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WO2008052563A1 - Procédé de fabrication d'un article comprenant un réseau polymère interpénétré (ipn) et un article comprenant un ipn - Google Patents

Procédé de fabrication d'un article comprenant un réseau polymère interpénétré (ipn) et un article comprenant un ipn Download PDF

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Publication number
WO2008052563A1
WO2008052563A1 PCT/DK2007/000479 DK2007000479W WO2008052563A1 WO 2008052563 A1 WO2008052563 A1 WO 2008052563A1 DK 2007000479 W DK2007000479 W DK 2007000479W WO 2008052563 A1 WO2008052563 A1 WO 2008052563A1
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WIPO (PCT)
Prior art keywords
monomer
article according
producing
monomers
rubber substrate
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Ceased
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PCT/DK2007/000479
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English (en)
Inventor
Martin Alm
Maike Benter
Anne Marie Jensen
Joachim KARTHÄUSER
Kjeld Schaumburg
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NANON AS
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NANON AS
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Publication of WO2008052563A1 publication Critical patent/WO2008052563A1/fr
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    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/02—Solvent extraction of solids
    • B01D11/0203—Solvent extraction of solids with a supercritical fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00038—Production of contact lenses
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a method of producing an article comprising an interpenetrating polymer network (IPN) as well as an article comprising an IPN optionally being produced according to the method of the invention.
  • IPN interpenetrating polymer network
  • IPNs have been known for more than 40 years. IPNs are defined as macromolecular assemblies comprising two or more polymers wherein at least one is in the form of a network, the polymers are at least partially interlaced on a molecular scale but not covalently bonded to each other.
  • each network may retain its individual properties independently of its individual proportion in the blend. As a result an improvement can be attained in properties such as mechanical strength, impact resistance, and toughness and other.
  • IPPNs viz semi-IPN where at least one component is not in network form, and full IPN where all species are in network form.
  • IPN as used herein comprises both semi-IPNs and full IPNs.
  • US 2002/01222946 relates to a process of producing an IPN comprising: providing a liquid mixture comprising silicone oligomers and silsesquioxane oligomers; and curing the liquid mixture to form a composition of first and second polymers, the first polymer comprising the silsesquioxane oligomers cross-linked by siloxane bonds and the second polymer comprising a cross- linked silicone network formed in part from the silicone oligomers.
  • US 20030000028 provides a colorant for use in tinting contact lenses in which the binding polymer used is capable of forming an interpenetrating polymer network with the lens material.
  • the binding polymer forms an interpenetrating polymer network with the lens material embedding the colorant within the lens material, resulting in a stable, tinted lens.
  • the methods e.g. include simultaneously forming and cross-linking the polymer networks in the presence of each other.
  • Other methods include forming a first network and thereafter swelling this network with monomers, cross-linking agents and optionally initiator/catalyst with or without solvents where after this monomer may form a polymer and optionally a network, e.g. as disclosed in US 2002/0052448 and WO 98/40425
  • Applicant's co-pending US 2006/0148985 relates to a method of producing an IPN by forming a first polymer substrate and thereafter swelling this substrate with monomers in the presence of CO 2 in supercritical or liquid state.
  • the monomers may be induced to form a polymer and optionally cross-linked to form a network.
  • the inventors of the present invention have surprisingly found a method of producing an IPN comprising article which is essentially transparent.
  • This new method thus provides the possibility of obtaining essentially transparent articles of new materials and combinations of materials.
  • articles made of IPN rubbers have had a very poor transparency due to difference between the refractive index of the substrate and the refractive index of the interpenetrating polymer.
  • the method provides the possibility of producing new articles with desired properties which simultaneously are essentially transparent.
  • the method of the invention comprises
  • said at least one first monomer and said at least one second monomer are selected such that n and r 2 independently of each other are 3 or less, where
  • Qi denotes the intrinsic reactivity of the first monomer
  • Q 2 denotes the intrinsic reactivity of the second monomer
  • e1 denotes the polarity of the first monomer
  • e2 denotes the polarity of the second monomer.
  • the interpenetrating copolymer may e.g. be cross-linked as explained further below.
  • essentially transparent means that visible light of at least one wavelength can pass through the material.
  • the rubber substrate as well as the produced article may preferably be essentially transparent to visible light in the wavelengths from about 400 to about 700 nm.
