyl methacrylate as a first hydrophobic fluorine-containing monomer;

[0348] Preferably, the first hydrophobic fluorine-containing monomer is C1-C10 fluorine-containing alkyl methacrylate, preferably C1-C6 fluorine-containing alkyl methacrylate, preferably C2-C5 fluorine-containing alkyl methacrylate, more preferably C2-C3 fluorine-containing alkyl methacrylate; preferably, the first hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate; more preferably, the first hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl methacrylate and hexafluoroisopropyl methacrylate;

[0349] and

[0350] (1-2) an optional second hydrophobic fluorine-containing monomer component based on a fluorine-containing alkyl acrylate as a second hydrophobic fluorine-containing monomer;

[0351] 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, preferably the same;

[0352] Preferably, the second hydrophobic fluorine-containing monomer is C1-C10 fluorine-containing alkyl acrylate, preferably C1-C6 fluorine-containing alkyl acrylate, preferably C2-C5 fluorine-containing alkyl acrylate, more preferably C2-C3 fluorine-containing alkyl acrylate; preferably, the second hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl acrylate, hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate; more preferably, the second hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl acrylate and hexafluoroisopropyl acrylate;

[0353] Preferably, the first hydrophobic fluorine-containing monomer is selected from one or more of hexafluoroisopropyl methacrylate and trifluoroethyl methacrylate, and the second hydrophobic fluorine-containing monomer is selected from one or more of hexafluoroisopropyl acrylate and trifluoroethyl acrylate; preferably, the first hydrophobic fluorine-containing monomer is hexafluoroisopropyl methacrylate and the second hydrophobic fluorine-containing monomer is hexafluoroisopropyl acrylate, or the first hydrophobic fluorine-containing monomer is trifluoroethyl methacrylate and the second hydrophobic fluorine-containing monomer is trifluoroethyl acrylate;

[0354] (2) a monoolefin-functional hydrophobic silicon-containing monomer component comprising or consisting of:

[0355] (2-1) a first hydrophobic silicon-containing monomer component based on a silicon-containing methacrylate as a first hydrophobic silicon-containing monomer,

[0356] 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 , wherein L1 is a C1-C10, preferably C3-C6 divalent alkylene group, which optionally includes one or more of an ether -O-atom group and an -OH group, R1 is the same as or different from each other and is independently a C1-C6 alkyl group, preferably a methyl group, R2 is the same as or different from each other and is independently a C1-C6 alkyl group, preferably a methyl group, or -Si(R3)3, wherein R3 is the same as or different from each other and is independently a C1-C6 alkyl group, preferably a methyl group, and m is 0, 1, 2, or 3, preferably 0 or 1;

[0357] Preferably, the first hydrophobic silicon-containing monomer is selected from one or more of methacryloxypropyl tris(trimethylsiloxy)silane and (3-methacryloxy-2-hydroxypropoxy)propyl bis(trimethylsiloxy)methylsilane;

[0358] and

[0359] (2-2) an optional second hydrophobic silicon-containing monomer component based on a silicon-containing acrylate or a vinylphenyl-containing silane as the second hydrophobic silicon-containing monomer,

[0360] 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 , wherein Ph is a phenylene group such as a 1,4-phenylene group, L2 is the same as or different from L1 and is a C1-C10, preferably a C3-C6 divalent alkylene group which optionally includes one or more of an ether -O-atom group and a -OH group; R4 is the same as or different from each other and is the same as or different from R1 and is each independently a C1-C6 alkyl group, preferably a methyl group, R5 is the same as or different from each other and is the same as or different from R2 and is each independently a C1-C6 alkyl group, preferably a methyl group or -Si(R6)3, wherein R6 is the same as or different from each other and is the same as or different from R3 and is each independently a C1-C6 alkyl group, preferably a methyl group, and n is the same as or different from m and is 0, 1, 2 or 3, preferably 0 or 1;

[0361] Preferably, -Si(R4) n (OR5) 3-n Partially with -Si(R1)m(OR2) 3-m The parts are identical or different, preferably identical;

[0362] Preferably, -L2-Si(R4) n (OR5) 3-n Partially with -L1-Si(R1)m(OR2) 3-m The parts are identical or different, preferably identical;

[0363] Preferably, the second hydrophobic silicon-containing monomer is selected from one or more of acryloxypropyl tris(trimethylsiloxy)silane, (3-acryloxy-2-hydroxypropoxy)propyl bis(trimethylsiloxy)methylsilane and p-vinylphenyl tris(trimethylsiloxy)silane;

[0364] Preferably, the first hydrophobic silicon-containing monomer is selected from methacryloxypropyl tris(trimethylsiloxy)silane, and the second hydrophobic silicon-containing monomer is selected from one or more of acryloxypropyl tris(trimethylsiloxy)silane and p-vinylphenyl tris(trimethylsiloxy)silane, preferably acryloxypropyl tris(trimethylsiloxy)silane;

[0365] (3) a monoolefin-functional hydrophilic monomer component comprising or consisting of:

[0366] (3-1) a first hydrophilic monomer component based on a first hydrophilic monomer containing a methacryloyl group;

[0367] Preferably, the first hydrophilic monomer is selected from one or more of methacrylic acid, hydroxyethyl methacrylate, methacrylamide, and N,N-dimethylmethacrylamide;

[0368] and / or

[0369] (3-2) a second hydrophilic monomer component based on a second hydrophilic monomer containing an acryloxy group, an acrylamido group and / or an N-vinylamido group;

[0370] Preferably, 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;

[0371] Preferably, the second hydrophilic monomer is selected from one or more of acrylic acid, hydroxyethyl acrylate, acrylamide, N,N-dimethylacrylamide, N-vinyl pyrrolidone, and N-methyl-N-vinylacetamide;

[0372] 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-vinyl pyrrolidone (NVP) and N,N-dimethylacrylamide, preferably acrylic acid;

[0373] (4) optionally, a crosslinker component based on a diene-functional or higher crosslinker;

[0374] Preferably, the crosslinking agent with more than bis-alkenyl functionality is selected from: alkyl glycol dimethacrylate, preferably neopentyl glycol dimethacrylate; a siloxane-containing oligomer, preferably 1,3-bis(methacryloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, bis(methylpropoxy)butylpolydimethylsiloxane; or any combination thereof; for example, neopentyl glycol dimethacrylate and 1,3-bis(methacryloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, which are present in a mass ratio of, for example, 10:90-90:10, for example, 30:70-70:30, for example, 50:50-60:40;

[0375] (5) free radical initiators, such as azobisisobutyronitrile or azobisisoheptanenitrile;

[0376] (6) optionally, a UV absorber, such as 2-hydroxy-4-(methacryloyloxy)benzophenone; and

[0377] (7) optionally, 0.001-0.5 mass %, for example 0.005-0.01 mass %, of a coloring agent;

[0378] The composition may satisfy one, two or three of the following conditions (i)-(iii):

[0379] (i) when the first hydrophilic monomer is present, one, two or three of a second hydrophobic fluorine-containing monomer, a second hydrophobic silicon-containing monomer, and a second hydrophilic monomer are present; and / or

[0380] (ii) the content of the first hydrophobic fluorine-containing monomer in the first hydrophobic fluorine-containing monomer component, and / or the content of the second hydrophobic fluorine-containing monomer in the second hydrophobic fluorine-containing 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 crosslinker based on a diene-functional or higher crosslinker component are each independently 98% by mass or more, preferably 99% by mass or more; and / or

[0381] The content of the polymerization inhibitor in the first hydrophobic fluorine-containing monomer component, and / or the second hydrophobic fluorine-containing 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 cross-linking agent component is independently 50 ppm by mass or less; and / or

[0382] (iii) the composition further comprises a reactive dye, such as a reactive dye containing an alkenyl group, such as a reactive dye containing a methacryloyl group, which is selected from, for example, one or more reactive dyes selected from 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone, 1,4-bis((2-hydroxyethyl)amino)-9,10-anthracenedione bis(2-propylene OIC)ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenethyl)methacrylamide, and the amount thereof is, for example, 0.001-0.5% by mass, such as 0.005-0.01% by mass.

[0383] Preferably, the composition may include, based on the total mass of the composition:

[0384] (1) 30-60 mass %, for example 40-50 mass %, of a monoethylenically functional hydrophobic fluorinated monomer component;

[0385] (2) 20-45 mass %, for example 30-40 mass %, of a monoethylenic functional hydrophobic silicon-containing monomer component;

[0386] (3) 3-20 mass %, for example 5-10 mass %, of a monoethylenic functional hydrophilic monomer component;

[0387] (4) optionally, 1-20 mass %, e.g., 5-15 mass %, of a crosslinker component based on a diene-functional or higher crosslinker; and

[0388] (5) 0.1-2.0 mass %, for example 0.5-1.0 mass % of a free radical initiator; and

[0389] (6) Optionally, 0.1-5.0 mass %, such as 0.2-1.0 mass %, such as 0.4-0.6 mass % of an ultraviolet absorber.

