Ultraviolet absorbing polymers and methods for making the same

Abstract

The present invention relates to a UV-absorbing polymer composition comprising a polyolefin and a UV-absorbing agent, wherein the polyolefin contains at least one benzo-cyclobutene (BCB) pendant group, the UV-absorbing agent contains at least one dienophilic group, the polyolefin is capable of forming a cross-linked polyolefin by reaction between the BCB pendant groups, and the polyolefin and the UV-absorbing agent are covalently linked by reaction between the BCB pendant groups and the dienophilic groups. The present invention also relates to a process for the preparation of a UV-absorbing polymer and to a UV-absorbing polymer prepared thereby and to the use thereof.

Description

Technical Field

[0001] This invention relates to polymers with ultraviolet absorption capabilities and methods for their preparation. These polymers are particularly suitable for biomedical applications, such as components of intraocular lenses. Background Technology

[0002] Polyisobutylene-based polymers exhibit excellent biostability, making them particularly suitable for biomedical applications. The initial commercial application of polyisobutylene-based polymers was at Boston Scientific Corporation. The styrene-isobutylene-styrene block copolymer (SIBS) used in stents is considered one of the most successful biomedical device deployments in history. SIBS is a triblock copolymer composed of polyisobutylene (PIB) as the rubber central block and polystyrene (PS) as the two hard blocks on both sides. Due to the immiscibility of PIB and PS, this SIBS material has a microphase-separated morphology, in which the PS phase forms physical crosslinks within the rubber PIB phase matrix. Due to the thermoplastic nature of this crosslinking, SIBS material creeps and can lose its dimensions. Patent CN105330775B discloses a thermosetting polyisobutylene-based material—crosslinked polyolefin. This crosslinked polyolefin is first cationic copolymerized from isobutylene monomer and at least one olefin monomer with benzocyclobutene (BCB) side groups, and then the BCB side groups react at high temperature to form chemical crosslinks. Although this crosslinked polyolefin material overcomes the creep problem of SIBS, none of its structural units have the function of absorbing ultraviolet light, limiting its application in ophthalmic implants. If an artificial lens made of this material were to replace the natural lens of the human eye, ultraviolet rays would reach the retina without being filtered out, causing retinal damage.

[0003] Intraocular lens materials must contain ultraviolet (UV) absorbers to protect the retina from UV damage. Patent US4390676 discloses a method for introducing UV absorbers into acrylate materials, wherein acrylate monomers and UV absorbers containing acrylate groups are subjected to free radical copolymerization, causing the UV absorber to be covalently fixed in a cross-linked network. Patent US5729322 discloses a UV absorber containing styrene groups, which can copolymerize with various monomers capable of free radical polymerization. Patent US4868251 discloses a method for introducing UV absorbers into silicone rubber, wherein the UV absorber contains carbon-carbon double bonds and can undergo an addition reaction with the silicon-hydrogen bonds in silicone rubber under the action of a platinum-based catalyst, thereby covalently bonding to the silicone rubber cross-linked network.

[0004] However, the above methods of introducing ultraviolet absorbers are not applicable to cross-linked polyolefin materials because US4390676 and US5729322 use free radical reactions to copolymerize the ultraviolet absorber and monomers together, while the monomers of cross-linked polyolefins can only undergo cationic polymerization, and cross-linked polyolefin materials are composed only of carbon and hydrogen, and do not contain the silane-hydrogen bonds required by the method of US4868251.

[0005] Therefore, there is a need for a polymer material with excellent biostability and UV absorption function, as well as a method for preparing the same. Advantageously, a composition is provided that can be used to prepare a cross-linked polyolefin material covalently linked to a UV absorber. Advantageously, a cross-linked polyolefin material covalently linked to a UV absorber is provided, which exhibits excellent biocompatibility, biostability, and UV absorption function, and is particularly suitable for manufacturing ophthalmic medical devices, such as intraocular contact lenses and / or ocular implants, protecting the retina from UV damage. Advantageously, a method for preparing a UV-absorbing polymer is provided, which solves the problems of cross-linked polyolefin materials lacking UV absorption function and the difficulty in covalently bonding UV absorbers. More advantageously, a method for preparing a UV-absorbing polymer is provided, which enables the simple and reliable synthesis of cross-linked polyolefins with UV absorption function. Summary of the Invention

[0006] In one aspect, the present invention provides an ultraviolet-absorbing polymer composition comprising a polyolefin and an ultraviolet absorber, wherein the polyolefin contains at least one benzocyclobutene (BCB) side group, the ultraviolet absorber contains at least one dienophilic group, the polyolefin can be formed into a cross-linked polyolefin by a reaction between the benzocyclobutene side groups, and the polyolefin and the ultraviolet absorber can be covalently linked by a reaction between the benzocyclobutene side groups and the dienophilic groups.

[0007] In another aspect, the present invention provides a method for preparing an ultraviolet-absorbing polymer, comprising:

[0008] (a) Mixing at least one polyolefin and at least one ultraviolet absorber, wherein the polyolefin contains at least one benzocyclobutene (BCB) side group and the ultraviolet absorber contains at least one dienophilic group;

[0009] (b) Applying heat to cause the polyolefin to form a cross-linked polyolefin through a reaction between the benzocyclobutene side groups, and covalently linking the polyolefin and the ultraviolet absorber through a reaction between the benzocyclobutene side groups and the dienophilic groups.

[0010] In another aspect, the present invention provides an ultraviolet absorbing polymer prepared by the method according to the present invention.

[0011] In another aspect, the present invention provides a medical device wherein at least a portion of the medical device is composed of an ultraviolet-absorbing polymer prepared according to the method of the present invention or an ultraviolet-absorbing polymer according to the present invention.

[0012] In another aspect, the present invention provides a method for preparing a medical device, comprising injecting an ultraviolet-absorbing polymer composition according to the invention into a mold for processing to form at least a portion of the medical device, wherein the processing includes applying heat.

[0013] To address the problems of existing cross-linked polyolefin materials lacking UV absorption capabilities and the difficulty in covalently bonding UV absorbers, the inventors of this invention made various attempts and surprisingly discovered that cross-linked polyolefins with UV absorption capabilities can be obtained by using UV absorbers containing dienophilic groups and polyolefins containing benzocyclobutene (BCB) side groups. Therefore, this invention offers one or more of the following advantages: 1) a simple and reliable preparation method; 2) excellent biocompatibility; 3) excellent biostability; 4) excellent UV absorption capabilities; and 5) providing more material options for the manufacture of biomedical devices, especially ophthalmic medical devices. Attached Figure Description

[0014] The present invention will be explained in detail below with reference to specific embodiments and accompanying drawings, so that those skilled in the art can better understand the present invention, but it should not be construed as limiting the scope of the present invention in any way.

[0015] Figure 1 Infrared spectra of cross-linked poly(isobutylene-co-vinylbenzocyclobutene) with different UV absorber contents are shown.

[0016] Figure 2 The spectral transmittance of cross-linked poly(isobutylene-co-vinylbenzocyclobutene) with different UV absorber contents is shown.

[0017] Figure 3 The infrared spectra of cross-linked poly(isobutylene-co-vinylbenzocyclobutene) containing different types of ultraviolet absorbers are shown.

[0018] Figure 4 The spectral transmittance of cross-linked poly(isobutylene-co-vinylbenzocyclobutene) containing different types of UV absorbers is shown.

