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WO2009085754A1 - Copolymères séquencés segmentés interactifs - Google Patents

Copolymères séquencés segmentés interactifs Download PDF

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Publication number
WO2009085754A1
WO2009085754A1 PCT/US2008/086988 US2008086988W WO2009085754A1 WO 2009085754 A1 WO2009085754 A1 WO 2009085754A1 US 2008086988 W US2008086988 W US 2008086988W WO 2009085754 A1 WO2009085754 A1 WO 2009085754A1
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Prior art keywords
block
hydrophilic
interactive
block copolymer
interactive segmented
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Ceased
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English (en)
Inventor
Jeffrey G. Linhardt
Devon A. Shipp
Jay Friedrich Kunzler
David Paul Vanderbilt
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Bausch and Lomb Inc
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Bausch and Lomb Inc
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Priority claimed from US12/334,615 external-priority patent/US20090171027A1/en
Application filed by Bausch and Lomb Inc filed Critical Bausch and Lomb Inc
Publication of WO2009085754A1 publication Critical patent/WO2009085754A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers

Definitions

  • This invention relates to a new class of tailored polymers useful as surface coatings for ophthalmic devices. These polymers can be specifically tailored using controlled radical polymerization processes and contain functional domains. Controlled radical polymerization allows the facile synthesis of segmented block copolymers with tunable chemical composition that, as a result, show different chemical properties than those prepared via conventional free radical polymerization. Segmented block copolymers with substrate binding domain(s) containing functional groups such as boronic acids, hydrogen bonding groups and electrostatic groups and hydrophilic domain(s) show good surface properties when interactively bound to substrates containing complimentary functionality. BACKGROUND OF THE INVENTION
  • Medical devices such as ophthalmic lenses are made from a wide variety of materials.
  • materials are broadly categorized into conventional hydrogels or silicone hydrogels.
  • silicone-containing materials silicone hydrogels
  • These materials can vary greatly in water content.
  • silicone materials tend to be relatively hydrophobic, non-wettable, and have a high affinity for lipids.
  • Methods to modify the surface of silicone devices by increasing their hydrophilicity and improving their biocompatibility are of great importance.
  • US Pat. No. 6,858,310 discloses a method of modifying the surface of a medical device to increase its biocompatibility or hydrophilicity by coating the device with a removable hydrophilic polymer by means of reaction between reactive functionalities on the hydrophilic polymer with functionalities that are complementary on or near the surface of the medical device.
  • US Pat. No. 6,599,559 discloses a method of modifying the surface of a medical device to increase its biocompatibility or hydrophilicity by coating the device with a removable hydrophilic polymer by means of reaction between reactive functionalities on the hydrophilic polymer which functionalities are complementary to reactive functionalities on or near the surface of the medical device.
  • US Pat. No. 6,428,839 discloses a method for improving the wettability of a medical device, comprising the steps of: (a) providing a medical device formed from a monomer mixture comprising a hydrophilic monomer and a silicone-containing monomer, wherein said medical device has not been subjected to a surface oxidation treatment; (b) contacting a surface of the medical device with a solution comprising a proton-donating wetting agent, whereby the wetting agent forms a complex with the hydrophilic monomer on the surface of the medical device in the absence of a surface oxidation treatment step and without the addition of a coupling agent.
  • copolymers are currently made using conventional free radical polymerization techniques with the structure of the polymer being completely random or controlled by the reactivity ratios of the respective monomers.
  • controlled free radical polymerization techniques one is able to assemble copolymers in a controlled fashion and, in turn, they show completely different solution and coating properties than copolymers prepared using conventional free radical polymerization techniques.
  • Controlled free radical polymerization can be conducted by a variety of methods, such as ATRP (atom transfer radical polymerization) and RAFT (Reversible addition- fragmentation chain transfer polymerization).