[0390] Preferably, in the composition:

[0391] A second hydrophobic fluorinated monomer is present, preferably the first hydrophobic fluorinated monomer and the second hydrophobic fluorinated monomer are present in a mass ratio of 30:70-80:20, such as 50:50-80:20, such as 70:30-80:20; and / or

[0392] A second hydrophobic silicon-containing monomer is present, 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, such as 50:50-75:25; and / or

[0393] The first hydrophilic monomer and the second hydrophilic monomer are present, preferably the first hydrophilic monomer and the second hydrophilic monomer are present in a mass ratio of 0:100-85:15, such as 25:75-80:20, such as 40:60-75:25.

[0394] Preferably, a second hydrophobic fluorine-containing monomer, a second hydrophobic silicon-containing monomer, a first hydrophilic monomer and a second hydrophilic monomer are present in the composition.

[0395] The composition is particularly suitable for preparing medical polymers requiring high biocompatibility. In particular, by regulating the composition of the composition within the above range, the prepared polymer can also simultaneously achieve good hardness, oxygen permeability, water wettability and processability; and therefore, can be used to prepare, for example, corneal contact lenses such as hard oxygen permeable corneal contact lenses.

[0396] The above descriptions of all features, aspects and effects described in relation to the method of the first aspect of the present invention, including all descriptions of the composition of the second composition, such as the monoolefinic hydrophobic fluorine-containing monomer component and the first hydrophobic fluorine-containing monomer component and the optional second hydrophobic fluorine-containing monomer component contained therein, the monoolefinic hydrophobic silicon-containing monomer component and the first hydrophobic silicon-containing monomer component and the optional second hydrophobic silicon-containing monomer component contained therein, the monoolefinic hydrophilic monomer component and the first hydrophilic monomer component and / or the second hydrophilic monomer component contained therein, the crosslinker component and the crosslinker contained therein, the dye, the free radical initiator, the ultraviolet absorber, etc., are all applicable to the composition of the third aspect of the present invention and will not be described in detail herein.

[0397] The polymer prepared by 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:

[0398] (1) Total amount of known monomers remaining (mass %): 3.7 or less, 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 of them;

[0399] (2) Total amount of unknown impurities remaining (mass %): 2.4 or lower, 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 them;

[0400] (3) Total amount of residual monomers (mass %): 6.0 or less, for example, 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 the range defined by any two thereof;

[0401] (4) Shore D: 75 or higher, for example, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, or a range defined by any two thereof;

[0402] (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 48, 149, 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 a range limited by any two of them;

[0403] (6) Static contact angle (°): 45 or less, for example, 45, 44, 43, 42, 41, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26 or less, or a range defined by any two thereof;

[0404] (7) Water absorption (%): 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 limited by any two thereof;

[0405] (8) Visible spectrum transmittance (%): 89 or higher, for example, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, or even 100, or a range limited by any two of them.

[0406] In the present application, known monomer residues refer to residual unpolymerized monomers corresponding to the monomers used to prepare polymers; unknown impurity residues refer to residues other than known monomer residues; and total residual monomers refer to the sum of known monomer residues and unknown impurity residues.

[0407] Compared with the composition in which the monoalkenyl-functional hydrophobic fluorine-containing monomer component uses only methacrylic acid (e.g., C1-C10) fluorine-containing alkyl esters, the monoalkenyl-functional hydrophobic silicon-containing monomer component uses only methacrylate-type silicon-containing monomers, and the monoalkenyl-functional hydrophilic monomer component uses only methacryloyl-containing compounds, the polymer prepared by the composition of the third aspect of the present invention has a significantly reduced residual monomer content, and therefore has high biocompatibility, so that it is suitable for use as a medical polymer material. And the free radical polymerization does not require complex process control. And by regulating the composition of the composition, the prepared polymer can also simultaneously achieve good hardness, oxygen permeability, water wettability and processability; and therefore, it can be used to prepare, for example, corneal contact lenses such as hard oxygen permeable corneal contact lenses.

[0408] Therefore, preferably, the composition is a composition for preparing a medical polymer. In particular, the composition can be used to prepare a corneal contact lens, such as a hard oxygen permeable corneal contact lens.

[0409] Polymer preparation method

[0410] A fourth aspect of the present invention relates to a method for preparing a polymer, which comprises providing a composition according to the third aspect of the present invention, and subjecting the composition to free radical polymerization.

[0411] All the above descriptions about 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.

[0412] polymer

[0413] The fifth aspect of the present invention relates to a polymer obtained by free radical polymerization of a composition according to the third aspect of the present invention or a polymer obtained by a polymerization process according to the fourth aspect of the present invention.

[0414] Therefore, the polymer according to the fifth aspect of the present invention may be a medical polymer, in particular a polymer for contact lenses, such as a polymer for hard oxygen permeable contact lenses.

[0415] All the above descriptions about the third and fourth aspects of the present invention are applicable here.

[0416] use

[0417] The sixth aspect of the present invention relates to the use of the composition of the third aspect of the present invention in the preparation of polymers, such as medical polymers, in particular polymers for corneal contact lenses (or corneal contact lenses), such as polymers for hard gas permeable corneal contact lenses (or hard gas permeable corneal contact lenses).

[0418] All the above descriptions about the first to fifth aspects of the present invention are applicable here and will not be repeated here.

[0419] Example

[0420] The embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention.

[0421] Experimental raw materials

[0422] The information of the suppliers of experimental raw materials used in the examples is shown in Table 1 below:

[0423] Table 1

[0424]

[0425]

[0426]

[0427] Test Method

[0428] Monomer Residual Test

[0429] 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 by a precision lathe, and extracted with 10 mL of dichloromethane at a 37°C shaker for 48 hours. The obtained dichloromethane extract was detected by gas chromatography (detector FID, chromatographic column model DB200, injection port temperature 280°C, detector temperature 300°C, flow rate 1.0 mL / min, column temperature: starting temperature 30°C, maintained for 5 minutes, heated to 250°C at a rate of 10°C / min, maintained for 8 minutes, heated to 300°C at a rate of 10°C / min, maintained for 10 minutes). The standard curve prepared from the monomer substances of each copolymer component was taken to quantify the concentration of unpolymerized monomers in the dichloromethane extract, thereby calculating the residual amount of unpolymerized known monomers. The unknown monomer residue was calculated using a reference solution of one of the known monomers as a reference.

[0430] Hardness (Shore D)

[0431] The spare buckle pieces prepared in each embodiment were processed into samples with a diameter of 12 mm, a thickness of 3 mm, and flat, parallel and polished front and rear surfaces by a precision lathe. Two pieces of the above samples were superimposed on each other to form a sample with a thickness of 6 mm, and a Shore D hardness tester (model C022) equipped with an indenter specified in GB / T2411-2008 was used to perform three independent measurements at 20°C ± 5°C, and the arithmetic mean of the three measurements was calculated.

[0432] Oxygen permeability coefficient (Dk)

[0433] The spare buckle pieces prepared in each embodiment are processed into optical lenses with a diameter of 11 mm and 4 different thicknesses (thickness range 0.04-0.4 mm) by a precision lathe. The optical lens is set on a polarographic oxygen sensor, and then its upper side is covered with a mesh carrier. The polarographic oxygen sensor consists of a gold cathode with a diameter of 4 mm and a silver ring anode. The entire probe with the test sample is placed in a heating box at a temperature of 35°C ± 0.5°C. The box is stocked with water to maintain the relative humidity of the saturated water atmosphere on the exposed surface of the test sample to be not less than 98%. The stable current value is read and recorded. Calculate the t / Dk of the four samples with significantly different thickness (t) values, and perform a linear regression of t / Dk relative to t. The reciprocal of the regression slope is the Dk of the sample. The unit is unified as 10 -11 (cm 2 / s[mLO2 / (mL·mmHg]).

[0434] Static contact angle

[0435] The spare buckle pieces prepared in each embodiment are processed into buckle pieces with a diameter of 12 mm and a thickness of 4 mm by a precision lathe, and the surface is turned and polished to be consistent with the finished contact lens. Before measurement, the sample is placed in a standard PBS buffered saline solution (1L of water contains 8.300g of sodium chloride, 0.528g of sodium dihydrogen phosphate (containing 2 crystal waters), and 5.993g of disodium hydrogen phosphate (containing 12 crystal waters)) for deep rinsing. Then it is placed in a standard PBS buffered saline solution for at least 24 hours to allow it to reach equilibrium. Then use the contact angle measuring equipment of Ramé-Hart Instrument Co. to measure, read the value displayed by the contact angle equipment, measure 5 times independently, record 10 contact angle readings each time, and the arithmetic mean of the 50 readings is recorded as the "contact angle" of the surface of the sample being measured.