[0019] Figure 5 The spectral transmittance of cross-linked poly[(styrene-co-vinylbenzocyclobutene)-b-isobutylene-b-(styrene-co-vinylbenzocyclobutene)] containing a UV absorber is shown. Detailed Implementation

[0020] In the context of describing the invention (particularly in the context of the claims), unless otherwise stated herein or obviously contradicted by the context, the terms “an” and “the” and similar uses shall be construed as covering both singular and plural. Unless otherwise stated, the terms “comprising,” “having,” “including,” and “containing” shall be construed as open-ended terms (i.e., “including, but not limited to”), but also include partially closed or closed-ended terms such as “consistently consisting of” and “consisting of”. Unless otherwise stated, the term “and / or” means either or both. For example, “A and / or B” means only A, only B, or both A and B. Unless otherwise stated herein, the description of numerical ranges herein is intended only as a way of independently referring to each individual value falling within the range, and each individual value is incorporated into this specification as if it were independently described herein.

[0021] Unless otherwise stated herein or where the context clearly contradicts it, all methods described herein may be performed in any suitable order. Unless otherwise stated, the use of any and all instances or exemplary language (e.g., “such”) provided herein is intended only to better illustrate the invention and not to limit its scope. No language in this specification should be construed as indicating that any unclaimed element is necessary for the practice of this invention.

[0022] This document describes preferred embodiments of the invention, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments will become apparent to those skilled in the art upon reading this description. The inventors anticipate that those skilled in the art will be able to suitably employ such variations, and that the invention can be practiced in ways other than those specifically described herein. Therefore, the invention includes all variations and equivalents of the subject matter recited in the appended claims as permitted by applicable law. Moreover, unless otherwise stated herein or where the context clearly contradicts it, the invention covers any combination of all possible variations of the foregoing elements.

[0023] The following lists definitions of various terms used to describe the materials disclosed herein. These definitions apply to terms as used throughout this specification and claims, except where otherwise limited in certain circumstances, and these terms are used either individually or as part of a larger group.

[0024] As used in this article, the terms "optional," "optional," and "optionally" encompass both selection and non-selection. For example, "optional modification" includes both being modified and not being modified.

[0025] Throughout this specification, the terms "one aspect," "an aspect," "an embodiment," "some embodiments," "an embodiment," "a particular embodiment," "a related embodiment," "a certain embodiment," "an additional embodiment," or "a further embodiment," or combinations thereof, refer to a specific feature, structure, or characteristic described in conjunction with that embodiment being included in at least one embodiment of the invention. Therefore, the appearance of the foregoing phrases in various places throughout this specification does not necessarily refer to the same embodiment. Furthermore, specific features, structures, or characteristics can be combined in any suitable manner in one or more embodiments.

[0026] The terms "first," "second," and "third" in the "first structural unit," "second structural unit," and "third structural unit" used in this article are for convenience only and do not constitute any limitation or evaluation of the defined structural units.

[0027] The terms “covalent connection” and “covalent bond” used in this article are interchangeable and refer to two molecules or molecular structures that are connected together by a covalent bond.

[0028] The term "stoichiometry" as used in this article refers to the ratio of the amounts of substances participating in the reaction.

[0029] As used herein, the term "alkyl" refers to a straight-chain or branched alkyl group having 1 to 20 carbon atoms, wherein the number of carbon atoms may be in the range of any two of the following numbers: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20. Exemplary straight-chain alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, butyl, pentyl, and hexyl. Exemplary branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, tert-pentyl, isohexyl, and neohexyl.

[0030] As used herein, the term "alkenyl" refers to a straight-chain or branched alkenyl group having one or more carbon-carbon double bonds and having 2 to 20 carbon atoms, wherein the number of carbon atoms can be in the range of any two of the following numbers: 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20. Exemplary straight-chain alkenyl groups include, but are not limited to, vinyl, propenyl, 1-butenyl, 1-pentenyl, and 1-hexenyl. Exemplary branched alkenyl groups include, but are not limited to, isopropenyl, isobutenyl, sec-butenyl, tert-butenyl, isopentenyl, tert-pentenyl, isohexenyl, and neohexenyl.

[0031] As used herein, the term "alkynyl" refers to a straight-chain or branched alkynyl group having one or more carbon-carbon triple bonds and having 3 to 20 carbon atoms, wherein the number of carbon atoms can be in the range of any two of the following numbers: 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0032] As used herein, the term "aralkyl" means an aralkyl group having 7 to 20 carbon atoms, wherein the number of carbon atoms may be in the range of any two of the following numbers: 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20. Exemplary aralkyl groups include, but are not limited to, benzyl, phenethyl, and phenylpropyl.

[0033] As used herein, the term "halogenated alkyl" means an alkyl group substituted with one or more halogen atoms, wherein each halogen is independently F, Cl, Br, or I.

[0034] As used herein, the term "alkoxy" refers to a group derived from an alcohol having at least one carbon atom, attached to an alkyl group via an oxygen atom, wherein the number of carbon atoms can be any two of the following numbers: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20. Representative examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, 2-propoxy, butoxy, tert-butoxy, pentoxy, and hexoxy.

[0035] As used herein, the term "ester group" refers to a group derived from ester compounds with the structural formula -COOR, where R represents an alkyl group, preferably a straight-chain or branched alkyl group having 1 to 20 carbon atoms as defined above.

[0036] As used herein, the term "alkylene" refers to a divalent group having two connection points as described above for "alkyl," wherein the number of carbon atoms may be any two of the following numbers: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20. For example, methylene is a -CH2- group, and ethylene is a -CH2-CH2- group.

[0037] As used herein, the term “arylene alkyl” means a divalent group as described above for “aryl alkyl” but with two connection points, wherein the number of carbon atoms may be in the range of any two of the following numbers: 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0038] The term “oxoalkylene” as used in this article refers to a divalent group formed by the attachment of an alkylene group to an oxygen group, wherein the number of carbon atoms in the alkylene group can be any of the following two numbers: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0039] As used herein, the term "anhydride group" refers to a group derived from an anhydride compound with the structural formula -C(O)O(O)CR, where R represents an alkyl group, preferably a straight-chain or branched alkyl group having 1 to 20 carbon atoms as defined above.

[0040] The term "tertiary amine cation" used in this article can be represented as -N + R3, or with -N + R3A - It exists in the form of, where R represents an alkyl group, preferably a straight-chain or branched alkyl group having 1 to 20 carbon atoms as defined above, A - This refers to anion that can form compounds with tertiary amine cations, such as, but not limited to, halide ions, such as F. - Cl - ,Br - I - ,etc.

[0041] In this article, unless otherwise specified, variables represented by the same letter have the same meaning.

[0042] Advantageously, this invention utilizes the Diels-Alder reaction to achieve covalent bonding between polyolefins and UV absorbers, allowing the UV absorber to be covalently bonded to the crosslinked network while simultaneously forming the polyolefin crosslinked network, thereby endowing the crosslinked polyolefin with UV absorption functionality. Specifically, when a UV absorber containing a dienophilic group and a polyolefin containing a benzocyclobutene (BCB) side group are blended and heated to a certain temperature (e.g., 180°C or higher), the BCB group undergoes ring-opening to form a conjugated diene. This conjugated diene can react with another conjugated diene to form an eight-membered ring, thus crosslinking the polymer, or it can undergo a Diels-Alder reaction with the dienophilic group in the UV absorber to form a six-membered ring, thereby covalently bonding the UV absorber to the crosslinked network.

[0043] Therefore, the present invention provides an ultraviolet absorbing polymer composition comprising a polyolefin and an ultraviolet absorber, wherein the polyolefin contains at least one benzocyclobutene (BCB) side group, the ultraviolet absorber contains at least one dienophilic group, the polyolefin can be cross-linked to form a polyolefin by a reaction between the benzocyclobutene side groups, and the polyolefin and the ultraviolet absorber can be covalently linked by a reaction between the benzocyclobutene side groups and the dienophilic groups.