  • the invention relates generally to interactive segmented block copolymers useful for forming bound coatings in the manufacture of medical devices.
  • bound refers to various chemical interactions such as, electrostatic, ionic, complexation, hydrogen bond or other interaction between the interactive segmented block copolymer and the surface functionality of the device which results in the association of the coating composition with the device.
  • suitable devices include contact lenses, intraocular lenses, vascular stents, phakic intraocular lenses, aphakic intraocular lenses, intraocular lens inserters, corneal implants, catheters, implants, and the like.
  • polymers prepared using ATRP according to the invention herein would include those where X is a halogen capping group of the initiator for Atom Transfer Radical Polymerization and those polymers that have undergone post polymerization removal or transformation of the halogen capping group of an initiator for Atom Transfer Radical Polymerization (i.e., derivatized reaction product).
  • the polymers which contain halogen end-groups can be utilized in a host of traditional alkyl halide organic reactions.
  • tributyltin hydride to the polymeric alkyl halide in the presence of a radical source (AIBN, or Cu(I) complex) leads to a saturated hydrogen-terminated polymer.
  • a radical source AIBN, or Cu(I) complex
  • polymers with allyl end groups can be prepared.
  • the terminal halogen can also be displaced by nucleophilic substitution, free-radical chemistry, or electrophilic addition catalyzed by Lewis acids to yield a wide variety of telechelic derivatives, such as alkenes, alkynes, alcohols, thiols, alkanes, azides, amines, phosphoniums, or epoxy groups, to mention a few.
  • telechelic derivatives such as alkenes, alkynes, alcohols, thiols, alkanes, azides, amines, phosphoniums, or epoxy groups, to mention a few.
  • Interactive segmented block copolymers prepared through Reversible addition- fragmentation chain transfer polymerization (“RAFT”) methods in accordance with the invention herein have the following generic formula (II):
  • Ri is a radical forming residue of a RAFT agent or free radical initiator
  • A is a chemical binding unit block
  • B is a hydrophilic unit block
  • m is 1 to 10,000
  • n is 1 to 10,000
  • p and q are natural numbers
  • R 2 is a thio carbonyl thio fragment of the chain transfer agent with the proviso that when A is an ionic block, B will be a nonionic block.
  • RAFT agents based upon thio carbonyl thio chemistry are well known to those of ordinary skill in the art and would include, for example, xanthates, trithiocarbonates and dithio esters. It should be noted, that there are many processes for the post polymerization removal or transformation of the thio carbonyl thio fragment of the chain transfer agent which are known to one of ordinary skill in the art. Therefore polymers prepared using RAFT agent according to the invention herein would include those where R 2 is a thio carbonyl thio fragment of the chain transfer agent and those polymers that have undergone post polymerization removal or transformation of the thio carbonyl thio fragment of the chain transfer agent (i.e., a derivatized reaction product).
  • the order of the block units is not critical and the interactive segmented block copolymer can contain more than two blocks. Therefore the interactive segmented block copolymers can be multiblock copolymers and include repetition of one or more blocks.
  • the nonlimiting representations below each of which is intended to fall within generic formula I, II and III:
  • Interactive segmented block copolymers according to the invention herein may also contain blocks that would not be considered to be binding or hydrophilic, for example, polystyrene or polymethyl methacrylate.
  • the presence of non binding or non hydrophilic block(s) within a polymer is contemplated as being within the scope of the claimed reactive segmented block copolymers and formulae I, II and III of the invention herein.
  • FIG 1 is a schematic example of atom-transfer radical polymerization (ATRP) used to make a segmented block copolymer in which there is an oligomeric block of the chemical binding unit at one end of the polymer followed by a large hydrophilic block;
  • Figure 2 is the structural formula of various monomers which may be used to provide the interactive functionality of the segmented block copolymers of the invention herein;
  • Figure 3 is a reaction schematic showing how RAFT polymerization can be used to to polymerize block copolymers with functional domains.
  • the present invention relates generally to interactive segmented block copolymers.
  • the interactive segmented block copolymers are useful in various compositions including ophthalmic compositions comprising the interactive segmented block copolymers for use in providing surface bound coatings in the manufacture of medical devices.