[0436] Water absorption

[0437] The spare buckle pieces prepared in each embodiment were processed into buckle pieces with a diameter of 11 mm and a thickness of 4 mm by a precision lathe, with a mass of 6-7 g per group. After drying and constant weight, the weight (g) of each group was measured. After each group was immersed in a container containing 20 mL of 0.9% sodium chloride solution for 7 days, the surface moisture was quickly wiped off, and the wet weight (g) of each group was weighed. The water absorption rate of each piece was calculated according to the following formula; water absorption rate = (wet weight - initial weight) / initial weight × 100%.

[0438] Visible spectrum transmittance

[0439] The spare buckle pieces prepared in each embodiment are processed into lenses with a diameter of 11 mm and a thickness of 0.22 mm by a precision lathe. Use a Shimadzu UV-2600i ultraviolet visible spectrophotometer for testing. Place the sample on the sample holder, adjust the position of the sample to ensure that the light passes through the center of the sample, ensure that the light is vertically projected onto the sample, measure the transmitted light intensity, record the transmitted light intensity and the incident light intensity, and calculate the average transmittance of the visible spectrum according to the formula given in GB / T11417.5. Calculate the sample light transmittance under standard lighting bodies D65 and A respectively. Measure 3 times independently and calculate the arithmetic mean of the 3 times.

[0440] Example 1

[0441] According to the feed ratio (mass percentage) shown in Table 2, the copolymer was synthesized according to the following operation process.

[0442] The purchased monomer was taken out from a 2-8°C refrigerator (the purity of the specific materials and the content of the inhibitor are shown in Table 1) and placed at room temperature for 2 hours. The monomer was then transferred to an operating box containing a nitrogen atmosphere to ensure that the oxygen content in the box was less than 0.5%. Using a precision analytical balance, according to the specific formula of Example 1 shown in Table 2, HFPMA (hexafluoroisopropyl methacrylate), M-TRIS (methacryloxypropyl tris (trimethylsiloxy) silane), MAA (methacrylic acid), AIBN (azobisisobutyronitrile), NPGDMA (neopentyl glycol dimethacrylate), DIMER (1,3-bis (methacryloxypropyl) -1,1,3,3-tetrakis (trimethylsiloxy) disiloxane), HECB (2-hydroxy-4- (methacryloxy) benzophenone), Green 6# (blended dye) were weighed according to the mass percentage (equivalent to pure feed, the same in the following embodiments), and directly dissolved and mixed in a nitrogen atmosphere to obtain a reaction solution.

[0443] The obtained reaction solution was cooled to below -10°C, and the reaction solution was immediately connected using a three-way valve connected to nitrogen and negative pressure equipment, and the reaction solution atmosphere was repeatedly replaced by nitrogen for at least 1 minute. The reaction solution was then sealed at room temperature for 30 minutes. The above mixture was injected into a molding mold made of polypropylene (diameter 140mm, depth 20mm), and the bottom and top of the mold were both equipped with removable polypropylene sealing plugs. Transferred to a nitrogen-filled oxygen-free oven, the oxygen content was controlled to be less than 0.1%, kept at 40°C for 2 hours, heated to 60°C for 8 hours, heated to 90°C for 12 hours, and then slowly cooled to room temperature (cooling 20°C every hour) by program control to complete free radical copolymerization. At room temperature, the polypropylene sealing plugs on the upper and lower parts of the mold were removed, and the rod-shaped material in the polypropylene mold was ejected using an apparatus, and the rod was cut into a button-shaped sheet (button sheet) with a diameter of 12.7mm and a thickness of 4.25mm using a CNC lathe for standby use (polymerization conditions-method A).

[0444] The prepared buckle was tested. The test results are shown in Table 2.

[0445] Embodiment 2-7

[0446] Polymerization and preparation of buckle sheets were carried out in the same manner as in Example 1, except as follows: for the polymerization raw materials, according to the specific formula shown in Table 2, different types and amounts of other fluorinated monomers (the purity of the specific materials and the inhibitor content information are shown in Table 1) were used instead of HFPMA or TFEMA.

[0447] The prepared buckle was tested. The test results are shown in Table 2.

[0448] Table 2

[0449]

[0450]

[0451] Compared with Example 1, Examples 2-5 use 35, 25, 15, and 10 parts by mass of HFPA to replace the same parts by mass of HFPMA, respectively; as a result, the residual HFPMA-type fluorinated monomers are significantly reduced, and the residuals of other monomers (M-TRIS, MAA) that account for a large proportion in the copolymerization system are also reduced to varying degrees, so that the total amount of known monomer residues is significantly reduced relative to Example 1, and the total amount of unknown impurity residues is also slightly reduced, so that the total amount of residual monomers is significantly reduced relative to Example 1; among them, Examples 3 and 4 have the most obvious effect on reducing the residuals of various monomers. It is shown that using acrylate-terminated monomers to partially replace methacrylate-terminated monomers can improve the copolymerization environment of the system and reduce the amount of monomer residues. In addition, Examples 2-5 achieve oxygen permeability, contact angle, and water absorption data that are basically consistent with those of Example 1, and for hardness and oxygen permeability, compared with Example 1, Examples 2-5 can improve at least one or even both of them, and as the content of acrylate monomers increases, the oxygen permeability generally increases, but the hardness decreases.

[0452] Compared with Example 7, Example 6 uses 15 parts by mass of TFEA to replace the same part by mass of TFEMA; as a result, the residual TFEMA-type fluorinated monomers are significantly reduced, and the residuals of other monomers (M-TRIS, MAA) that account for a large proportion in the copolymerization system are also significantly reduced, so that the total amount of known monomer residues is significantly reduced relative to Example 7, and the total amount of unknown impurity residues is also slightly reduced, so that the total amount of residual monomers is significantly reduced relative to Example 7. It is shown that using acrylate-terminated monomers to partially replace methacrylate-terminated monomers can improve the copolymerization environment of the system and reduce the amount of monomer residues. In addition, compared with Example 7, Example 6 achieves substantially consistent contact angle and water absorption data, and achieves better hardness and oxygen permeability coefficient.

[0453] Examples 8-12

[0454] The polymerization and the preparation of the buckle sheet were carried out in the same manner as in Example 1, except as follows: for the polymerization raw materials, according to the specific formula shown in Table 3, different types and amounts of other silicon-containing monomers (the purity of the specific materials and the inhibitor content information are shown in Table 1) were used instead of M-TRIS.

[0455] The prepared buckle was tested. The test results are shown in Table 3.

[0456] Table 3

[0457]

[0458] Compared with Example 1, Examples 8-10 use 20, 15, and 10 parts by mass of TRIS to replace the same parts by mass of M-TRIS, respectively. As a result, the residual M-TRIS-type siloxane-containing monomers are significantly reduced, and the residuals of other monomers (HFPMA, MAA) that account for a large proportion in the copolymerization system are also reduced to varying degrees, so that the total amount of known monomer residues is significantly reduced relative to Example 1 (and the reduction effect is more obvious compared to Examples 2-6), and the total amount of unknown impurity residues is also slightly reduced, so that the total amount of residual monomers is significantly reduced relative to Example 1. It shows that using acrylic acid-terminated silicon-containing monomers to partially replace methacrylic acid-terminated silicon-containing monomers can improve the copolymerization environment of the system and reduce the amount of monomer residues. In addition, Examples 8-10 achieved substantially the same oxygen permeability, contact angle and water absorption data as compared with Example 1, and for hardness and oxygen permeability, compared with Example 1, Examples 8-10 were able to improve at least one or even both of them, and in Examples 8-10, as the content of acrylate monomer increased, the oxygen permeability slightly decreased, the static contact angle slightly increased, and the hardness slightly decreased (but the hardness reduction trend was relatively weaker than that of Examples 2-6). Among them, Examples 9 and 10 had a particularly significant effect on reducing various monomer residues, with the total amount of known monomer residues being <2%, and compared with Example 1, the hardness, oxygen permeability, contact angle and water absorption data were unchanged or even slightly improved.