[0044] In some embodiments, the UV-absorbing polymer composition according to the invention further includes a reaction product of the polyolefin and the UV absorber, the reaction product comprising a cross-linked polyolefin covalently bonded to the UV absorber. The reaction of the polyolefin and the UV absorber includes a reaction in which a cross-linking network is formed between the benzocyclobutene side groups of the polyolefin, and a Diels-Alder reaction in which the UV absorber is covalently bonded to the cross-linking network by covalent bonding between the benzocyclobutene side groups of the polyolefin and the dienophilic groups of the UV absorber, and these two reactions together form a cross-linked polyolefin covalently bonded to the UV absorber.

[0045] The ultraviolet-absorbing polymer composition may not contain any catalysts and / or initiators.

[0046] In some embodiments, the polyolefin includes a first structural unit, a second structural unit, and an optional third structural unit, wherein the first structural unit is derived from at least one cationically polymerizable branched olefin monomer, the second structural unit is derived from at least one cationically polymerizable olefin monomer having a benzocyclobutene side group, and the third structural unit is derived from at least one monomer capable of forming a glassy substance. The first, second, and third structural units each appear in the polyolefin molecule at a frequency of at least 2 times, more typically at least 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, or more times.

[0047] The polyolefin can exhibit various structures, such as cyclic, linear, and / or branched structures. Branched structures include star structures (e.g., structures in which three or more chains emanate from a single region), comb structures (e.g., graft copolymers having a main chain and multiple side chains), and dendritic structures (including arborescent or hyperbranched copolymers). In some embodiments, the polyolefin is one or more of linear random copolymers, linear block copolymers, star random copolymers, star block copolymers, and other hyperbranched copolymers.

[0048] The polyolefin can undergo a crosslinking reaction at high temperatures, for example, within a temperature range defined by any two of the following values: 180°C, 200°C, 220°C, 240°C, 260°C, and 280°C. Preferably, the polyolefin undergoes a crosslinking reaction at elevated temperatures (e.g., 200°C or higher).

[0049] The cationically polymerizable branched olefin monomer can be any monomer that is both branched and contains a single double bond. In some embodiments, the branched olefin monomer is selected from C4-C14 branched olefins, preferably from C4-C10 or C4-C7 olefins, and more preferably from isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, β-pinene, and combinations thereof. Preferably, the branched olefin monomer is selected from isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, and combinations thereof.

[0050] The cationically polymerizable olefin monomer having a benzocyclobutene (BCB) side group can be any olefin monomer containing at least one BCB-functional moiety in the olefin. In some embodiments, the olefin monomer having a benzocyclobutene side group is selected from compounds shown in structural formula 1:

[0051]

[0052] When n is 0, R is hydrogen or alkyl, preferably methyl, ethyl or propyl; or when n is an integer selected from 1 to 3, R is alkyl, preferably methyl, ethyl or propyl.

[0053] In some embodiments, the olefin monomer having a benzocyclobutene side group is selected from 4-vinylbenzocyclobutene, 4-(α-alkylvinyl)benzocyclobutene (e.g., 2-(4-benzocyclobutenyl)-propylene and 2-(4-benzocyclobutenyl)-1-butene), 4-(2-methyl-alkenyl)benzocyclobutene (e.g., 2-methyl-3-(4-benzocyclobutenyl)-1-propylene and 2-methyl-4-(4-benzocyclobutenyl)-1-butene), and combinations thereof.

[0054] The monomer capable of forming a glassy substance can be any monomer known to those skilled in the art that can form a glassy substance. In some embodiments, the monomer capable of forming a glassy substance is selected from styrene, α-alkylstyrene (e.g., α-methylstyrene), 4-alkylstyrene (e.g., p-tert-butylstyrene), 4-alkoxystyrene, aromatic ring-substituted styrene, diphenylethylene, norbornadiene, norbornene, p-chlorostyrene, indene, and combinations thereof.

[0055] The polyolefin may also include structural units derived from other cationically polymerizable olefin monomers. For example, the polyolefin may contain one or more structural units derived from 1,3-diene, vinyl ether, N-vinyl ether, N-vinylcarbazole, N-vinylpyrrolidone, aldehyde, ketone, or combinations thereof. In some embodiments, the polyolefin further includes one or more structural units derived from 1,3-diene. Preferred 1,3-dienes include isoprene, 1,3-butadiene, and combinations thereof.

[0056] In some embodiments, the polyolefin is selected from random copolymers of isobutylene and vinylbenzocyclobutene, random copolymers of isobutylene and styrene and vinylbenzocyclobutene, random copolymers of isobutylene and α-methylstyrene and vinylbenzocyclobutene, block copolymers of isobutylene and vinylbenzocyclobutene, (styrene-co-vinylbenzocyclobutene)-isobutylene-(styrene-co-vinylbenzocyclobutene) block copolymers, (α-methylstyrene-co-vinylbenzocyclobutene)-isobutylene-(α-methylstyrene-co-vinylbenzocyclobutene) block copolymers, and combinations thereof. Preferably, the polyolefin is selected from random copolymers of isobutylene and vinylbenzocyclobutene, (styrene-co-vinylbenzocyclobutene)-isobutylene-(styrene-co-vinylbenzocyclobutene) block copolymers, and combinations thereof.

[0057] The UV absorber of this invention contains a dienophilic group, which can form a covalent bond with the side group of the polyolefin benzocyclobutene under heating conditions via a Diels-Alder reaction. The reaction process does not require a catalyst or initiator and does not release small molecule residues, resulting in high biocompatibility of the material. In some embodiments, the dienophilic group is selected from the carbon-carbon double bond shown in structural formula 2, the carbon-carbon triple bond shown in structural formula 3, and combinations thereof.

[0058]

[0059] R1, R2, and R3 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, alkoxy, hydroxyl, formyl, ester, carboxyl, cyano, nitro, halogen, acid anhydride, haloalkyl, sulfonyl, amino, amide, tertiary amine cation, and combinations thereof, and optionally, any two of R1, R2, and R3 can be cyclically linked by covalent bonds.

[0060]

[0061] R4 is selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, alkoxy, hydroxyl, formyl, ester, carboxyl, cyano, nitro, halogen, acid anhydride, haloalkyl, sulfonyl, amino, amide, tertiary amine cation and combinations thereof.

[0062] In some embodiments, the ultraviolet absorber is selected from benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, and combinations thereof.

[0063] In some embodiments, the ultraviolet absorber is selected from ultraviolet absorbers of structural formulas 4-6 and combinations thereof:

[0064]

[0065] R5, R6, and R7 are independently selected from dienophilic groups, hydrogen, alkyl, aralkyl, alkoxy, hydroxyl, formyl, ester, carboxyl, cyano, nitro, halogen, amino, and combinations thereof, and at least one of R5, R6, and R7 is a dienophilic group. A linking group may exist between the dienophilic group and the conjugated cyclic structure of the UV absorber, such as alkylene, aralkylene, oxyalkylene, ether bond, carbonyl, carbonyloxy, imino, and combinations thereof.