  • the article produced is preferably essentially free of internal refractive borderlines, i.e. borderlines with different refractive index on the respective sides of the borderline.
  • an essentially transparent IPN article by providing an substrate with refractive index no, and an interpenetrating copolymer made from at least one first and at least one second monomer, wherein the at least one first monomer has a refractive index ni in homopolymerized condition, where ni is lower than n 0 , and the least one second monomer has a refractive index n 2 in homopolymerized condition, where n 2 is higher than no, and wherein said first and second monomers will react with each other to form an interpenetrating copolymer, an essentially transparent IPN article can be provided.
  • n and r 2 indicate to which degree the first and the second monomers are likely to react with each other.
  • an ⁇ value is determined for each first monomer in relation to at least one second monomer, and each r ⁇ value may preferably be within the value specified.
  • an r 2 value is determined for each second monomer in relation to at least one first monomer, and each r 2 value may preferably be within the value specified.
  • ⁇ and r 2 may preferably independently of each other be 2.5 or less, preferably Ti and r 2 independently of each other are 2 or less, more preferably ⁇ and r 2 independently of each other are 1.5 or less, even more preferably ⁇ and r 2 independently of each other are 1 or less.
  • n and r 2 independently of each other are 0.7 or less, preferably ri and r 2 independently of each other are 0.5 or less, more preferably n and r 2 independently of each other are 0.3 or less.
  • ⁇ and r 2 independently of each other are 0.1 or less, a true alternating copolymer will normally be produced.
  • At least one of the T 1 and r 2 is 1.3 or less, preferably at least one of the ⁇ and r 2 is 1 or less, at least one of the ⁇ and r 2 is 0.5 or less.
  • n and r 2 independently of each other are 0.7 or more and 1.3 or less, e.g. 1.0 or less, a random copolymer will normally be produced.
  • the absolute value of n - r 2 is 1 or less, more preferably 0.5 or less, such as 0.2 or less. It has thus been found that when the difference between T 1 and r 2 is relatively small, the first and the second monomers are even more likely to react with each other.
  • the rubber substrate may preferably have a refractive index n 0 between 1.33 and 1.75, such as between 1.335 and 1.65, such as between 1.4 and 1.5.
  • An interval stated using the term "between” e.g. between 1 and 2 means herein that the values in the upper and lower end of the interval - in this example 1 and 2 - are included in the interval.
  • each of the first and the second monomers should preferably in homopolymerized condition have a refractive index which is relatively close to the refractive index no of the rubber substrate.
  • the at least one first monomer in homopolymerized condition has a refractive index which is up to 0.3 lower than n 0 , such as up to 0.2 lower than n 0 , such as between 0.01 and 0.2 lower than n 0 .
  • the at least one second monomer in homopolymerized condition has a refractive index n 2 which is up to 0.3 higher than no, such as up to 0.2 higher than n 0 , such as between 0.01 and 0.2 higher than no.
  • the relative molar amount of the first and the second monomers also influences the transparency of the produced article.
  • the rubber substrate may preferably be exposed to the first and the second monomers in the reaction chamber, where the molar amount Mi of the at least one first monomer relative to the molar amount M 2 of the at least one second monomer introduced into the reaction chamber prior to and/or during the impregnation is between 1 :100 and 100:1, such as between 1:50 and 50:1, such as between 1:10 and 10:1, such as 1:1.
  • the rubber substrate may in one embodiment be exposed to the first and the second monomers in the reaction chamber, wherein the molar amount Mi of the at least one first monomer relative to the molar amount M 2 of the at least one second monomer introduced into said reaction chamber is selected to fulfill the conditions
  • N is n o +O.4 or less, such as n o +O.3 or less, such as no+0.2 or less, such as n o +O.1 or less, such as about no.
  • N is n o -O.4 or more, such as n o -O.3 or more, such as n 0 - 0.2 or more, such as no-0.1 or more.
  • volume fractions ⁇ i and ⁇ 2 of the respective monomers can be used in determine the resulting refractive index n p of the interpenetrating copolymer polymerized from said monomers according to the following:
  • Np is the refractive index of the resulting interpenetrating copolymer
  • ni is the refractive index of the first monomer in homopolymerized condition
  • n 2 is the refractive index of the second monomer in homopolymerized condition
  • ⁇ i is the volume fraction of the first monomer
  • ⁇ 2 is the volume fraction of the second monomer
  • ⁇ i + ⁇ 2 1
  • n 0 is the refractive index of the rubber substrate.