[0459] Examples 11-12 use a vinyl-terminated siloxane monomer, p-vinylphenyl tris(trimethylsiloxy)silane (TTMS), which has a different structure from M-TRIS but the same functional side chain as M-TRIS to replace M-TRIS. The results show that compared with Example 1, Examples 11 and 12 also significantly reduce the total amount of known monomer residues (compared with Examples 9 and 10, the reduction trend is slightly smaller); at the same time, the total amount of unknown impurities residues is also slightly reduced, so the total amount of residual monomers is significantly reduced relative to Example 1. It shows that using vinyl-terminated silicon-containing monomers to partially replace methacrylic acid-terminated silicon-containing monomers can also improve the copolymerization environment of the system and reduce the amount of monomer residues. In addition, compared with Example 1, Examples 11-12 achieve significantly higher oxygen permeability coefficients, but the hardness is relatively reduced, and the static contact angle is increased.

[0460] Examples 13-20

[0461] The polymerization and the preparation of the buckle sheet were carried out in the same manner as in Example 1, except as follows: for the polymerization raw materials, according to the specific formulation shown in Table 4, different types and amounts of other hydrophilic monomers (the purity of the specific materials and the content of the inhibitor are shown in Table 1) were used instead of MAA.

[0462] The prepared buckle was tested. The test results are shown in Table 4.

[0463] Table 4

[0464]

[0465]

[0466] Compared with Example 1, Examples 13-16 use 7, 4, 3, and 2 parts by mass of AA to replace the same parts by mass of MAA, respectively. As a result, the monomer residue of MAA is significantly reduced, and the residues of other monomers (HFPMA, M-TRIS) that account for a large proportion in the copolymerization system are also greatly reduced, so that the total amount of known monomer residues is significantly reduced relative to Example 1, and the total amount of unknown impurity residues is also significantly reduced, thereby significantly reducing the total amount of residual monomers relative to Example 1. The total amount of known impurities in Examples 14 and 15 is controlled within 1%. It shows that the use of acrylic acid-type hydrophilic monomers to partially replace methacrylic acid-type hydrophilic monomers can improve the copolymerization environment of the system and reduce the amount of monomer residues. However, compared with Example 1, the hardness and oxygen permeability coefficient of the polymer prepared in Example 13, in which AA is used to completely replace MAA, are significantly reduced. Compared with Example 1, Examples 14-16 in which AA is partially used to replace MAA can improve at least one or even both of the hardness and oxygen permeability coefficient of Examples 8-10, and achieve substantially consistent contact angle and water absorption data compared with Example 1, wherein the hardness of the copolymers prepared in Examples 15-16 is significantly higher than that in Example 1, showing good processability.

[0467] Examples 17-20 use hydrophilic monomers N-vinylpyrrolidone (NVP) and N,N-dimethylacrylamide (DMAA) that are consistent with the side chain function of MAA to completely or partially replace MAA. As a result, it also shows a strong effect of reducing the residual known hydrophobic monomers (HFPMA, M-TRIS), so that the total amount of known monomer residues is significantly reduced relative to Example 1, and the total amount of unknown impurities is also slightly reduced, so that the total amount of residual monomers is significantly reduced relative to Example 1: Examples 17-20 can also control the residual known monomers to about 1%, or even lower than 1%. Compared with Example 1, Examples 17-19 can improve the hardness, which is believed to be because the rigid pyrrolidone ring is connected to the vinyl group in NVP. The presence of the rigid ring hinders the rotation of the overall macromolecular chain segment after copolymerization, and the chain segment becomes hard, so the corresponding material hardness becomes higher; and in addition, compared with Example 1, Examples 17-19 can also basically maintain or even improve the oxygen permeability coefficient; but the water absorption rate of this series of materials is lower than that of other examples. However, the material of Example 19 was fragile during lathe processing, indicating that the use of NVP alone still had a certain impact on the mechanical properties of the material. Example 20 showed that compared with NVP, DMAA replacing part of MAA had a slightly weaker control over residual impurities, and the hardness of the copolymer was also slightly worse, but the oxygen permeability coefficient of the copolymer could be slightly improved.

[0468] Examples 21-22

[0469] The polymerization and the preparation of the buckle plate are carried out in the same manner as in Example 1, except as follows: for the polymerization raw materials, according to the specific formula shown in Table 5, the corresponding raw materials are weighed according to the mass percentage (equivalent to pure feed) (the purity of the specific materials and the content of inhibitors are shown in Table 1).

[0470] The prepared buckle was tested. The test results are shown in Table 5.

[0471] Table 5

[0472]

[0473]

[0474] As can be seen from the above table, 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 MAA with NVP, the residual amount of known monomers is significantly reduced, and it is slightly better than Example 15 and Example 19. In addition, compared with Example 1, the total amount of unknown impurities is also slightly reduced, so the total amount of residual monomers is significantly reduced relative to Example 1. In addition, compared with Example 1, Examples 21-22 slightly increase the oxygen permeability coefficient while maintaining or improving the hardness, and also maintain the static contact angle and water absorption rate that are basically consistent with Example 1.

[0475] As described above, Example 19 uses the hydrophilic monomer 7% NVP to replace 7% MAA. As a result, although the monomer residue is significantly reduced, the material hardness is high and brittle, which is not conducive to processing. Compared with Example 19, in Example 22, HFPMA is partially replaced by FPMA, and M-TRIS is partially replaced by TRIS, so that the hardness of the prepared copolymer is adjusted within a suitable range, and the processing performance of the material is significantly improved.

[0476] Embodiment 23-24

[0477] The polymerization and buckle preparation are carried out in the same manner as in Example 1, except as follows: for the polymerization raw materials, according to the specific formula shown in Table 6, the corresponding raw materials are weighed according to the mass percentage (equivalent to pure feed) (the purity of the specific materials and the content of inhibitors are shown in Table 1).

[0478] Hereinafter, when "mixed monomers" are mentioned, it refers to the following mixture: NPGDMA 7%, TTMS 9%, DIMER 8%, HECB 0.49%, Green6# 0.01%, wherein "%" refers to the mass % in the formula.

[0479] The prepared buckle was tested. The test results are shown in Table 6.

[0480] Table 6

[0481]

[0482] Compared with Example 23, Example 24 partially replaced M-TRIS with TRIS and partially replaced MAA with AA, and as a result, the total amount of residual known monomers, the total amount of residual unknown monomers, and the total amount of residual monomers were reduced 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, and it had excellent hardness and water absorption, and the static contact angle was slightly reduced.

[0483] Examples 25-26

[0484] The polymerization and the buckle sheet were prepared in the same manner as in Example 21, except as follows: the polymerization was carried out by using different curing equipment and curing procedures, wherein after the reaction solution was injected into the molding mold, in Example 25, it was transferred to a forced air drying oven, kept at 40°C for 2 hours, heated to 60°C for 24 hours, heated to 90°C for 12 hours, and then the program was controlled to slowly cool to room temperature (10°C every hour), thereby completing free radical copolymerization (polymerization conditions-method B); in Example 26, it was transferred to a constant temperature water bath, kept at 40°C for 2 hours, heated to 60°C for 48 hours, heated to 70°C for 12 hours, and then the program was controlled to slowly cool to room temperature (10°C every hour), thereby completing free radical copolymerization (polymerization conditions-method C). The purity and inhibitor content information of the specific materials used in Examples 25-26 are shown in Table 1.

[0485] The prepared buckle was tested. The test results are shown in Table 7.

[0486] Table 7

[0487]

[0488] Curing method B uses a forced air drying oven instead of a nitrogen-filled oxygen-free oven. The air circulation will cause the chain initiation stage to be slow, so the 60°C holding time is extended for curing B. The advantages of water bath curing are uniform temperature and fast heat dissipation, but it is limited by the fact that water vapor will be generated at high temperatures. When setting the curing program, the temperature of the high temperature section is lowered and the holding time is extended. This is how curing method C is determined.

[0489] By comparing the test data of Examples 21 with those of Examples 25 and 26, it can be determined that the method of the present invention for regulating the residual monomer content by adjusting the composition of the hydrophobic fluorine-containing monomer, the hydrophobic silicon-containing monomer and the hydrophilic monomer is still effective under various curing conditions.

[0490] The schemes and test data of Examples 1-26 show that by regulating the composition of the hydrophobic fluorine-containing monomer, the hydrophobic silicon-containing monomer and the hydrophilic monomer, the total amount of known monomer residues, the total amount of unknown impurity residues and the total amount of residual monomers in the obtained polymer can be effectively reduced, and the physical parameters of the RGP copolymer such as oxygen permeability, wettability, mechanical properties, and processing properties can also be optimized, thereby further expanding the scope of application of the present invention.

[0491] Examples 27-28

[0492] The polymerization and the preparation of the clips were carried out in the same manner as in Example 1, except as follows: for the polymerization raw materials, the raw materials with the purity and inhibitor content shown in Table 8 were weighed respectively according to the mass percentage (equivalent to the pure feed).