[0066]

[0067] R8 and R9 are independently selected from dienophilic groups, hydrogen, alkyl, aralkyl, alkoxy, hydroxy, formyl, ester, carboxyl, cyano, nitro, halogen, amino, and combinations thereof, and at least one of R8 and R9 is a dienophilic group, wherein a linking group may exist between the dienophilic group and the conjugated cyclic structure of the ultraviolet absorber, such as alkylene, aralkylene, oxyalkylene, ether bond, carbonyl, carbonyloxy, imino, and combinations thereof;

[0068]

[0069] R10, R11, R12, R13, and R14 are independently selected from dienophilic groups, hydrogen, alkyl, aralkyl, alkoxy, hydroxyl, formyl, ester, carboxyl, cyano, nitro, halogen, amino, and combinations thereof, and at least one of R10, R11, R12, R13, and R14 is a dienophilic group, wherein a linking group may exist between the dienophilic group and the conjugated cyclic structure of the UV absorber, such as alkylene, aralkylene, oxyalkylene, ether bond, carbonyl, carbonyloxy, imino, and combinations thereof;

[0070] Preferably, the ultraviolet absorber is selected from ultraviolet absorbers and combinations thereof shown in structural formulas 7-12:

[0071]

[0072]

[0073] The present invention also provides a method for preparing an ultraviolet absorbing polymer, comprising:

[0074] (a) Mixing at least one polyolefin and at least one ultraviolet absorber, wherein the polyolefin contains at least one benzocyclobutene (BCB) side group and the ultraviolet absorber contains at least one dienophilic group;

[0075] (b) Applying heat to cause the polyolefin to form a cross-linked polyolefin through a reaction between the benzocyclobutene side groups, and covalently linking the polyolefin and the ultraviolet absorber through a reaction between the benzocyclobutene side groups and the dienophilic groups.

[0076] Step (a) can be performed using either a wet or dry process. A wet process can be achieved by uniformly mixing the at least one polyolefin and the at least one UV absorber in an organic solvent, followed by evaporation of the organic solvent. A dry process can be achieved by uniformly mixing the at least one polyolefin and the at least one UV absorber through extrusion from a twin-screw extruder. Other wet or dry processes known to those skilled in the art can also be used to mix the polyolefin and the UV absorber.

[0077] Wet mixing can be performed using any suitable organic solvent known to those skilled in the art. Examples of such organic solvents include, but are not limited to, benzene, toluene, chlorobenzene, dichloromethane, chloroform, n-pentane, n-hexane, n-heptane, n-octane, and combinations thereof. The organic solvent can then be evaporated or removed, for example, by vacuum drying.

[0078] Step (b) is performed under conditions of applied heat. In some embodiments, step (b) is performed at high temperatures, for example, at temperatures ranging from any two of the following values: 180°C, 200°C, 220°C, 240°C, 260°C, and 280°C.

[0079] The reaction in step (b) generally does not require a catalyst or initiator.

[0080] In some embodiments, the reaction time of step (b) can be within a range consisting of any two of the following values ​​as endpoints: 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 25 hours, 30 hours, 35 hours, and 40 hours.

[0081] In some embodiments, step (b) is performed at a temperature of at least 180°C (e.g., at least 200°C, at least 220°C, at least 240°C, at least 260°C, or at least 280°C) for 0.5 to 20 hours (e.g., 1 to 18 hours, 1 to 15 hours, 1 to 10 hours, 2 to 8 hours, or 5 to 10 hours).

[0082] The molar ratio of the polyolefin to the UV absorber can be adjusted as needed. Since the crosslinking reaction between the BCB side groups of the polyolefin and the Diels-Alder reaction between the BCB of the polyolefin and the dienophilic groups of the UV absorber are competitive, adding too much UV absorber will reduce the degree of crosslinking of the polymer. In some embodiments, the molar ratio of the dienophilic groups to the benzocyclobutene (BCB) side groups is within a range consisting of any two of the following ratios as endpoints: 1:100, 2:100, 3:100, 4:100, 5:100, 6:100, 7:100, 8:100, 9:100, 10:100, 11:100, 12:100, 13:100, 14:100, 15:100. The molar ratios are 16:100, 17:100, 18:100, 19:100, 20:100, 22:100, 24:100, 26:100, 28:100, 30:100, 32:100, 34:100, 36:100, 38:100, 40:100, 42:100, 44:100, 46:100, 48:100, 50:100, 55:100, and 60:100. Preferably, the molar ratio of the dienophilic group to the benzocyclobutene (BCB) side group is 1:100-50:100, more preferably 5:100-30:100.

[0083] In some embodiments, the polyolefin is prepared by cationic polymerization comprising a mixture of the following components: i) at least one cationically polymerizable branched olefin monomer, ii) at least one cationically polymerizable olefin monomer having a benzocyclobutene side group, and iii) optionally, at least one monomer capable of forming a glassy substance. The cationic polymer can be carried out in the presence of at least one initiator and optionally at least one Lewis acid co-initiator. In some embodiments, the polyolefin can be prepared by the method described in patent CN105330775B, the entire contents of which are incorporated herein by reference.

[0084] In some embodiments, the method further includes step (c), which involves extracting the product of step (b) with an organic solvent to remove the UV absorber that is not covalently linked to the crosslinked polyolefin. Organic solvents that can be used for extraction include, but are not limited to, benzene, toluene, chlorobenzene, dichloromethane, chloroform, n-pentane, n-hexane, n-heptane, n-octane, and combinations thereof.

[0085] In some embodiments, the steps of the method are carried out independently of each other, in or out of a non-reactive gas. The non-reactive gas includes nitrogen, inert gases such as argon (Ar), nitrogen (N2), helium (He), neon (Ne), and mixtures thereof. In some embodiments, step (b) of the method is carried out in a non-reactive gas, preferably in a nitrogen atmosphere, to avoid high-temperature thermal oxidation of the raw materials and / or products.

[0086] The present invention also provides an ultraviolet absorbing polymer, which is prepared by the method described above according to the present invention.

[0087] The present invention also provides a medical device wherein at least a portion of the medical device is composed of an ultraviolet-absorbing polymer according to the present invention.

[0088] The ultraviolet-absorbing polymers of the present invention are particularly suitable for manufacturing medical devices for the eye, which further protect the retina from ultraviolet damage while maintaining excellent biocompatibility and / or biostability. In some embodiments, the medical devices include intraocular contact lenses and / or ocular implants such as intraocular lenses, artificial corneas, artificial corneal endothelium, artificial irises, glaucoma drainage tubes, artificial lacrimal ducts, punctal plugs, and combinations thereof.

[0089] This invention also provides a method for preparing a medical device using the ultraviolet-absorbing polymer composition of this invention. In some embodiments, the method for preparing the medical device includes injecting the ultraviolet-absorbing polymer composition of this invention into a mold and then heat-treating it to form at least a portion of the medical device. In some embodiments, the method for preparing the medical device includes heat-treating the ultraviolet-absorbing polymer composition of this invention and then machining it to form at least a portion of the medical device. Those skilled in the art can select a suitable mold and / or a suitable machining method according to actual needs. Suitable machining methods include, but are not limited to, cutting and pressure processing. Cutting includes, for example, turning, milling, drilling, grinding, or combinations thereof. Pressure processing includes, for example, casting, forging, stamping, welding, or combinations thereof.

[0090] In some embodiments, the heat treatment includes applying heat to cure the UV-absorbing polymer composition to a temperature within a range consisting of any two of the following values: 180°C, 200°C, 220°C, 240°C, 260°C, and 280°C. Preferably, the heat treatment includes applying heat to cure the UV-absorbing polymer composition to a temperature of at least 200°C. In some embodiments, the duration of the heat treatment can be within a range consisting of any two of the following values ​​as endpoints: 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 25 hours, 30 hours, 35 hours, and 40 hours. Preferably, the duration of the heat treatment is 0.5-20 hours, more preferably 1-10 hours.

[0091] The product or its blank can be obtained by heat treatment in a mold or by machining after heat treatment.