  • the present invention relates to interactive segmented block copolymers having interactive functionality that is complimentary to surface functionality of a medical device such as an ophthalmic lens.
  • a medical device such as an ophthalmic lens.
  • the term "surface” is not to be limited to meaning "at least one complete surface”. Surface coverage does not have to be even or complete to be effective for surface functionality.
  • the interactive segmented block copolymers of the present invention are useful as coatings for biocompatible materials including both soft and rigid materials commonly used for ophthalmic lenses, including contact lenses.
  • Ri is the reactive residue of a moiety capable of acting as an initiator for Atom Transfer Radical Polymerization
  • A is a chemical binding unit block
  • B is a hydrophilic unit block
  • m is 1 to 10,000
  • n is 1 to 10,000
  • p and q are natural numbers
  • X is a halogen capping group of the initiator for Atom Transfer Radical Polymerization with the proviso that when A is an ionic block, B will be a nonionic block.
  • X being an alkyl halide can be converted to another functionality through subsequent chemical reaction.
  • polymers prepared using ATRP according to the invention herein would include those where X is a halogen capping group of the initiator for Atom Transfer Radical Polymerization and those polymers that have undergone post polymerization removal or transformation of the halogen capping group of an initiator for Atom Transfer Radical Polymerization (i.e., derivatized reaction product).
  • the polymers which contain halogen end-groups can be utilized in a host of traditional alkyl halide organic reactions.
  • tributyltin hydride to the polymeric alkyl halide in the presence of a radical source (AIBN, or Cu(I) complex) leads to a saturated hydrogen-terminated polymer.
  • AIBN a radical source
  • Cu(I) complex a radical source
  • polymers with allyl end groups can be prepared.
  • the terminal halogen can also be displaced by nucleophilic substitution, free-radical chemistry, or electrophilic addition catalyzed by Lewis acids to yield a wide variety of telechelic derivatives, such as alkenes, alkynes, alcohols, thiols, alkanes, azides, amines, phosphoniums, or epoxy groups, to mention a few.
  • telechelic derivatives such as alkenes, alkynes, alcohols, thiols, alkanes, azides, amines, phosphoniums, or epoxy groups, to mention a few.
  • Interactive segmented block copolymers prepared through Reversible addition- fragmentation chain transfer polymerization (“RAFT”) methods in accordance with the invention herein have the following generic formula (II):
  • Ri-KA n Jp-KB) 1 Jq-R 2 (II)
  • Ri is a radical forming residue of a RAFT agent or free radical initiator
  • A is a chemical binding unit block
  • B is a hydrophilic unit block
  • m is 1 to 10,000
  • n is 1 to 10,000
  • p and q are natural numbers
  • R 2 is a thio carbonyl thio fragment of the chain transfer agent with the proviso that when A is an ionic block, B will be a nonionic block. It would be recognized by one of ordinary skill in the art that R 2 being a thio carbonyl thio fragment can be cleaved from the end of the polymer or converted to another functionality through subsequent chemical reaction.
  • RAFT agents based upon thio carbonyl thio chemistry are well known to those of ordinary skill in the art and would include, for example, xanthates, trithiocarbonates and dithio esters. It should be noted, that there are many processes for the post polymerization removal or transformation of the thio carbonyl thio fragment of the chain transfer agent which are known to one of ordinary skill in the art. Therefore polymers prepared using RAFT agent according to the invention herein would include those where R 2 is a thio carbonyl thio fragment of the chain transfer agent and those polymers that have undergone post polymerization removal or transformation of the thio carbonyl thio fragment of the chain transfer agent (i.e., a derivatized reaction product).
  • Reactive segmented block copolymers prepared through reversible addition- fragmentation chain transfer polymerization (“RAFT”) methods in accordance with the invention herein have the following generic formula (III):
  • the order of the block units is not critical and the interactive segmented block copolymer can contain more than two blocks. Therefore the interactive segmented block copolymers can be multiblock copolymers and include repetition of one or more blocks.
  • the nonlimiting representations below each of which is intended to fall within generic formula I, II and III:
  • Interactive segmented block copolymers according to the invention herein may also contain blocks that would not be considered to be binding or hydrophilic, for example, polystyrene or polymethyl methacrylate.