  • no-0.05 ⁇ n p ⁇ no+0.05 In an even more preferred embodiment no-0.05 ⁇ n p ⁇ no+0.05.
  • the amount of monomers introduced into the reaction chamber there is no upper limit to the amount of monomers introduced into the reaction chamber.
  • the amount of monomer impregnated into the rubber substrate depends on several things, including the type of monomers, the impregnation conditions and time and the concentration of monomers in the reaction chamber.
  • the total amount of monomers introduced to the reaction chamber is up to 500 % by weight of the rubber substrate, such as up to 200%, such as up to 100%, such as up to 10% by weight of the rubber substrate.
  • the rubber substrate may be any kind of transparent rubber substrate e.g. selected from the group consisting of silicone rubber, styrene-butadiene rubber (SBR), urethane rubber, latex and thermoplastic elastomers (TPE).
  • SBR styrene-butadiene rubber
  • TPE thermoplastic elastomers
  • a useful styrene-butadiene rubber is of a material as described in US Patent 6849690.
  • the rubber substrate comprises at least 10 %, such as at least 20 %, such as at least 40 %, such as at least 60 % by weight of polymer having a backbone consisting of Si and O atoms or consisting of Si atoms, said rubber substrate preferably comprising one or more polymers selected from the group consisting of poly(dimethyl siloxane), poly(methylphenyl siloxane), fluorosilicone rubber, silicone esters, polysiloxanes, polysilanes, chlorosilanes, alkoxysilanes, aminosilanes, polysilanes polydialkylsiloxanes, polysiloxanes containing phenyl substituents, said polymers of the rubber substrate optionally being vinyl- functionalized and/or optionally being partially or fully fluohnated.
  • the rubber substrate is a silicone substrate.
  • the silicone substrate may e.g. be a silicone copolymer, or a grafted silicone e.g. grafted with HEMA. By grafting a silicone the refractive index may be modified to thereby obtain a preferred refractive index.
  • the rubber substrate may preferably be at least partially vulcanized, such as up to a vulcanization degree (cross-linking degree) of at least 10 %, such as at least 50 %, such as at least 80 % or wholly, such as at least 96 %, such as at least 97 %, such as at least 98 %.
  • a vulcanization degree cross-linking degree
  • the degree of vulcanization may depend on the type of rubber used and the article produced. The skilled person will for a given rubber and a given article in aim, be able to select a useful vulcanization degree.
  • the rubber substrate may e.g. be of a composite material or e.g. be a substrate of two or more elements fixed to each other e.g. by gluing or other well known methods, wherein at least one of the elements is of rubber.
  • the rubber substrate may be pre-coated if desired e.g. using plasma deposition or wet chemical application, provided that the monomer still can be impregnated into the rubber substrate.
  • the rubber substrate may additionally be subjected to heat treatment and/or cold tempering (e.g. ad described in WO06045320).
  • the rubber substrate comprises low molecular weight residuals
  • the method further comprises extracting at least a part of the low molecular weight residuals from the rubber substrate prior to subjecting the rubber substrate to the monomers.
  • the extraction may preferably be performed by subjecting the rubber substrate to a CO2 containing extraction solvent under conditions wherein CO 2 is in its liquid or its supercritical state.
  • Low molecular weight residuals are herein defined as residuals which are in liquid state at 1 atm. and 50 0 C.
  • the rubber substrate may be shaped using any method e.g. by use of stamping, extrusion, injection molding, calendaring, casting, cutting, pressing or a combination thereof.
  • the shaping is performed prior to the vulcanization. In one embodiment the shaping is performed after the vulcanization. In one embodiment the shaping is performed simultaneously with the vulcanization.
  • the monomers used may in principle be any monomers which are reactable with each other and fulfill the condition with respect to refractive index.
  • the monomer(s) is/are free radical polymerizable monomer(s).
  • the monomers(s) are ring opening polymerizable ( ⁇ -lactones), or anionic (Urethanes).
  • the at least one monomer comprises one or more of the monomers selected from the group consisting of silicone containing monomers, such as silanes, e.g. tetraethylorthosilicate or tetraethoxysilane (TEOS) or chloro- or alkoxy-functional silanes; olefins such as ethylene, propylene, n-vinyl pyrolidone (nVP), styrene; oxygen-, phenyl, amino and nitrogen-containing monomers, such as acrylic and methacrylic derivatives, e.g.