[0493] The raw materials used in Examples 27 and 28 are obtained by further purifying the monomers used in Example 1 (the purity of the specific materials and the content of inhibitors are shown in Table 1), wherein the monomers used in Example 27 are monomers obtained by purifying the commercially available monomers used in Example 1 once, and the monomers used in Example 28 are monomers obtained by purifying the commercially available monomers used in Example 1 twice or more; wherein for materials that are solid at room temperature (initiator, dye and ultraviolet absorber), recrystallization is used for purification, and for materials that are liquid at room temperature (fluorine-containing monomer, silicon-containing monomer, hydrophilic monomer and cross-linking agent), reduced pressure distillation is used for purification.

[0494] The prepared buckle was tested. The test results are shown in Table 8.

[0495] Table 8

[0496]

[0497]

[0498] The test data of Examples 1, 27 and 28 in the above table show that increasing the purity of the monomers and reducing the content of the polymerization inhibitor in the monomers can significantly reduce the residual unknown impurities, and the effect of reducing the unknown impurities has a significant upward trend with the gradual reduction of the polymerization inhibitor. The monomer purity of Examples 27 and 28 is the same, and the content of the polymerization inhibitor is different. The total content of the polymerization inhibitor of each monomer in Example 28 is controlled below 50ppm, which is significantly smaller than that of Example 27. As a result, the total residual unknown impurities can be controlled below 0.3%. At the same time, it is found that increasing the purity of the polymerized monomers and reducing the content of the polymerization inhibitor can also reduce the residual amount of the known monomers. Although this reduction is not very significant, it also shows that the presence of impurities in the monomers has a certain influence on the polymerization process of the copolymer.

[0499] Examples 29-33

[0500] The polymerization and preparation of the buckle sheet were carried out in the same manner as in Example 1, except as follows: for the polymerization raw materials, according to the formulation composition shown in Table 10, the corresponding raw materials of purity and inhibitor content shown in Table 9 were weighed according to the mass percentage (equivalent to pure feed).

[0501] The prepared buckle was tested. The test results are shown in Table 10.

[0502] Table 9

[0503]

[0504]

[0505] Table 10

[0506]

[0507]

[0508] Compared with Examples 4, 9, 14, 21, and 24 using raw materials with lower purity and higher inhibitor content, the hardness, oxygen permeability coefficient, contact angle, and water absorption rate of the materials obtained after copolymerization of Examples 29-33 using raw materials with higher purity and lower inhibitor content have no significant difference; however, the total amount of unknown impurity residues of the prepared copolymers has changed significantly, and the total amount of unknown impurity residues has decreased by an average of 2%, which is consistent with the technical effect embodied in Example 28. At the same time, compared with Examples 4, 9, 14, 21, and 24, the residual amount of known monomers of the copolymers prepared by Examples 29-33 has also been slightly reduced. This further illustrates that controlling the purity of the monomers and the content of the inhibitor can significantly improve the residual amount of unknown impurities in the copolymers, and can reduce the residual amount of known monomers, thereby significantly reducing the total amount of residual monomers. Example 33 is an ultra-high oxygen permeability material. After solving the problem of chemical residues, its true DK value can reach 187, and the hydrophilicity and processability are not reduced.

[0509] Examples 34-37

[0510] Polymerization and preparation of buckles were carried out in the same manner as in Example 32, except as follows: for the polymerization raw materials, in Examples 34-37, mass fractions of 0.005% RB246, 0.005% RP247, 0.01% RY8739, 0.005% RB246 and 0.007% RY8739 were used respectively to replace 0.01% of Green 6# in Example 32, thereby preparing ice blue, ice purple, bright yellow and ice green RGP materials, respectively.

[0511] The prepared RGP material was tested. The test results are shown in Table 11 below.

[0512] Table 11

[0513]

[0514]

[0515] In clinical applications, RGP materials often add masterbatches and other dyes to copolymer materials in order to increase product recognition. In particular, with the popularity of orthokeratology lenses in recent years, there are more and more RGP products that require personalized fitting and custom processing. Because the fitting parameters and processing data for the left and right eyes are not completely consistent, the color of the product is often used to distinguish between the left and right lenses in clinical practice. Therefore, RGP materials must be made into materials of different colors to increase recognition and distinguish colors.

[0516] There are two ways to add dyes. One is direct dyes; this type of dye is used to color the carrier by physical blending. It has a simple dyeing method, a complete color spectrum, and low cost. However, its washing and aging fastness are poor. The other is active dyes; also known as reactive dyes, this type of dye contains one or more active groups in its molecular structure. Under appropriate conditions, it can react chemically with the carrier to form a covalent bond. This type of dye is strong, but the coloring method is complicated, there are not many colors to choose from, and the cost is high.

[0517] Most of the RGP materials used in the Class 3 medical devices currently on the market in China use physical blended direct dyes; a typical example is Boston The blue color used in the material is D&C Green 6# dye, the green color used is D&C Green 6# and Yellow 18# dye, Paragon HDS D&C Green 6# and Yellow 18# are also used. Although the amount of direct dyes added in this type of blend is very small, generally within 100ppm (0.01%) by mass, this type of dye interacts with the copolymer material by physical action. When in contact with the cornea for a long time, it will cause the lens to fade due to material aging, tear erosion and other interactions. It may even be absorbed by the ocular surface through tear exchange or passive diffusion during wearing, causing biosafety issues.

[0518] Examples 34-37 use dyes with polymerization-reactive groups (active dyes) instead of directly blended dyes, thereby improving the biosafety of RGP materials in one step. The active dye contains vinyl or (methyl) vinyl end-capping, which can participate in free radical copolymerization. Different from the existing physical blending direct dyes used in the field of RGP materials, the active dye is combined in the copolymer of the material by a covalent chemical reaction, so the dyeing efficiency and stability of the active dye are higher, which fundamentally avoids the use or wearing of RGP materials. The dye fades and the dissolved dye interacts with the cornea to cause poor biosafety risks.

[0519] Although the active dye can participate in the polymerization reaction, the addition amount is very low (0.005%-0.012%), so theoretically the performance of the polymer segment is very small. This is verified by comparing the physical and chemical performance parameters of Examples 34-37 with those of Example 32. RB246 and RP247 are active dyes terminated with dimethacrylic acid, which also act as partial crosslinking agents when participating in the copolymerization reaction, making the reaction between the segments more stable, and can further reduce the content of oligomers in unknown impurities. However, due to their relatively low addition amount, this reduction trend is not very obvious. The total amount of unknown impurities in the formula using RB246 and RP247 dyes in Examples 34, 35, and 37 can be controlled within 0.3%, slightly lower than 0.4% in Example 36. The total amount of residual monomers in Examples 34-37 is less than 1%, showing good biocompatibility, further proving the feasibility and effectiveness of the strategy for controlling monomer residues of the present 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 spectrum transmittance of the dyed material is above 93%, which is higher than the spectral transmittance of not less than 89% required for contact lenses in the visible light region in GB11417.3. This series of materials shows good light transmittance.

[0520] Although the specific embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that various modifications and substitutions may be made to those details based on all the teachings disclosed, and these changes are within the scope of protection of the present invention. The full scope of the present invention is given by the attached claims and any equivalents thereof.

Claims

1. A method for reducing the residual monomer content in a polymer composition, wherein the polymer composition is a polymer composition prepared by free radical polymerization using a first composition capable of free radical polymerization, wherein the first composition capable of free radical polymerization comprises a mixture of: a first ethylenically unsaturated monomer component based on a first ethylenically unsaturated monomer, wherein the olefinic bond in the first ethylenically unsaturated monomer is derived from an isopropenyl group (CH2=C(CH3)-), Free radical initiators, Optionally, a UV absorber, and Optionally, a coloring agent; The method comprises: Providing a second free radical polymerizable composition by replacing a portion of the first ethylenically unsaturated monomer component with a second ethylenically unsaturated monomer component based on a second ethylenically unsaturated monomer as follows: wherein the olefinic bond of the second ethylenically unsaturated monomer is derived from a vinyl group (CH2=CH-); The second free radical polymerizable composition is then free radically polymerized.

2. The method according to claim 1, wherein the olefinic bond in the first ethylenically unsaturated monomer is derived from a methacryloxy group, and the olefinic bond in the second ethylenically unsaturated monomer is derived from one or more of the following: acryloxy, acrylamido, N-vinylamido, vinylphenyl.

3. The method according to any one of claims 1 to 2, wherein the first ethylenically unsaturated monomer and the second ethylenically unsaturated monomer have the same olefinic functionality; Preferably the first ethylenically unsaturated monomer is a monoethylenically functional ethylenically unsaturated monomer and the second ethylenically unsaturated monomer is a monoethylenically functional ethylenically unsaturated monomer.