  • the presence of non binding or non hydrophilic block(s) within a polymer is contemplated as being within the scope of the claimed interactive segmented block copolymers and formulae I, II and III of the invention herein.
  • the present invention provides materials useful for surface modifying contact lenses and like medical devices through the use of complementary interactive functionality. Although only contact lenses will be referred to hereinafter for purposes of simplicity, such reference is not intended to be limiting since the subject method is suitable for surface modification of other medical devices such as phakic and aphakic intraocular lenses and corneal implants as well as contact lenses.
  • the preferred interactive segmented block copolymers in the present invention are selected based on the specific interactive surface groups of the polymeric material to be coated.
  • the one or more interactive segmented block copolymers selected for surface modification should have complementary interactive chemical functionality to that of the surface of the substrate. Such complementary interactive chemical functionality enables a chemical reaction between the interactive segmented block copolymers and the complementary surface functionality of the substrate to form electrostatic, ionic, complexation, hydrogen bond or other interactions there between.
  • the one or more interactive segmented block copolymers are thus bound to the surface of the contact lens or like medical device to achieve surface modification thereof.
  • the interactive segmented block copolymer comprises a chemical binding unit block to provide the desired surface binding of the molecule.
  • the chemical binding unit block can be varied and is determined based upon the intended use of the interactive segmented block copolymers. That is, the chemical binding unit block of the interactive segmented block copolymers is selected to provide functionality that is complementary with the surface functionality of the device.
  • the chemical binding unit block will contain functional groups such as boronic acids, hydrogen bonding groups and electrostatic groups.
  • the contact lens material could include a hydroxyl containing monomer such as 2-Hydroxyethyl methacrylate or glycerol methacrylate to interact with the surface modifying agent boronic acid functionality.
  • a contact lens is formed from material having a residue providing boronic acid, a surface modifying agent containing a 2-hydroxyethyl methacrylate or glycerol methacrylate functionality could be used for surface modification in accordance with the present invention.
  • Such complementary chemical functionality enables binding to occur between the surface of the contact lens and the interactive groups of the one or more surface modifying agent's. This binding between functional groups forms chemical interactions there between.
  • Methods of coating the substrate include dip coating of the substrate into a solution containing the surface modifying agent.
  • the solution containing the surface modifying agent may contain substantially the surface modifying agent in solvent or may contain other materials such as cleaning and extracting materials.
  • Other methods could include spray coating the device with the surface modifying agent.
  • suitable catalysts for example, condensation catalyst.
  • the substrate and the other surface modifying agent may be subjected to autoclave conditions.
  • the substrate and the surface modifying agent may be autoclaved in the packaging material that will contain the coated substrate. Once the reaction between the substrate and the surface modifying agent has occurred, the remaining surface modifying agent could be substantially removed and packaging solution be added to the substrate packaging material. Sealing and other processing steps then proceed as they usually do.
  • the surface modifying agent could be retained in the substrate packaging material during storage and shipping of the substrate device to the end user.
  • the interactive segmented block copolymers useful in certain embodiments of the present invention may be prepared according to syntheses well known in the art and according to the methods disclosed in the following examples.
  • Test sample A was coated with the polymer of Example A
  • Test sample B was coated with the polymer of Example B.
  • Atomic concentrations were determined by XPS, as described below.
  • XPS X-ray Photoelectron Spectroscopy