  • silicone containing monomers such as silanes, e.g. tetraethylorthosilicate or tetraethoxysilane (TEOS) or chloro- or alkoxy-functional silanes
  • olefins such as ethylene, propylene, n-vinyl pyrolidone (nVP), styrene
  • acrylic esters acrylic acids, methacrylic acid and -esters, alkyl and hydroxyalkyl acrylates and methacrylates; functionalized methacrylates such as 2-hydroxyethyl methacrylate (HEMA), glycerol monomethacrylate (GMMA), heptaflurobutyl acrylate (HFBA) 1 2-methacryloyloxyethyl phosphorylcholine (MPC) and [2-(methacryloyloxy)ethyl]-dimethyl-(3- sulfopropyl)-ammonium hydroxide (Betain); alkyl substituted acrylates and methacrylates such as methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate (BMA), dodecyl methacrylate (DMA); urethanes; mono- and di-functional alcohols; carboxylic acids; amines; isocyanates; epoxides; aromatic
  • the at least one monomer comprises one or more of the monomers selected from the group consisting of silicone containing monomers, such as silanes, e.g. tetraethylorthosilicate or tetraethoxysilane (TEOS) or chloro- or alkoxy-functional silanes; olefins such as ethylene, propylene, n-vinyl pyrolidone (nVP), styrene; oxygen-, phenyl, amino and nitrogen-containing monomers, such as acrylic and methacrylic derivatives, e.g.
  • silicone containing monomers such as silanes, e.g. tetraethylorthosilicate or tetraethoxysilane (TEOS) or chloro- or alkoxy-functional silanes
  • olefins such as ethylene, propylene, n-vinyl pyrolidone (nVP), styrene
  • acrylic esters acrylic acids, methacrylic acid and -esters, alkyl and hydroxyalkyl acrylates and methacrylates; functionalized methacrylates such as 2-hydroxyethyl methacrylate (HEMA), glycerol monomethacrylate (GMMA), heptaflurobutyl acrylate (HFBA), 2-methacryloyloxyethyl phosphorylcholine (MPC) and [2-(methacryloyloxy)ethyl]-dimethyl-(3- sulfopropyl)-ammonium hydroxide (Betain); alkyl substituted acrylates and methacrylates such as methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate (BMA), dodecyl methacrylate (DMA); urethanes; mono- and di-functional alcohols; carboxylic acids; amines; isocyanates; epoxides; aromatic compounds
  • Functionalization of monomers e.g. of methacrylates may e.g. be performed prior or post to exposing the silicone rubber to the monomers.
  • the at least one first monomer is selected from the group of functionalized acrylates, preferably flouro-containing acrylates, such as heptaflourobutyl acrylate (HFBA).
  • functionalized acrylates preferably flouro-containing acrylates, such as heptaflourobutyl acrylate (HFBA).
  • the at least one second monomer is selected from the group of functionalized methacrylate, MPC, GMMA and Betain, preferably a hydroxyalkyl methacrylate, more preferably 2-hydroxyethyl methacrylate (HEMA).
  • the first and second monomers comprise heptaflourobutyl acrylate (HFBA) and 2-hydroxyethyl methacrylate (HEMA).
  • the first and second monomers may be introduced into the reaction chamber one-by-one, simultaneously, or partly overlapping with each other in time.
  • the molar amount of the respective monomers may be equal or different from each other.
  • the introduction of said one or more monomers into the reaction chamber may take place before, during or after the CO2 and optional co-solvent is introduced.
  • At least one first monomer and said at least one second monomer are introduced one after the other.
  • the molar amount of the respective monomers may be equal or different from each other as explained above.
  • the velocity of the feeding flow of the respective monomers may be equal or different. The velocity may e.g. vary during the feeding of the respective monomers.
  • the impregnation solvent may preferably comprise at least 10%, such as at least 30%, such as at least 50 %, such as at least 75 %, such as at least 90
  • the impregnation solvent/polymerization solvent may preferably comprise at least 50 %, such as at least 90 % of CO 2 .
  • the impregnation solvent may further comprise a surfactant preferably selected from the group of anionic, cationic, non-ionic and amphoteric surfactants, said impregnation solvent preferably comprising up to 5 % by weight, such as between 0.001-50 grams of surfactant per kg impregnation solvent.