4. The method according to any one of claims 1 to 3, wherein The first ethylenically 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 ethylenically 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 ethylenically 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 by an acryloxy group, a 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 by an acryloxy group in the second hydrophilic monomer; Preferably, the first ethylenically unsaturated monomer includes or is a first hydrophobic fluorine-containing monomer containing methacryloyl, such as a hydrophobic fluorine-containing alkyl methacrylate monomer, a first hydrophobic silicon-containing monomer containing methacryloyl, such as a silicon-containing hydrophobic methacrylate monomer, a first hydrophilic monomer containing methacryloyl, or any combination thereof; preferably, the first ethylenically unsaturated monomer includes or is a first hydrophobic fluorine-containing monomer containing methacryloyl, such as a hydrophobic fluorine-containing alkyl methacrylate monomer, a first hydrophobic silicon-containing monomer containing methacryloyl, such as a silicon-containing hydrophobic methacrylate monomer, and a first hydrophilic monomer containing methacryloyl, and the second ethylenically unsaturated monomer includes or is a second hydrophobic fluorine-containing monomer, such as a hydrophobic fluorine-containing alkyl acrylate. Monomer, a second hydrophobic silicon-containing monomer such as a silicon-containing hydrophobic acrylate monomer and / or a vinylphenyl-containing silane, a second hydrophilic monomer, or a combination thereof; preferably, the first hydrophobic fluorine-containing monomer differs from the second hydrophobic fluorine-containing monomer only in that the methacryloxy group in the first hydrophobic fluorine-containing monomer is replaced by an acryloxy group in the second hydrophobic fluorine-containing monomer; preferably, the first hydrophobic silicon-containing monomer differs from the second hydrophobic silicon-containing monomer only in that the methacryloxy group in the first hydrophobic silicon-containing monomer is replaced by an acryloxy group, vinylphenyl or a combination thereof in the second hydrophobic silicon-containing monomer; preferably, the first hydrophilic monomer differs from the second hydrophilic monomer only in that the methacryloxy group in the first hydrophilic monomer is replaced by an acryloxy group in the second hydrophilic monomer; Preferably, the first ethylenically unsaturated monomer includes or is a monoolefinic first hydrophobic fluorinated monomer containing methacryloyl, such as a hydrophobic fluorinated alkyl methacrylate monomer, a monoolefinic first hydrophobic silicon-containing monomer containing methacryloyl, such as a silicon-containing hydrophobic methacrylate monomer, a monoolefinic first hydrophilic monomer containing methacryloyl, or any combination thereof; preferably, the first ethylenically unsaturated monomer includes or is a monoolefinic first hydrophobic fluorinated monomer containing methacryloyl, such as a hydrophobic fluorinated alkyl methacrylate monomer, a monoolefinic first hydrophobic silicon-containing monomer containing methacryloyl, such as a silicon-containing hydrophobic methacrylate monomer, and a monoolefinic first hydrophilic monomer containing methacryloyl, and the second ethylenically unsaturated monomer includes or is a monoolefinic second hydrophobic fluorinated monomer Preferably, the first hydrophobic fluorine-containing monomer and the second hydrophobic fluorine-containing monomer differ only in that the methacryloxy group in the first hydrophobic fluorine-containing monomer is replaced by the acryloxy group in the second hydrophobic fluorine-containing monomer; preferably, the first hydrophobic silicon-containing monomer and the second hydrophobic silicon-containing monomer differ only in that the methacryloxy group in the first hydrophobic silicon-containing monomer is replaced by the acryloxy group, vinylphenyl group or a combination thereof in the second hydrophobic silicon-containing monomer; preferably, the first hydrophilic monomer and the second hydrophilic monomer differ only in that the methacryloxy group in the first hydrophobic silicon-containing monomer is replaced by the acryloxy group in the second hydrophobic silicon-containing monomer.

5. The method according to any one of claims 1 to 4, wherein the second free radical polymerizable composition comprises: (1) A monoethylenically functional hydrophobic fluorinated monomer component comprising or consisting of: (1-1) a first hydrophobic fluorine-containing monomer component based on a fluoroalkyl methacrylate as a first hydrophobic fluorine-containing monomer; Preferably, the first hydrophobic fluorine-containing monomer is C1-C10 fluorine-containing alkyl methacrylate, preferably C1-C6 fluorine-containing alkyl methacrylate, preferably C2-C5 fluorine-containing alkyl methacrylate, more preferably C2-C3 fluorine-containing alkyl methacrylate; preferably, the first hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate; more preferably, the first hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl methacrylate and hexafluoroisopropyl methacrylate; and (1-2) an optional second hydrophobic fluorine-containing monomer component based on a fluorine-containing alkyl acrylate as a second hydrophobic fluorine-containing monomer; 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, preferably the same; Preferably, the second hydrophobic fluorine-containing monomer is C1-C10 fluorine-containing alkyl acrylate, preferably C1-C6 fluorine-containing alkyl acrylate, preferably C2-C5 fluorine-containing alkyl acrylate, more preferably C2-C3 fluorine-containing alkyl acrylate; preferably, the second hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl acrylate, hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate; more preferably, the second hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl acrylate and hexafluoroisopropyl acrylate; Preferably, the first hydrophobic fluorine-containing monomer is selected from one or more of hexafluoroisopropyl methacrylate and trifluoroethyl methacrylate, and the second hydrophobic fluorine-containing monomer is selected from one or more of hexafluoroisopropyl acrylate and trifluoroethyl acrylate; preferably, the first hydrophobic fluorine-containing monomer is hexafluoroisopropyl methacrylate and the second hydrophobic fluorine-containing monomer is hexafluoroisopropyl acrylate, or the first hydrophobic fluorine-containing monomer is trifluoroethyl methacrylate and the second hydrophobic fluorine-containing monomer is trifluoroethyl acrylate; (2) a monoolefin-functional hydrophobic silicon-containing monomer component comprising or consisting of: (2-1) a first hydrophobic silicon-containing monomer component based on a silicon-containing methacrylate as a first hydrophobic silicon-containing monomer, 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 , wherein L1 is a C1-C10, preferably C3-C6 divalent alkylene group, which optionally includes one or more of an ether -O-atom group and an -OH group, R1 is the same as or different from each other and is independently a C1-C6 alkyl group, preferably a methyl group, R2 is the same as or different from each other and is independently a C1-C6 alkyl group, preferably a methyl group, or -Si(R3)3, wherein R3 is the same as or different from each other and is independently a C1-C6 alkyl group, preferably a methyl group, and m is 0, 1, 2, or 3, preferably 0 or 1; Preferably, the first hydrophobic silicon-containing monomer is selected from one or more of methacryloxypropyl tris(trimethylsiloxy)silane and (3-methacryloxy-2-hydroxypropoxy)propyl bis(trimethylsiloxy)methylsilane; and (2-2) an optional second hydrophobic silicon-containing monomer component based on a silicon-containing acrylate or a vinylphenyl-containing silane as the second hydrophobic silicon-containing monomer, 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 , wherein Ph is a phenylene group such as a 1,4-phenylene group, L2 is the same as or different from L1 and is a C1-C10, preferably C3-C6 divalent alkylene group optionally including one or more of an ether -O-atom group, a -OH group; R4 are the same or different from each other and the same or different from R1 and are each independently C1-C6 alkyl, preferably methyl, R5 are the same or different from each other and the same or different from R2 and are each independently C1-C6 alkyl, preferably methyl or -Si(R6)3, wherein R6 are the same or different from each other and the same or different from R3 and are each independently C1-C6 alkyl, preferably methyl, n and m are the same or different and are 0, 1, 2 or 3, preferably 0 or 1; Preferably, -Si(R4) n (OR5) 3-n Partially with -Si(R1)m(OR2) 3-m The parts are identical or different, preferably identical; Preferably, -L2-Si(R4) n (OR5) 3-n Partially with -L1-Si(R1)m(OR2) 3-m The parts are identical or different, preferably identical; Preferably, the second hydrophobic silicon-containing monomer is selected from one or more of acryloxypropyl tris(trimethylsiloxy)silane, (3-acryloxy-2-hydroxypropoxy)propyl bis(trimethylsiloxy)methylsilane and p-vinylphenyl tris(trimethylsiloxy)silane; Preferably, the first hydrophobic silicon-containing monomer is selected from methacryloxypropyl tris(trimethylsiloxy)silane, and the second hydrophobic silicon-containing monomer is selected from one or more of acryloxypropyl tris(trimethylsiloxy)silane and p-vinylphenyl tris(trimethylsiloxy)silane, preferably acryloxypropyl tris(trimethylsiloxy)silane; (3) a monoolefin-functional hydrophilic monomer component comprising or consisting of: (3-1) a first hydrophilic monomer component based on a first hydrophilic monomer containing a methacryloyl group; Preferably, the first hydrophilic monomer is selected from one or more of methacrylic acid, hydroxyethyl methacrylate, methacrylamide, and N,N-dimethylmethacrylamide; and / or (3-2) a second hydrophilic monomer component based on a second hydrophilic monomer containing an acryloxy group, an acrylamido group and / or an N-vinylamido group; Preferably, 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; Preferably, the second hydrophilic monomer is selected from one or more of acrylic acid, hydroxyethyl acrylate, acrylamide, N,N-dimethylacrylamide, N-vinyl pyrrolidone, and N-methyl-N-vinylacetamide; 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-vinyl pyrrolidone (NVP) and N,N-dimethylacrylamide, preferably acrylic acid; (4) optionally, a crosslinker component based on a diene-functional or higher crosslinker; Preferably, the crosslinking agent with more than bis-alkenyl functionality is selected from: alkyl glycol dimethacrylate, preferably neopentyl glycol dimethacrylate; a siloxane-containing oligomer, preferably 1,3-bis(methacryloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, bis(methylpropoxy)butylpolydimethylsiloxane; or any combination thereof; for example, neopentyl glycol dimethacrylate and 1,3-bis(methacryloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, which are present in a mass ratio of, for example, 10:90-90:10, for example, 30:70-70:30, for example, 50:50-60:40; (5) free radical initiators, such as azobisisobutyronitrile or azobisisoheptanenitrile; (6) optionally, a UV absorber, such as 2-hydroxy-4-(methacryloyloxy)benzophenone; When the first hydrophilic monomer is present, one, two or three of the second hydrophobic fluorine-containing monomer, the second hydrophobic silicon-containing monomer, and the second hydrophilic monomer are present.