[0092] Optionally, the method may further include an extraction step with an organic solvent after the heat treatment step to remove UV absorbers that are not covalently bonded to the crosslinked network. Organic solvents that can be used for extraction include, but are not limited to, benzene, toluene, chlorobenzene, dichloromethane, chloroform, n-pentane, n-hexane, n-heptane, n-octane, and combinations thereof.

[0093] The method may also include a step of further processing the product or its blank, depending on the requirements of the final product.

[0094] In some embodiments, the resulting product is selected from one or more of intraocular contact lenses and ocular implants such as artificial lenses, artificial corneas, artificial corneal endothelium, artificial irises, glaucoma drainage tubes, artificial lacrimal ducts, and punctal plugs.

[0095] In some implementations, the resulting product is an artificial lens and / or an artificial cornea.

[0096] In some embodiments, the ultraviolet-absorbing polymer or product obtained according to the present invention has an ultraviolet cutoff wavelength of not less than 360 nm, more preferably not less than 380 nm, and even not less than 390 nm or 400 nm, to have sufficient ultraviolet filtering capability. For example, according to the requirements of intraocular lens standard YY0290.2, for an intraocular lens or equivalent with an optical power of 20D, when the wavelength corresponding to 10% spectral transmittance is used as the ultraviolet cutoff wavelength, this wavelength should be not less than 360 nm. In this document, the ultraviolet cutoff wavelength is used to characterize the material's ability to absorb ultraviolet light. The larger the ultraviolet cutoff wavelength, the stronger the absorption capability of ultraviolet light.

[0097] In some embodiments, the refractive index of the ultraviolet-absorbing polymer or product obtained according to the present invention is 1.4-1.6. In some embodiments, the refractive index of the ultraviolet-absorbing polymer or product obtained according to the present invention can be any of the following values ​​or within a range consisting of any two of the following values ​​as endpoints: 1.40, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, 1.60.

[0098] Example

[0099] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0100] Unless otherwise specified, the experimental techniques and methods used in this embodiment are conventional techniques and methods. Unless otherwise specified, the materials and reagents used in the embodiment can be synthesized by well-known methods or obtained through commercial means. The synthesis techniques and conditions used are also easily understood by those skilled in the art.

[0101] Appropriate modifications and adjustments to various conditions, formulations, and other parameters commonly encountered in the art, as well as modifications and adjustments that are obvious to those skilled in the art based on the content of this disclosure, are all within the spirit and scope of this invention.

[0102] The following examples use ultraviolet absorbers with structural formulas 7, 8, and 11 as examples to illustrate the present invention.

[0103]

[0104]

[0105] The following tests were performed on the samples in the examples:

[0106] 1. Infrared Spectroscopy

[0107] Infrared spectra were measured using a Spectrum Two FT-IR infrared spectrometer (PerkinElmer).

[0108] 2. Spectral transmittance

[0109] Spectral transmittance was tested using a UV-Vis spectrophotometer (P9 UV-Vis spectrophotometer, Shanghai Meipuda Instrument Co., Ltd.).

[0110] Example 1: Crosslinked poly(isobutylene-co-vinylbenzocyclobutene) with different amounts of UV absorber

[0111] Crosslinked poly(isobutylene-co-vinylbenzocyclobutene) with different contents of ultraviolet absorber were prepared using the ultraviolet absorber shown in structural formula 8.

[0112] Weigh 2.106 g of poly(isobutylene-co-vinylbenzocyclobutene) (molecular weight 50,000, with a vinylbenzocyclobutene molar percentage of 8% based on the total amount of isobutylene repeating units and vinylbenzocyclobutene repeating units). Weigh 0.025 g of the UV absorber shown in structural formula 8. This ensures a molar ratio of dienophilic groups to benzocyclobutene (BCB) side groups of 3:100. Dissolve the poly(isobutylene-co-vinylbenzocyclobutene) in 10 mL of n-hexane, and dissolve the UV absorber shown in structural formula 8 in 0.5 mL of chloroform. Mix the two thoroughly and remove the solvent in a 100°C oven until constant weight is achieved. The resulting uniformly mixed material is sandwiched between two glass plates spaced 1 mm apart and cured in a 240℃ constant temperature hot press (TS-C40DX-HC, Taikesheng Automation Systems Co., Ltd.) for 40 minutes to obtain cross-linked poly(isobutylene-co-vinylbenzocyclobutene) sheet A containing UV absorber.

[0113] Weigh 2.006 g of poly(isobutylene-co-vinylbenzocyclobutene) (molecular weight 50,000, with a vinylbenzocyclobutene molar percentage of 8% based on the total amount of isobutylene repeating units and vinylbenzocyclobutene repeating units). Weigh 0.048 g of the UV absorber shown in structural formula 8. This ensures a molar ratio of dienophilic groups to benzocyclobutene (BCB) side groups of 6:100. Dissolve the poly(isobutylene-co-vinylbenzocyclobutene) in 10 mL of n-hexane, and dissolve the UV absorber shown in structural formula 8 in 0.5 mL of chloroform. Mix the two thoroughly and remove the solvent in a 100°C oven until constant weight is achieved. The resulting uniformly mixed material is sandwiched between two glass plates spaced 1 mm apart and cured for 40 minutes in a constant temperature hot press at 240℃ (TS-C40DX-HC, Taikesheng Automation Systems Co., Ltd.) to obtain cross-linked poly(isobutylene-co-vinylbenzocyclobutene) sheet B containing ultraviolet absorber.

[0114] Weigh 2.243 g of poly(isobutylene-co-vinylbenzocyclobutene) (molecular weight 50,000, with a vinylbenzocyclobutene molar percentage of 8% based on the total amount of isobutylene repeating units and vinylbenzocyclobutene repeating units). Weigh 0.081 g of the UV absorber shown in structural formula 8. This ensures a molar ratio of dienophilic groups to benzocyclobutene (BCB) side groups of 10:100. Dissolve the poly(isobutylene-co-vinylbenzocyclobutene) in 10 mL of n-hexane, and dissolve the UV absorber shown in structural formula 8 in 0.5 mL of chloroform. Mix the two thoroughly and remove the solvent in a 100°C oven until constant weight is achieved. The resulting uniformly mixed material is sandwiched between two glass plates spaced 1 mm apart and cured for 40 minutes in a constant temperature hot press at 240℃ (TS-C40DX-HC, Taikesheng Automation Systems Co., Ltd.) to obtain cross-linked poly(isobutylene-co-vinylbenzocyclobutene) sheet C containing ultraviolet absorber.

[0115] Sheets A, B, and C were extracted in hexane, dried, and then their performance was tested.

[0116] Figure 1 The infrared spectra of cross-linked poly(isobutylene-co-vinylbenzocyclobutene) sheets A, B, and C with different UV absorber contents are shown. (Figure 745cm) -1 The peak at 745 cm⁻¹ belongs to the UV absorber shown in structural formula 8, indicating successful covalent bonding of the UV absorber. With increasing UV absorber content, the peak at 745 cm⁻¹... -1 The enhanced absorption peak at that location indicates that the method of the present invention can be applied to different contents of ultraviolet absorbers.

[0117] Figure 2The spectral transmittance of cross-linked poly(isobutylene-co-vinylbenzocyclobutene) sheets A, B, and C with different UV absorber contents is shown. The transmittance of the material is essentially zero at wavelengths below 380 nm, indicating that the material can effectively filter out ultraviolet light. The transmittance of the material is greater than 90% at wavelengths above 450 nm, indicating good transmittance of visible light. When the molar ratio of the diephilic group and the benzocyclobutene (BCB) side group of the UV absorber shown in Formula 8 increases from 3:100 to 6:100 and 10:100, the UV cutoff wavelength (the wavelength corresponding to the point of 10% transmittance) of the material gradually increases to 385 nm, 390 nm, and 393 nm, respectively, indicating that the spectral transmittance curve can be controlled by the content of the UV absorber.