  • a surfactant preferably selected from the group of anionic, cationic, non-ionic and amphoteric surfactants, said impregnation solvent preferably comprising up to 5 % by weight, such as between 0.001-50 grams of surfactant per kg impregnation solvent.
  • the impregnation solvent may further comprise a co-solvent, preferably selected from water and the group consisting of organic solvents such as hexane, benzene, methanol, ethanol, chloroform, xylene, iso-butanol, propanol, acetone, ethylene glycol and mixtures thereof including mixtures of organic solvent(s) and water.
  • a co-solvent preferably selected from water and the group consisting of organic solvents such as hexane, benzene, methanol, ethanol, chloroform, xylene, iso-butanol, propanol, acetone, ethylene glycol and mixtures thereof including mixtures of organic solvent(s) and water.
  • At least one radical starter (also called initiator) is incorporated into the rubber substrate, preferably by physical compounding, by swelling or impregnation in dissolved condition, or by co-impregnation with the monomers.
  • the amount of radical starter should preferably be sufficient to initiate the polymerization and preferably be sufficient to ensure a sufficient molecular weight (Mw).
  • the molecular weight of the resulting interpenetrating copolymer can be adjusted by controlling the amount of added radical starter.
  • radical starters (often called free radical initiators) are available; they may be classified into four major types: 1) Peroxides and hydroperoxides, 2) azo compounds, 3) redox initiators, and 4) compounds that form radicals under the influence of light (photo initiators). Any of these types of radical starters may in principle be used.
  • the radical starter is selected from the group consisting of peroxides such as diethyl peroxydicarbonate (DEPDC), benzoyl peroxide (BPO) and dicumylperoxide; hydro-peroxide; azo-compounds such as azo- bis-iso-butyronitril (AIBN); redox initiators and photoinitiators such as benzoyl-based radical starters.
  • the radical starter is activated by heat, pressure, irradiation and/or chemical activation, the latter e.g. by providing an exotermic process.
  • BPO is used as radical starter the polymerization should preferably be performed in the absence of CO 2 because CO 2 has been found to inhibit the decomposition of BPO and thereby inhibit the generation of free radical by the BPO.
  • At least one cross-linking agent is incorporated into the rubber substrate, preferably by physical compounding, by swelling or impregnation in dissolved condition, or by co-impregnation with the one or more monomers.
  • a useful amount and type of cross-linking agent may easily be found by the skilled person.
  • An example of cross-linking agent includes 1 ,3,5-Triallyl-1 ,3,5-triazine-2 ,4,6(1 H,3H,5H)-trione (TTT) and ethylene glycol dimethacrylate (EGDMA).
  • the method further comprises extracting at least a part of said non-polymerized monomers from the article after termination of polymerization:
  • the extraction of non- polymerized monomers preferably is performed by subjecting the article to a CO 2 containing extraction solvent under conditions wherein CO 2 is in its liquid or its supercritical state e.g. as described in US WO06045320 and e.g. using an extraction solvent which independently of the composition of the impregnation solvent has a composition as described above for the impregnation solvent.
  • the polymerization of the at least one first monomer and the at least one second monomer is performed in a solvent, referred to as the polymerization solvent, wherein said monomers are partly or totally in dissolved state.
  • the polymerization solvent and the polymerization conditions may be as described in the co-pending patent applications filed simultaneously with the present patent application.
  • the polymerization solvent independently of the impregnation solvent used has a composition as described above for the impregnation solvent.
  • the polymerization of the monomers may be performed under conditions where a layer of polymer, preferably a copolymer is polymerized from said monomers onto at least one surface part of said rubber article.
  • the layer of polymer may preferably be a copolymer essentially identical with the interpenetrating copolymer.
  • the layer of polymer is made from one or more monomers different from the combination of monomers providing the interpenetrating copolymer.
  • the at least one first monomer and the at least one second monomer are polymerized to form an alternating copolymer.
  • the at least one first monomer and the at least one second monomer are polymerized to form a random copolymer.
  • the depth of the interpenetrating copolymer into the rubber substrate depends largely on the type of monomers, the type and cross-linking degree of the rubber substrate and the impregnation condition, including the time of impregnation.
  • the rubber substrate may preferably be exposed to said monomers and said impregnation solvent for a sufficient time to impregnate a sufficient amount of said monomers into the rubber substrate for providing an interpenetrating copolymer from said monomers into a depth of at least 0.1 ⁇ m, preferably at least 1 ⁇ m of said rubber substrate upon polymerization of said monomers.