6. The method according to any one of claims 1 to 5, wherein: The second free radical polymerizable composition comprises, based on the total mass of the second free radical polymerizable composition: (1) 30-60 mass %, for example 40-50 mass %, of a monoethylenically functional hydrophobic fluorinated monomer component; (2) 20-45 mass %, for example 30-40 mass %, of a monoethylenic functional hydrophobic silicon-containing monomer component; (3) 3-20 mass %, for example 5-10 mass %, of a monoethylenic functional hydrophilic monomer component; (4) optionally, 1-20 mass %, e.g., 5-15 mass %, of a crosslinker component based on a diene-functional or higher crosslinker; and (5) 0.1-2.0 mass %, for example 0.5-1.0 mass % of a free radical initiator; and (6) Optionally, 0.1-5.0 mass %, such as 0.2-1.0 mass %, such as 0.4-0.6 mass % of an ultraviolet absorber.

7. A method according to any one of claims 4 to 6, wherein In the second free-radically polymerizable composition: A second hydrophobic fluorinated monomer is present, preferably the first hydrophobic fluorinated monomer and the second hydrophobic fluorinated monomer are present in a mass ratio of 30:70-80:20, such as 50:50-80:20, such as 70:30-80:20; and / or A second hydrophobic silicon-containing monomer is present, 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, such as 50:50-75:25; and / or The first hydrophilic monomer and the second hydrophilic monomer are present, preferably the first hydrophilic monomer and the second hydrophilic monomer are present in a mass ratio of 0:100-85:15, such as 25:75-80:20, such as 40:60-75:

25.

8. The method according to any one of claims 4 to 7, wherein a second hydrophobic fluorine-containing monomer, a second hydrophobic silicon-containing monomer, a first hydrophilic monomer and a second hydrophilic monomer are present in the second free-radically polymerizable composition.

9. The method according to any one of claims 1 to 8, wherein the method comprises, before polymerization and before providing the second free radical polymerizable composition, performing the following purification step: Purifying the first ethylenically unsaturated monomer component to increase the content of the first ethylenically unsaturated monomer and / or reduce the content of the polymerization inhibitor therein, for example, to make the content of the first ethylenically unsaturated monomer therein 98 mass % or more, preferably 99 mass % or more and / or the content of the polymerization inhibitor therein is 50 ppm by mass or less; and / or The second ethylenically unsaturated monomer component is purified to increase the second ethylenically unsaturated monomer content and / or reduce the polymerization inhibitor content therein, for example, so that the second ethylenically unsaturated monomer content therein is 98% by mass or more, preferably 99% by mass or more and / or the polymerization inhibitor content therein is 50 ppm by mass or less.

10. The method according to any one of claims 4 to 9, wherein the method comprises, before polymerization and before providing the second free radical polymerizable composition, performing the following purification step: Purifying the first hydrophobic fluorine-containing monomer component to increase the content of the first hydrophobic fluorine-containing monomer and / or reduce the content of the polymerization inhibitor therein, for example, to make the content of the first hydrophobic fluorine-containing monomer therein 98 mass % or more, preferably 99 mass % or more and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or Purifying the second hydrophobic fluorine-containing monomer component to increase the content of the second hydrophobic fluorine-containing monomer and / or reduce the content of the polymerization inhibitor therein, for example, to make the content of the second hydrophobic fluorine-containing monomer therein 98 mass % or more, preferably 99 mass % or more and / or the content of the polymerization inhibitor is 50 ppm by mass or less; and / or Purifying the first hydrophobic silicon-containing monomer component to increase the content of the first hydrophobic silicon-containing monomer and / or reduce the content of the polymerization inhibitor, for example, to make the content of the first hydrophobic silicon-containing monomer greater than 98 mass %, preferably greater than 99 mass % and / or the content of the polymerization inhibitor less than 50 ppm by mass; and / or Purifying the second hydrophobic silicon-containing monomer component to increase the content of the second hydrophobic silicon-containing monomer and / or reduce the content of the polymerization inhibitor, for example, to make the content of the second hydrophobic silicon-containing monomer greater than 98 mass %, preferably greater than 99 mass % and / or the content of the polymerization inhibitor less than 50 ppm by mass; and / or Purifying the first hydrophilic monomer component to increase the content of the first hydrophilic monomer and / or reduce the content of the polymerization inhibitor therein, for example, to make the content of the first hydrophilic monomer therein 98 mass % or more, preferably 99 mass % or more and / or the content of the polymerization inhibitor therein be 50 ppm by mass or less; and / or Purifying the second hydrophilic monomer component to increase the content of the second hydrophilic monomer and / or reduce the content of the polymerization inhibitor therein, for example, to make the content of the second hydrophilic monomer therein 98 mass % or more, preferably 99 mass % or more and / or the content of the polymerization inhibitor therein 50 ppm by mass or less; and / or The crosslinker component based on a diene-functional or higher crosslinker is purified to increase the crosslinker content and / or reduce the polymerization inhibitor content therein, for example, so that the crosslinker content therein 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.

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

12. The method according to any one of claims 1 to 11, wherein the polymer is a medical polymer, preferably a polymer used for preparing corneal contact lenses, preferably a polymer used for preparing hard oxygen permeable corneal contact lenses.