[0118] Example 2: Crosslinked poly(isobutylene-co-vinylbenzocyclobutene) containing different types of UV absorbers

[0119] Crosslinked poly(isobutylene-co-vinylbenzocyclobutene) containing different types of ultraviolet absorbers was prepared using ultraviolet absorbers shown in structural formulas 7, 8, and 11.

[0120] Weigh 2.106 g of poly(isobutylene-co-vinylbenzocyclobutene) (molecular weight 50,000, with a vinylbenzocyclobutene molar percentage of 8% based on the total amount of isobutylene repeating units and vinylbenzocyclobutene repeating units). Weigh 0.025 g of the UV absorber shown in structural formula 8. This ensures that the molar ratio of the dienophilic group to the benzocyclobutene (BCB) side group is 3:100. Dissolve the poly(isobutylene-co-vinylbenzocyclobutene) in 10 mL of n-hexane, and dissolve the UV absorber shown in structural formula 8 in 0.5 mL of chloroform. Mix the two thoroughly and remove the solvent in a 100°C oven until constant weight is achieved. The resulting uniformly mixed material is sandwiched between two glass plates spaced 1 mm apart and cured in a 240℃ constant temperature hot press (TS-C40DX-HC, Taikesheng Automation Systems Co., Ltd.) for 40 minutes to obtain cross-linked poly(isobutylene-co-vinylbenzocyclobutene) sheet A containing UV absorber.

[0121] Weigh 2.261 g of poly(isobutylene-co-vinylbenzocyclobutene) (molecular weight 50,000, with a vinylbenzocyclobutene molar percentage of 8% based on the total amount of isobutylene repeating units and vinylbenzocyclobutene repeating units). Weigh 0.041 g of the UV absorber shown in structural formula 7. This ensures a molar ratio of dienophilic groups to benzocyclobutene (BCB) side groups of 3:100. Dissolve the poly(isobutylene-co-vinylbenzocyclobutene) in 10 mL of n-hexane, and dissolve the UV absorber shown in structural formula 7 in 0.5 mL of chloroform. Mix the two thoroughly and remove the solvent in a 100°C oven until constant weight is achieved. The resulting uniformly mixed material is sandwiched between two glass plates spaced 1 mm apart and cured in a 240℃ constant temperature hot press (TS-C40DX-HC, Taikesheng Automation Systems Co., Ltd.) for 40 minutes to obtain cross-linked poly(isobutylene-co-vinylbenzocyclobutene) sheet D containing ultraviolet absorber.

[0122] Weigh 2.357 g of poly(isobutylene-co-vinylbenzocyclobutene) (molecular weight 50,000, with a vinylbenzocyclobutene molar percentage of 8% based on the total amount of isobutylene repeating units and vinylbenzocyclobutene repeating units). Weigh 0.033 g of the UV absorber shown in structural formula 11. This ensures a molar ratio of dienophilic groups to benzocyclobutene (BCB) side groups of 3:100. Dissolve the poly(isobutylene-co-vinylbenzocyclobutene) in 10 mL of n-hexane, and dissolve the UV absorber shown in structural formula 11 in 0.5 mL of chloroform. Mix the two thoroughly and remove the solvent in a 100°C oven until constant weight is achieved. The resulting uniformly mixed material is sandwiched between two glass plates spaced 1 mm apart and cured in a 240℃ constant temperature hot press (TS-C40DX-HC, Taikesheng Automation Systems Co., Ltd.) for 40 minutes to obtain cross-linked poly(isobutylene-co-vinylbenzocyclobutene) sheet E containing ultraviolet absorber.

[0123] Sheets A, D, and E were extracted in hexane, dried, and then their performance was tested.

[0124] Figure 3 The infrared spectra of cross-linked poly(isobutylene-co-vinylbenzocyclobutene) sheets A, D, and E containing different types of ultraviolet absorbers are shown. In the infrared spectrum of sheet A, at 745 cm⁻¹... -1 The peak at 745 cm⁻¹ belongs to the ultraviolet absorber shown in structural formula 8; in the infrared spectrum of sheet D, the peak at 745 cm⁻¹... -1 The peak at 698 cm⁻¹ belongs to the ultraviolet absorber shown in structural formula 7; in the infrared spectrum of sheet E, the peak at 698 cm⁻¹... -1 The peaks at these locations belong to the UV absorber shown in structural formula 11. The appearance of these peaks indicates that the UV absorber has been successfully covalently linked to the polymer. The method of this invention is applicable to different types of UV absorbers containing different dienophilic groups.

[0125] Figure 4 The spectral transmittance of cross-linked poly(isobutylene-co-vinylbenzocyclobutene) sheets A, D, and E containing different types of UV absorbers is shown. The transmittance of the materials is essentially zero at wavelengths below 380 nm, indicating that the materials can effectively filter ultraviolet light. The transmittance of the materials is greater than 90% at wavelengths above 450 nm, indicating good transmittance of visible light. When the molar ratio of the diephilic group to the benzocyclobutene (BCB) side group of the UV absorber is 3:100, the UV cutoff wavelengths (wavelengths corresponding to the point of 10% transmittance) of sheets A, D, and E are 385 nm, 414 nm, and 385 nm, respectively. Sheet D also shows significant absorption in the blue light region above 400 nm, indicating that the material has the ability to filter blue light. The UV absorption performance of the materials of this invention can be controlled by using different UV absorbers and their combinations, and even the materials can be made to have blue light filtering function. It is readily apparent that the material of the present invention can also possess dual ultraviolet / blue light filtering capabilities by using a combination of an ultraviolet absorber with a dienophilic group and a yellow dye with a dienophilic group. Alternatively, the material can possess ultraviolet filtering capabilities and a specific color by using a combination of an ultraviolet absorber with a dienophilic group and a colored dye with a dienophilic group.

[0126] Example 3: Crosslinked poly[(styrene-co-vinylbenzocyclobutene)-b-isobutylene-b-] containing UV absorber (Styrene-co-vinylbenzocyclobutene)

[0127] Crosslinked poly[(styrene-co-vinylbenzocyclobutene)-b-isobutene-b-(styrene-co-vinylbenzocyclobutene)] containing ultraviolet absorber was prepared using the ultraviolet absorber shown in structural formula 8.

[0128] Take 6.7g of poly[(styrene-co-vinylbenzocyclobutene)-b-isobutylene-b-(styrene-co-vinylbenzocyclobutene)] (molecular weight 70,000, with a styrene molar percentage of 17% and a vinylbenzocyclobutene molar percentage of 8% based on the total amount of styrene repeating units, vinylbenzocyclobutene repeating units, and isobutylene repeating units). Also weigh 0.134g of the UV absorber shown in structural formula 8. The molar ratio of the dienophilic group to the benzocyclobutene (BCB) side group should be 6:100. Place both in a beaker and add 30mL of toluene to dissolve them completely. Pour the solution into a 10cm x 10cm metal dish and place it in a 100℃ oven to evaporate the solvent until constant weight is achieved, yielding a sheet approximately 1mm thick. The sheet is placed between two glass plates and cured for 40 minutes in a 240℃ constant temperature hot press (TS-C40DX-HC, Taikesheng Automation Systems Co., Ltd.) to obtain cross-linked poly[(styrene-co-vinylbenzocyclobutene)-b-isobutylene-b-(styrene-co-vinylbenzocyclobutene)] sheet F containing ultraviolet absorbers.