  • the rubber substrate is exposed to said monomers and said impregnation solvent under conditions where CO 2 is in its liquid and/or its supercritical state, and under conditions where polymerization of said at least monomers is not initiated and for a sufficient time to impregnate a sufficient amount of said monomers into said rubber substrate for providing an interpenetrating network from said monomers into a depth of at least 0.1 ⁇ m, preferably least 1 ⁇ m of said rubber substrate upon polymerization of said monomers.
  • the pressure and the temperature may be varied during the impregnation and/or during the polymerization.
  • Variation of the temperature and or pressure may e.g. be used to initiate the polymerization of the monomers.
  • the rubber substrate is exposed to the monomers and the impregnation solvent at a first pressure, followed by an increase in the pressure to thereby initiate polymerization of said monomers.
  • the rubber substrate is exposed to the monomers and the impregnation solvent at a first temperature, followed by an increase in the temperature to thereby initiate polymerization of said monomers.
  • the polymerization is initiated by heat e.g. in the presence of a polymerization solvent which may e.g. be in liquid and/or gas form.
  • the polymerization is initiated by irradiation e.g. using infrared irradiation (IR) or ultraviolet irradiation (UV).
  • IR infrared irradiation
  • UV ultraviolet irradiation
  • a laser may e.g. be used for performing the irradiation.
  • the rubber substrate is exposed to the monomers and the impregnation solvent where after the polymerization of said monomers is initiated using UV light.
  • the rubber substrate is exposed to the radical starter and the impregnation solvent (e.g. in the presence of monomers or preferably not in the presence of monomers), where after the rubber substrate is exposed to monomers and said impregnation solvent while said radical starter is simultaneously being initiated using UV light.
  • the impregnation solvent e.g. in the presence of monomers or preferably not in the presence of monomers
  • the rubber substrate is exposed to the monomers and the impregnation solvent for a sufficient time to impregnate at least a part of the monomers, where after the impregnation solvent is removed and a polymerization solvent having another composition than the removed impregnation solvent is introduced and polymerization of said monomers is initiated.
  • the polymerization solvent may likely be free of CO 2 .
  • the polymerization of said monomers may e.g. be performed under conditions where a layer of polymer/copolymer is polymerized from monomers onto at least one surface part of said polymer substrate.
  • a layer of polymer/copolymer is polymerized from monomers onto at least one surface part of said polymer substrate.
  • the method may in principle be used to produce any type of rubber based article including implants, contact lens, medical articles, hearing aid elements, baby care articles and other elements for use in contact with humans and/or animals.
  • Silicone rubber is accepted for use in close contact with the mammal body including contact with mammal mucous membranes. In particular when using silicone rubber as the rubber substrate, many new articles with desired properties may be produced.
  • the article of the method may accordingly comprise any rubber based article such as implants, contact lens, medical articles, hearing aid elements, baby care articles and other elements for use in contact with humans and/or animals.
  • the article of the invention is a contact lens.
  • the article of the invention comprises a body formed of a rubber substrate and an interpenetrating copolymer.
  • the article should preferably be essentially transparent.
  • the interpenetrating copolymer may e.g. be a network of a non-rubber copolymer.
  • the interpenetrating copolymer is an alternating or a random copolymer from at least two monomers, preferably selected from the group consisting of silicone containing monomers, such as silanes, e.g. tetraethylorthosilicate or tetraethoxysilane (TEOS) or chloro- or alkoxy- functional silanes; olefins such as ethylene, propylene, n-vinyl pyrolidone (nVP), styrene; oxygen-, phenyl, amino and nitrogen-containing monomers, such as acrylic and methacrylic derivatives, e.g.