13. Polymer composition obtainable by the process according to any one of claims 1 to 12.

14. A free radical polymerizable composition comprising: (1) A monoethylenically functional hydrophobic fluorinated monomer component comprising or consisting of: (1-1) a first hydrophobic fluorine-containing monomer component based on a fluoroalkyl methacrylate as a first hydrophobic fluorine-containing monomer; Preferably, the first hydrophobic fluorine-containing monomer is C1-C10 fluorine-containing alkyl methacrylate, preferably C1-C6 fluorine-containing alkyl methacrylate, preferably C2-C5 fluorine-containing alkyl methacrylate, more preferably C2-C3 fluorine-containing alkyl methacrylate; preferably, the first hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate; more preferably, the first hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl methacrylate and hexafluoroisopropyl methacrylate; and (1-2) an optional second hydrophobic fluorine-containing monomer component based on a fluorine-containing alkyl acrylate as a second hydrophobic fluorine-containing monomer; 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, preferably the same; Preferably, the second hydrophobic fluorine-containing monomer is C1-C10 fluorine-containing alkyl acrylate, preferably C1-C6 fluorine-containing alkyl acrylate, preferably C2-C5 fluorine-containing alkyl acrylate, more preferably C2-C3 fluorine-containing alkyl acrylate; preferably, the second hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl acrylate, hexafluoroisopropyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate; more preferably, the second hydrophobic fluorine-containing monomer is selected from one or more of trifluoroethyl acrylate and hexafluoroisopropyl acrylate; Preferably, the first hydrophobic fluorine-containing monomer is selected from one or more of hexafluoroisopropyl methacrylate and trifluoroethyl methacrylate, and the second hydrophobic fluorine-containing monomer is selected from one or more of hexafluoroisopropyl acrylate and trifluoroethyl acrylate; preferably, the first hydrophobic fluorine-containing monomer is hexafluoroisopropyl methacrylate and the second hydrophobic fluorine-containing monomer is hexafluoroisopropyl acrylate, or the first hydrophobic fluorine-containing monomer is trifluoroethyl methacrylate and the second hydrophobic fluorine-containing monomer is trifluoroethyl acrylate; (2) a monoolefin-functional hydrophobic silicon-containing monomer component comprising or consisting of: (2-1) a first hydrophobic silicon-containing monomer component based on a silicon-containing methacrylate as a first hydrophobic silicon-containing monomer, 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 , wherein L1 is a C1-C10, preferably C3-C6 divalent alkylene group, which optionally includes one or more of an ether -O-atom group and an -OH group, R1 is the same as or different from each other and is independently a C1-C6 alkyl group, preferably a methyl group, R2 is the same as or different from each other and is independently a C1-C6 alkyl group, preferably a methyl group, or -Si(R3)3, wherein R3 is the same as or different from each other and is independently a C1-C6 alkyl group, preferably a methyl group, and m is 0, 1, 2, or 3, preferably 0 or 1; Preferably, the first hydrophobic silicon-containing monomer is selected from one or more of methacryloxypropyl tris(trimethylsiloxy)silane and (3-methacryloxy-2-hydroxypropoxy)propyl bis(trimethylsiloxy)methylsilane; and (2-2) an optional second hydrophobic silicon-containing monomer component based on a silicon-containing acrylate or a vinylphenyl-containing silane as the second hydrophobic silicon-containing monomer, 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 , wherein Ph is a phenylene group such as a 1,4-phenylene group, L2 is the same as or different from L1 and is a C1-C10, preferably a C3-C6 divalent alkylene group which optionally includes one or more of an ether -O-atom group and a -OH group; R4 is the same as or different from each other and is the same as or different from R1 and is each independently a C1-C6 alkyl group, preferably a methyl group, R5 is the same as or different from each other and is the same as or different from R2 and is each independently a C1-C6 alkyl group, preferably a methyl group or -Si(R6)3, wherein R6 is the same as or different from each other and is the same as or different from R3 and is each independently a C1-C6 alkyl group, preferably a methyl group, and n is the same as or different from m and is 0, 1, 2 or 3, preferably 0 or 1; Preferably, -Si(R4) n (OR5) 3-n Partially with -Si(R1)m(OR2) 3-m The parts are identical or different, preferably identical; Preferably, -L2-Si(R4) n (OR5) 3-n Partially with -L1-Si(R1)m(OR2) 3-m The parts are identical or different, preferably identical; Preferably, the second hydrophobic silicon-containing monomer is selected from one or more of acryloxypropyl tris(trimethylsiloxy)silane, (3-acryloxy-2-hydroxypropoxy)propyl bis(trimethylsiloxy)methylsilane and p-vinylphenyl tris(trimethylsiloxy)silane; Preferably, the first hydrophobic silicon-containing monomer is selected from methacryloxypropyl tris(trimethylsiloxy)silane, and the second hydrophobic silicon-containing monomer is selected from one or more of acryloxypropyl tris(trimethylsiloxy)silane and p-vinylphenyl tris(trimethylsiloxy)silane, preferably acryloxypropyl tris(trimethylsiloxy)silane; (3) a monoolefin-functional hydrophilic monomer component comprising or consisting of: (3-1) a first hydrophilic monomer component based on a first hydrophilic monomer containing a methacryloyl group; Preferably, the first hydrophilic monomer is selected from one or more of methacrylic acid, hydroxyethyl methacrylate, methacrylamide, and N,N-dimethylmethacrylamide; and / or (3-2) a second hydrophilic monomer component based on a second hydrophilic monomer containing an acryloxy group, an acrylamido group and / or an N-vinylamido group; Preferably, 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; Preferably, the second hydrophilic monomer is selected from one or more of acrylic acid, hydroxyethyl acrylate, acrylamide, N,N-dimethylacrylamide, N-vinyl pyrrolidone, and N-methyl-N-vinylacetamide; 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-vinyl pyrrolidone (NVP) and N,N-dimethylacrylamide, preferably acrylic acid; (4) optionally, a crosslinker component based on a diene-functional or higher crosslinker; Preferably, the crosslinking agent with more than bis-alkenyl functionality is selected from: alkyl glycol dimethacrylate, preferably neopentyl glycol dimethacrylate; a siloxane-containing oligomer, preferably 1,3-bis(methacryloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, bis(methylpropoxy)butylpolydimethylsiloxane; or any combination thereof; for example, neopentyl glycol dimethacrylate and 1,3-bis(methacryloxypropyl)-1,1,3,3-tetra(trimethylsiloxy)disiloxane, which are present in a mass ratio of, for example, 10:90-90:10, for example, 30:70-70:30, for example, 50:50-60:40; (5) free radical initiators, such as azobisisobutyronitrile or azobisisoheptanenitrile; (6) optionally, a UV absorber, such as 2-hydroxy-4-(methacryloyloxy)benzophenone; When the first hydrophilic monomer is present, one, two or three of the second hydrophobic fluorine-containing monomer, the second hydrophobic silicon-containing monomer, and the second hydrophilic monomer are present.

15. The composition according to claim 14, wherein The composition comprises, based on the total mass of the composition: (1) 30-60 mass %, for example 40-50 mass %, of a monoethylenically functional hydrophobic fluorinated monomer component; (2) 20-45 mass %, for example 30-40 mass %, of a monoethylenic functional hydrophobic silicon-containing monomer component; (3) 3-20 mass %, for example 5-10 mass %, of a monoethylenic functional hydrophilic monomer component; (4) optionally, 1-20 mass %, e.g., 5-15 mass %, of a crosslinker component based on a diene-functional or higher crosslinker; and (5) 0.1-2.0 mass %, for example 0.5-1.0 mass % of a free radical initiator; and (6) Optionally, 0.1-5.0 mass %, such as 0.2-1.0 mass %, such as 0.4-0.6 mass % of an ultraviolet absorber.

16. A composition according to any one of claims 14-15, wherein in the composition: A second hydrophobic fluorinated monomer is present, preferably the first hydrophobic fluorinated monomer and the second hydrophobic fluorinated monomer are present in a mass ratio of 30:70-80:20, such as 50:50-80:20, such as 70:30-80:20; and / or A second hydrophobic silicon-containing monomer is present, 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, such as 50:50-75:25; and / or The first hydrophilic monomer and the second hydrophilic monomer are present, preferably the first hydrophilic monomer and the second hydrophilic monomer are present in a mass ratio of 0:100-85:15, such as 25:75-80:20, such as 40:60-75:

25.

17. The composition of any one of claims 14 to 16, wherein a second hydrophobic fluorine-containing monomer, a second hydrophobic silicon-containing monomer, a first hydrophilic monomer, and a second hydrophilic monomer are present.

18. The composition according to any one of claims 14 to 17, wherein The content of the first hydrophobic fluorine-containing monomer in the first hydrophobic fluorine-containing monomer component, and / or the content of the second hydrophobic fluorine-containing monomer in the second hydrophobic fluorine-containing 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 crosslinker in the crosslinker component based on a diene-functional or higher crosslinker are each independently 98% by mass or more, preferably 99% by mass or more; and / or The content of the polymerization inhibitor in the first hydrophobic fluorine-containing monomer component, and / or the second hydrophobic fluorine-containing 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 each independently 50 ppm by mass or less.

19. The composition according to any one of claims 14 to 18, wherein the composition further comprises a dye, the amount of which is, for example, 0.001-0.5% by mass, for example, 0.005-0.01% by mass; preferably, the dye is selected from reactive dyes, for example, reactive dyes containing alkenyl groups, for example, containing methacryloyl groups, for example, selected from one or more of 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone, 1,4-bis((2-hydroxyethyl)amino)-9,10-anthracenedione bis(2-propylene OIC)ester, and N-(4-hydroxy-3-(2-methylphenylazo)phenethyl)methacrylamide.

20. The composition according to any one of claims 14 to 19, wherein the composition is a composition for preparing a medical polymer, preferably a composition for preparing a contact lens, preferably a hard oxygen permeable contact lens.

21. A method for preparing a polymer, comprising: Providing a composition according to any one of claims 14 to 20, and subjecting the composition to free radical polymerization.

22. A polymer obtained by the method of claim 21, preferably the polymer is a medical polymer, preferably a polymer for contact lenses, preferably hard gas permeable contact lenses.

23. Use of the composition according to any one of claims 14 to 20 in preparing a polymer, preferably the polymer is a medical polymer, preferably the medical polymer is a polymer for corneal contact lenses, preferably the corneal contact lenses are hard oxygen permeable corneal contact lenses.

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