[0129] Sheet F was extracted in n-hexane, dried, and then its performance was tested.

[0130] Figure 5 The spectral transmittance of cross-linked poly[(styrene-co-vinylbenzocyclobutene)-b-isobutylene-b-(styrene-co-vinylbenzocyclobutene)] sheet F containing a UV absorber is shown. The material has a UV cutoff wavelength of 394 nm, and the transmittance is essentially zero at wavelengths below 380 nm, indicating that the material can effectively filter out ultraviolet light, and the UV absorber is successfully attached to the polymer.

[0131] Although the word "about" is not used to describe the numerical values ​​and ranges mentioned in this application, it should be understood that these numerical values ​​and ranges can vary within ±5% without departing from the scope of the invention.

[0132] Unless expressly stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. While some methods and materials are specifically described herein, similar or equivalent methods and materials, though not specifically mentioned herein, may also be used to practice the invention. For example, the various specific parameter variations described herein are not an exhaustive list of all structures that can be used to construct the glaucoma drainage tubes provided herein. Furthermore, features of one or more shown parameters may be combined with features of one or more other shown parameters to produce many different combinations that are within the scope of this application. All published materials, patent applications, patents, and other references mentioned herein are incorporated herein by reference in their entirety. In case of conflict, the definitions in this application shall prevail. Moreover, these materials, methods, and examples are merely illustrative and should not be construed as limiting the scope of protection claimed herein.

[0133] Although this specification contains details of numerous specific embodiments, these details should not be construed as limiting the scope of any invention or the content that may be claimed, but rather as specific descriptions of features of particular embodiments that may be part of a particular invention. Certain features described in the context of individual embodiments may also be implemented in combination in a single embodiment, and various features described in the context of a single embodiment may also be implemented individually or in any suitable sub-combination in multiple embodiments.

Claims

1. A UV-absorbing polymer composition comprising a polyolefin and a UV absorber, wherein the polyolefin contains at least one benzocyclobutene (BCB) side group, the UV absorber contains at least one dienophilic group, the polyolefin can be cross-linked to form a polyolefin by a reaction between the benzocyclobutene side groups, and the polyolefin and the UV absorber can be covalently linked by a reaction between the benzocyclobutene side groups and the dienophilic groups.

2. The ultraviolet-absorbing polymer composition according to claim 1, further comprising a reaction product of the polyolefin and the ultraviolet absorber, the reaction product comprising a cross-linked polyolefin covalently linked to the ultraviolet absorber.

3. The UV-absorbing polymer composition according to claim 1 or 2, wherein the polyolefin comprises a first structural unit, a second structural unit, and optionally a third structural unit, the first structural unit being derived from at least one cationically polymerizable branched olefin monomer, the second structural unit being derived from at least one cationically polymerizable olefin monomer having a benzocyclobutene side group, and the third structural unit being derived from at least one monomer capable of forming a glassy substance.

4. The ultraviolet-absorbing polymer composition according to claim 3, wherein the branched olefin monomer is selected from C4-C14 branched olefins, preferably from C4-C10 olefins or C4-C7 olefins, and more preferably from isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, β-pinene and combinations thereof.

5. The ultraviolet-absorbing polymer composition according to claim 3, wherein the olefin monomer having a benzocyclobutene side group is selected from the compounds shown in structural formula 1: When n is 0, R is hydrogen or alkyl, preferably methyl, ethyl or propyl; or when n is an integer selected from 1 to 3, R is alkyl, preferably methyl, ethyl or propyl.

6. The UV-absorbing polymer composition according to claim 3, wherein the olefin monomer having a benzocyclobutene side group is selected from 4-vinylbenzocyclobutene, 4-(α-alkylvinyl)benzocyclobutene (e.g., 2-(4-benzocyclobutenyl)-propylene and 2-(4-benzocyclobutenyl)-1-butene), 4-(2-methyl-alkenyl)benzocyclobutene (e.g., 2-methyl-3-(4-benzocyclobutenyl)-1-propylene and 2-methyl-4-(4-benzocyclobutenyl)-1-butene), and combinations thereof.

7. The ultraviolet-absorbing polymer composition according to claim 3, wherein the monomer capable of forming a glassy substance is selected from styrene, α-alkylstyrene (e.g., α-methylstyrene), 4-alkylstyrene (e.g., p-tert-butylstyrene), 4-alkoxystyrene, aromatic ring-substituted styrene, diphenylethylene, norbornadiene, norbornene, p-chlorostyrene, indene, and combinations thereof.

8. The ultraviolet-absorbing polymer composition according to claim 1 or 2, wherein the polyolefin is selected from random copolymers of isobutylene and vinylbenzocyclobutene, random copolymers of isobutylene and styrene and vinylbenzocyclobutene, random copolymers of isobutylene and α-methylstyrene and vinylbenzocyclobutene, block copolymers of isobutylene and vinylbenzocyclobutene, (styrene-co-vinylbenzocyclobutene)-isobutylene-(styrene-co-vinylbenzocyclobutene) block copolymers, (α-methylstyrene-co-vinylbenzocyclobutene)-isobutylene-(α-methylstyrene-co-vinylbenzocyclobutene) block copolymers, and combinations thereof.

9. The ultraviolet-absorbing polymer composition according to claim 1 or 2, wherein the dienophilic group is selected from carbon-carbon double bonds shown in structural formula 2, carbon-carbon triple bonds shown in structural formula 3, and combinations thereof: in, R1, R2, and R3 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, alkoxy, hydroxyl, formyl, ester, carboxyl, cyano, nitro, halogen, acid anhydride, haloalkyl, sulfonyl, amino, amide, tertiary amine cation, and combinations thereof, and optionally, any two of R1, R2, and R3 can be cyclically linked by covalent bonds. R4 is selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, alkoxy, hydroxyl, formyl, ester, carboxyl, cyano, nitro, halogen, acid anhydride, haloalkyl, sulfonyl, amino, amide, tertiary amine cation and combinations thereof.

10. The ultraviolet-absorbing polymer composition according to claim 1 or 2, wherein the ultraviolet absorber is selected from benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, and combinations thereof.

11. The ultraviolet-absorbing polymer composition according to claim 1 or 2, wherein the ultraviolet absorber is selected from ultraviolet absorbers of structural formulas 4-6 and combinations thereof: R5, R6, and R7 are independently selected from dienophilic groups, hydrogen, alkyl, aralkyl, alkoxy, hydroxyl, formyl, ester, carboxyl, cyano, nitro, halogen, amino, and combinations thereof, and at least one of R5, R6, and R7 is a dienophilic group. A linking group may exist between the dienophilic group and the conjugated cyclic structure of the UV absorber, such as alkylene, aralkylene, oxyalkylene, ether bond, carbonyl, carbonyloxy, imino, and combinations thereof. in, R8 and R9 are independently selected from dienophilic groups, hydrogen, alkyl, aralkyl, alkoxy, hydroxy, formyl, ester, carboxyl, cyano, nitro, halogen, amino, and combinations thereof, and at least one of R8 and R9 is a dienophilic group, wherein a linking group may exist between the dienophilic group and the conjugated cyclic structure of the UV absorber, such as alkylene, aralkylene, oxyalkylene, ether bond, carbonyl, carbonyloxy, imino, and combinations thereof; Wherein, R10, R11, R12, R13, and R14 are independently selected from dienophilic groups, hydrogen, alkyl, aralkyl, alkoxy, hydroxyl, formyl, ester, carboxyl, cyano, nitro, halogen, amino, and combinations thereof, and at least one of R10, R11, R12, R13, and R14 is a dienophilic group, wherein a linking group may exist between the dienophilic group and the conjugated cyclic structure of the UV absorber, such as alkylene, aralkylene, oxyalkylene, ether bond, carbonyl, carbonyloxy, imino, and combinations thereof; preferably, the UV absorber is selected from the UV absorbers shown in structural formulas 7-12 and combinations thereof:

12. A method for preparing an ultraviolet-absorbing polymer, comprising: (a) Mixing at least one polyolefin and at least one ultraviolet absorber, wherein the polyolefin contains at least one benzocyclobutene (BCB) side group and the ultraviolet absorber contains at least one dienophilic group; (b) Applying heat to cause the polyolefin to form a cross-linked polyolefin through a reaction between the benzocyclobutene side groups, and covalently linking the polyolefin and the ultraviolet absorber through a reaction between the benzocyclobutene side groups and the dienophilic groups.