  • ESCA Microprobe This instrument utilizes a monochromatic Al anode operated at 18kV and 100 Watts in the high power mode and 15kV and 0.25Watts/micron in low power mode. AU high power acquisitions are rastered over a 1400 micron x 100 micron analysis area. Dual beam neutralization (ions and electrons) is used. The base pressure of the instrument was 5 x 10 "10 torr and during operation the pressure was less than or equal to 1 x 10 " torr. This instrument made use of a hemispherical analyzer operated in FAT mode. A gauze lens was coupled to a hemispherical analyzer in order to increase signal throughput. Assuming the inelastic mean free path for a carbon Is photoelectron is 35 A, the practical measure for sampling depth for this instrument at a sampling angle of 45 is approximately 75A. The governing equation for sampling depth in XPS is:
  • ⁇ sin3 d where d is the sampling depth, ⁇ is the photoelectron inelastic mean free path and ⁇ is the angle formed between the sample surface and the axis of the analyzer.
  • d is the sampling depth
  • ⁇ is the photoelectron inelastic mean free path
  • ⁇ is the angle formed between the sample surface and the axis of the analyzer.
  • Each specimen was analyzed utilizing a low-resolution survey spectra (0-110OeV) to identify the elements present on the sample surface. Quantification of elemental compositions was completed by integration of the photoelectron peak areas. Analyzer transmission, photoelectron cross-sections and source angle correction were taken into consideration in order to give accurate atomic concentration values.
  • Example D Synthesis of DMA -b-DMAPMA/MAAPBA/DMA
  • the addition funnel was charged with a solution of 1.37-g (0.0081 -mol) of deinhibited and distilled N- [3-(dimethylamino)propyl]methacrylamide (DMAPMA), 0.83-g (0.0040-mol) of 3- methacrylamidophenylboronic acid (MAAPBA) and 1.20-g (0.121 -mol) of distilled N,N- dimethylacrylamide (DMA) in 30 mL dioxane. Both solutions were individually sparged with nitrogen for at least 30-min before heating and were subsequently maintained under a nitrogen blanket for the duration of the reaction. The reaction was heated to 60 0 C. After 2.75 h, the addition funnel contents were added to the reaction flask.
  • DMAPMA deinhibited and distilled N- [3-(dimethylamino)propyl]methacrylamide
  • MAAPBA 3- methacrylamidophenylboronic acid
  • DMA distilled N,N- dimethylacrylamide
  • the copolymer was dissolved in 100-mL 2- propanol containing 0.53-g (0.0032-mol) of AIBN. The solution was sparged with nitrogen for Ih and then heated at 80 0 C for 12 h under a nitrogen blanket. The cooled solution was precipitated by dropwise addition into 6-L of mechanically stirred ethyl ether. The white solid was collected by vacuum filtration and vacuum dried at 85 0 C giving 18,75-g of product.
  • This polymerization yields a block copolymer, PDMA-block-( DMAPMA/MAAPBA/DMA), in which the second block is actually a statistical copolymerization of any remaining DMA that had not been polymerized at the time of the DMAPMA, MAAPBA, and DMA addition.
  • the second "block" is therefore compositionally heterogeneous.
  • a polymerization that yields a statistical copolymerization or compositionally heterogeneous block as the second block would also be considered to be a reactive segmented block copolymer according to the invention herein.
  • the product was characterized by proton NMR (methanol-d4),GPC, Karl-Fischer and elemental analysis. Resonances attributable to the phenyl protons of MAAPBA were observed at approximately 7.1 to 7.8 ppm. The DMAPMA resonances could not be cleanly distinguished from DMA resonances. GPC was performed at 35 0 C in DMF containing 0.01 M lithium nitrate. The column set consisted of three 8-mm by 300-mm GRAM Linear M columns from Polymer Standards Services. Narrow MW PMMA
  • the primary peak had a Mn of 17,900
  • Test Sample 500 ppm polymer 67.5 (0.4) 18.6 (0.1) 10.2 (0.7) 3.8 (0.3)
  • Reaction 2748-1 14 is described below as an example of the procedure used.
  • DMA N,N-Dimethylacrylamide
  • Both the first precipitate and the block copolymer of DMA and GMA were characterized by proton NMR (CDC13) and GPC.
  • the GPC shows a shift in the elution peak to shorter times (higher MW) after the addition of the GMA block.
  • the NMR spectra of the block copolymer shows peaks for the glycidol methacrylate contributions at 3.7 ppm and 4.3 ppm.
  • GPC data for these polymers using DMF as an eluent are shown below, using both PMMA standards and PVP standards as calibrants. Although the trends in MW are the same, PMMA standards show MWs much closer to the theoretically expected value for polyDMA.
  • DMAPMA N,N-dimethylaminopropyl methacrylate
  • the GPC shows a shift in the elution peak to shorter times (higher MW) after the addition of the DMAPMA block. (Mn shifts from 11,000 Daltons to 12,000 Daltons using PMMA standards).
  • the DMAPMA resonances could not be cleanly distinguished from the DMA resonances, however the influence of the N-methyl resonances could be seen at arpund 2.2 ppm (shape of the peak changed).
  • TMS-MA trimethylsilyl methacrylate