  • silicone containing monomers such as silanes, e.g. tetraethylorthosilicate or tetraethoxysilane (TEOS) or chloro- or alkoxy- functional silanes
  • olefins such as ethylene, propylene, n-vinyl pyrolidone (nVP
  • acrylic esters acrylic acids, methacrylic acid and -esters, alkyl and hydroxyalkyl acrylates and methacrylates; functionalized methacrylates such as 2-hydroxyethyl methacrylate (HEMA), glycerol monomethacrylate (GMMA), heptaflurobutyl acrylate (HFBA), 2-methacryloyloxyethyl phosphorylcholine (MPC) and [2- (methacryloyloxy)ethyl]-dimethyl-(3-sulfopropyl)-ammonium hydroxide
  • HEMA 2-hydroxyethyl methacrylate
  • GMMA glycerol monomethacrylate
  • HFBA heptaflurobutyl acrylate
  • MPC 2-methacryloyloxyethyl phosphorylcholine
  • alkyl substituted acrylates and methacrylates such as methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate (BMA), dodecyl methacrylate (DMA); urethanes; mono- and di-functional alcohols; carboxylic acids; amines; isocyanates; epoxides; aromatic compounds such as aromatics carrying substituents such as alkyl groups and sulfonated aromatics, aromatic resins, imidazol and imidazol derivatives; pyrazoles; quaternary ammonium compounds; polyurethane prepolymers; epoxy resins; substituted ⁇ - and ⁇ - lactones, lactic acid monomers; carbohydrides and fluorinated monomers.
  • MMA methyl methacrylate
  • EMA ethyl methacrylate
  • BMA butyl methacrylate
  • DMA dodecyl methacrylate
  • urethanes mono- and di
  • the interpenetrating copolymer is an alternating or a random copolymer from at least two monomers, preferably at least one first monomer selected from the group consisting of functionalized acrylates, preferably flour containing acrylates, such as heptaflourobutyl acrylate (HFBA) and at least one second monomer selected from the group consisting of functionalized methacrylate, , MPC, GMMA and Betain, preferably a hydroxyalkyl methacrylate, preferably 2-hydroxyethyl methacrylate (HEMA).
  • HFBA heptaflourobutyl acrylate
  • HEMA 2-hydroxyethyl methacrylate
  • the body formed of a rubber substrate has a refractive index n 0 as described above and said article has a refractive index n A , wherein n 0 - n A is between -0.2 and 0.2, such as between -0.1 and 0.1, such as between -0.01 and 0.01.
  • the body formed of a rubber substrate has a refractive index n 0 as described above and said interpenetrating copolymer has a refractive index n P , wherein no - n P is between -0.3 and 0.3, such as between -0.2 and 0.2, such as between -0.1 and 0.1, such as between -0.01 and 0.01.
  • the refractive index n A of the article may preferably be between 1.33 and 1.75, such as between 1.335 and 1.65, such as between 1.4 and 1.5.
  • the interpenetrating copolymer is made from at least one first monomer and at least one second monomer, wherein the type and amounts of monomers are as described above.
  • the molar amount Mi of the at least one first monomer relative to the molar amount M2 of the at least one second monomer is such that
  • the amount of interpenetrating copolymer relative to the amount of rubber substrate depends on the article produced and may e.g. comprise up to 200 % by weight.
  • the interpenetrating copolymer constitute up to about 80 % by weight of the total article, such as up to 50 % by weight, such as up to 10 % by weight.
  • the rubber substrate may preferably be as described above.
  • the article comprises a body formed of a rubber substrate and an interpenetrating copolymer and an outer surface layer on at least a part of its surface of a polymer, which preferably may be essentially identical with the interpenetrating polymer.
  • the outer surface layer covers essentially the entire surface of said rubber substrate.
  • the outer surface layer may have any desired thickness, for example the outer surface layer has a thickness of at least 100 nm, such as at least 100 ⁇ m.
  • the interpenetrating copolymer and/or the surface layer has a more hydrophilic surface than an exposed surface of the rubber substrate.
  • An exposed surface of the rubber substrate means a surface of the rubber substrate within the article exposed by cutting through the article.
  • the invention also relates to a contact lens comprising a body formed of a silicone substrate and an interpenetrating copolymer, said contact lens being essentially transparent.
  • the silicone substrate and the interpenetrating copolymer may be as described above.
  • a silicone rubber substrate was provided and impregnated with monomer A and monomer B.
  • the monomers A and B were polymerized.
  • Monomer A was selected to be 2-hydroxyethyl methacrylate.
  • Methyl methacrylate 0.78 0.4 0.319 1.677 1.4893 o-chlorostyrene 2.66 1.57 0.069 0.312 1.6098
  • Phenyl methacrylate 1.25 0.79 0.276 0.899 1.5706
  • p-methoxystyrene 1.53 -1.4 0.209 1.725 1.5967
  • Discs with a radius of 5.0 mm were punched out of a 1.00 mm thick sheet of Elastosil LR 3003/10 silicone rubber supplied by Wacker Silicones (Germany). The discs were used as substrate material for producing the interpenetrating polymer networks. All discs were extracted in SCCO2 to remove low molecular weight residuals, before they were used as substrate material.