13. The method of claim 12, wherein step (a) is performed by a wet or dry process.

14. The method according to claim 12, wherein step (b) is performed at a temperature of at least 180°C, preferably at least 200°C, for 0.5-20 hours, preferably 1-10 hours.

15. The method according to claim 12, wherein the molar ratio of the dienophilic group to the benzocyclobutene (BCB) side group is 1:100-50:100, preferably 5:100-30:

100.

16. The method according to any one of claims 12-15, wherein the polyolefin is prepared by cationic polymerization comprising a mixture of the following components: i) at least one cationicly polymerizable branched olefin monomer, ii) at least one cationicly polymerizable olefin monomer having a benzocyclobutene side group, and iii) optionally, at least one monomer capable of forming a glassy substance.

17. The method according to claim 16, wherein the branched olefin monomer is selected from C4-C14 branched olefins, preferably from C4-C10 olefins or C4-C7 olefins, and more preferably from isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, β-pinene and combinations thereof.

18. The method of claim 16, wherein the olefin monomer having a benzocyclobutene side group is selected from compounds shown in structural formula 1: When n is 0, R is hydrogen or alkyl, preferably methyl, ethyl or propyl; or when n is an integer selected from 1 to 3, R is alkyl, preferably methyl, ethyl or propyl.

19. The method of claim 16, wherein the olefin monomer having a benzocyclobutene side group is selected from 4-vinylbenzocyclobutene, 4-(α-alkylvinyl)benzocyclobutene (e.g., 2-(4-benzocyclobutenyl)-propylene and 2-(4-benzocyclobutenyl)-1-butene), 4-(2-methyl-alkenyl)benzocyclobutene (e.g., 2-methyl-3-(4-benzocyclobutenyl)-1-propylene and 2-methyl-4-(4-benzocyclobutenyl)-1-butene), and combinations thereof.

20. The method of claim 16, wherein the monomer capable of forming a glassy substance is selected from styrene, α-alkylstyrene (e.g., α-methylstyrene), 4-alkylstyrene (e.g., p-tert-butylstyrene), 4-alkoxystyrene, aromatic ring-substituted styrene, diphenylethylene, norbornadiene, norbornene, p-chlorostyrene, indene, and combinations thereof.

21. The method according to any one of claims 12-15, wherein the polyolefin is selected from random copolymers of isobutylene and vinylbenzocyclobutene, random copolymers of isobutylene and styrene and vinylbenzocyclobutene, random copolymers of isobutylene and α-methylstyrene and vinylbenzocyclobutene, block copolymers of isobutylene and vinylbenzocyclobutene, (styrene-co-vinylbenzocyclobutene)-isobutylene-(styrene-co-vinylbenzocyclobutene) block copolymers, (α-methylstyrene-co-vinylbenzocyclobutene)-isobutylene-(α-methylstyrene-co-vinylbenzocyclobutene) block copolymers, and combinations thereof.

22. The method according to any one of claims 12-15, wherein the dienophilic group is selected from the carbon-carbon double bond shown in structural formula 2, the carbon-carbon triple bond shown in structural formula 3, and combinations thereof: in, R1, R2, and R3 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, hydroxyl, formyl, ester, carboxyl, cyano, nitro, halogen, acid anhydride, haloalkyl, sulfonyl, amino, amide, tertiary amine cation, and combinations thereof, and optionally, any two of R1, R2, and R3 can be cyclically linked by covalent bonds. R4 is selected from hydrogen, alkyl, alkenyl, alkynyl, aralkyl, hydroxyl, formyl, ester, carboxyl, cyano, nitro, halogen, acid anhydride, haloalkyl, sulfonyl, amino, amide, tertiary amine cation and combinations thereof.

23. The method according to any one of claims 12-15, wherein the ultraviolet absorber is selected from benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, and combinations thereof.

24. The method according to any one of claims 12-15, wherein the ultraviolet absorber is selected from ultraviolet absorbers of structural formulas 4-6 and combinations thereof: R5, R6, and R7 are independently selected from dienophilic groups, hydrogen, alkyl, aralkyl, alkoxy, hydroxyl, formyl, ester, carboxyl, cyano, nitro, halogen, amino, and combinations thereof, and at least one of R5, R6, and R7 is a dienophilic group. A linking group may exist between the dienophilic group and the conjugated cyclic structure of the UV absorber, such as alkylene, aralkylene, oxyalkylene, ether bond, carbonyl, carbonyloxy, imino, and combinations thereof. in, R8 and R9 are independently selected from dienophilic groups, hydrogen, alkyl, aralkyl, alkoxy, hydroxy, formyl, ester, carboxyl, cyano, nitro, halogen, amino, and combinations thereof, and at least one of R8 and R9 is a dienophilic group, wherein a linking group may exist between the dienophilic group and the conjugated cyclic structure of the UV absorber, such as alkylene, aralkylene, oxyalkylene, ether bond, carbonyl, carbonyloxy, imino, and combinations thereof; Wherein, R10, R11, R12, R13, and R14 are independently selected from dienophilic groups, hydrogen, alkyl, aralkyl, alkoxy, hydroxyl, formyl, ester, carboxyl, cyano, nitro, halogen, amino, and combinations thereof, and at least one of R10, R11, R12, R13, and R14 is a dienophilic group, wherein a linking group may exist between the dienophilic group and the conjugated cyclic structure of the UV absorber, such as alkylene, aralkylene, oxyalkylene, ether bond, carbonyl, carbonyloxy, imino, and combinations thereof; preferably, the UV absorber is selected from the UV absorbers shown in structural formulas 7-12 and combinations thereof:

25. An ultraviolet absorbing polymer prepared by the method according to any one of claims 12-24.

26. A medical device wherein at least a portion of the medical device is composed of an ultraviolet-absorbing polymer prepared by any one of claims 12-24 or an ultraviolet-absorbing polymer according to claim 25.

27. The medical device of claim 26, wherein the medical device comprises an intraocular contact lens and / or an ocular implant such as an artificial lens, an artificial cornea, an artificial corneal endothelium, an artificial iris, a glaucoma drainage tube, an artificial lacrimal duct, a punctal plug, or a combination thereof.

28. A method for preparing a medical device, comprising injecting an ultraviolet-absorbing polymer composition according to any one of claims 1-11 into a mold and subjecting it to heat treatment to form at least a portion of the medical device.

29. A method for preparing a medical device, comprising heat-treating an ultraviolet-absorbing polymer composition according to any one of claims 1-11 and then machining it to form at least a portion of the medical device.

30. The method according to claim 28 or 29, wherein the heat treatment comprises applying heat to heat the ultraviolet-absorbing polymer composition to a temperature of at least 180°C, preferably at least 200°C, for curing.

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