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Abstract

La présente invention concerne des copolymères séquencés segmentés interactifs utiles pour traiter la surface d'un substrat au moyen de la liaison de fonctionnalités interactives du copolymère séquencé segmenté interactif avec les fonctionnalités de surface complémentaires du substrat polymère.
PCT/US2008/086988 2007-12-27 2008-12-16 Copolymères séquencés segmentés interactifs Ceased WO2009085754A1 (fr)

Applications Claiming Priority (4)

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US1684107P 2007-12-27 2007-12-27
US61/016,841 2007-12-27
US12/334,615 US20090171027A1 (en) 2007-12-27 2008-12-15 Segmented interactive block copolymers
US12/334,615 2008-12-15

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WO2013177506A3 (fr) * 2012-05-25 2014-04-10 Johnson & Johnson Vision Care, Inc. Polymères et matériaux nanogels, et leurs procédés de préparation et d'utilisation
US9170349B2 (en) 2011-05-04 2015-10-27 Johnson & Johnson Vision Care, Inc. Medical devices having homogeneous charge density and methods for making same
US9244196B2 (en) 2012-05-25 2016-01-26 Johnson & Johnson Vision Care, Inc. Polymers and nanogel materials and methods for making and using the same
US9297929B2 (en) 2012-05-25 2016-03-29 Johnson & Johnson Vision Care, Inc. Contact lenses comprising water soluble N-(2 hydroxyalkyl) (meth)acrylamide polymers or copolymers
US9522980B2 (en) 2010-05-06 2016-12-20 Johnson & Johnson Vision Care, Inc. Non-reactive, hydrophilic polymers having terminal siloxanes and methods for making and using the same
US9612364B2 (en) 2011-05-04 2017-04-04 Johnson & Johnson Vision Care, Inc. Medical devices having homogeneous charge density and methods for making same
CN106832158A (zh) * 2017-02-18 2017-06-13 湖南工业大学 一种pH响应性动态壳交联聚合物纳米粒子及其制备方法
US10073192B2 (en) 2012-05-25 2018-09-11 Johnson & Johnson Vision Care, Inc. Polymers and nanogel materials and methods for making and using the same
CN112126092A (zh) * 2020-09-16 2020-12-25 彭军文 一种超疏水抗菌聚丙烯薄膜及其制备方法

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US8133960B2 (en) 2009-06-16 2012-03-13 Bausch & Lomb Incorporated Biomedical devices
US20120283381A1 (en) * 2011-05-04 2012-11-08 Ryuta Tamiya Macroinitiator containing hydrophobic segment
CN103936925A (zh) * 2014-03-14 2014-07-23 厦门大学 一种具有离子响应和温度敏感性的无规共聚物的制备方法

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