  • Diethyl peroxydicarbonate was synthesized from 98 % Ethyl chloroformat (supplied by Fluka Chemie (Buchs CH)) and 30 % H 2 O 2 and NaOH pellets (Supplied by Bie & Berntsen (R ⁇ dovre, DK) and stored in hexane (0.15 M) under an argon atmosphere at -18 0 C. 98 %.
  • CO 2 N48 was supplied by Air Liquid Denmark A/S (Denmark) and used as received.
  • a 16 ml stainless steel high-pressure reactor was used for the experiments.
  • a Thar P-50 electrical driven pressure pump from That Design Inc. USA was applied for ensuring the operation pressure.
  • the pump was equipped with a heat exchanger and was supplied with cooling water at 5 0 C.
  • the treated discs with monomer A and B will be transparent and very clear since the material will be essentially free of internal deflections of light rays.
  • the interpenetrating copolymer is a random or an alternating copolymer and has a refractive index which is very close to the refractive index of the rubber substrate.
  • the treated discs with monomer A and C will be transparent or translucent. However they will not be completely clear since they will have internal differences in refractive indexes which result in deflections of light rays.
  • the interpenetrating polymer is a block copolymer or in the form of two or more homopolymers.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Ophthalmology & Optometry (AREA)
  • Mechanical Engineering (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention porte sur un procédé de fabrication d'un article comprenant un réseau polymère interpénétré (IPN) et un article pouvant par exemple être obtenu par le procédé. Le procédé comprend les opérations consistant à i) se procurer un substrat de caoutchouc sensiblement transparent ayant un indice de réfraction n0 et étant façonné pour fournir la forme désirée de l'article, et l'appliquer dans une chambre de réaction, ii) se procurer au moins un premier monomère ayant un indice de réfraction n1 dans une condition homopolymérisée, n1 étant inférieur à n0, iii) se procurer au moins un second monomère ayant un indice de réfraction n2 dans une condition homopolymérisée, n2 étant supérieur à n0, iv) exposer ledit substrat de caoutchouc dans ladite chambre de réaction auxdits premier et second monomères pour imprégner ledit substrat de caoutchouc par lesdits monomères en présence d'un solvant d'imprégnation comprenant CO2 dans des conditions dans lesquelles ledit CO2 est dans son état liquide ou supercritique, et v) copolymériser lesdits premier et second monomères afin de former un IPN, ledit premier monomère et ledit second monomère étant choisis de telle sorte que r1 et r2, indépendamment l'un de l'autre, soient 3 ou moins, où n = (Q1/Q2) exp [-e1 (e1 -e2)] et r2 = (Q2/Q1) exp [-e2(e2-e1 )] et Q1 désigne la réactivité intrinsèque du premier monomère, Q2 désigne la réactivité intrinsèque du second monomère, et e1 désigne la polarité du premier monomère et e2 désigne la polarité du second monomère. L'article comprend un corps formé d'un substrat de caoutchouc et d'un réseau interpénétré d'un copolymère interpénétré, et l'article est sensiblement transparent.
PCT/DK2007/000479 2006-11-03 2007-11-05 Procédé de fabrication d'un article comprenant un réseau polymère interpénétré (ipn) et un article comprenant un ipn Ceased WO2008052563A1 (fr)

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WO2012128740A1 (fr) * 2011-03-18 2012-09-27 Essilor International (Compagnie Generale D'optique) Procédé de préparation de revêtements durs durcissables par uv antistatiques, sur des articles optiques
CN109021174A (zh) * 2018-08-29 2018-12-18 华南理工大学 含氟胆碱类离子液体接枝“干荔枝型”聚合物微球的制备方法及应用
CN109814182A (zh) * 2019-03-15 2019-05-28 中国工程物理研究院激光聚变研究中心 一种提高高功率激光系统传输管道内壁抗杂散光损伤阈值的方法
WO2020049177A1 (fr) 2018-09-06 2020-03-12 Biomodics Aps Dispositif tubulaire médical
CN110964282A (zh) * 2019-12-23 2020-04-07 江阴市华盛印刷有限公司 一种ep/pmma-ipn环压增强剂及其制备方法
CN112262160A (zh) * 2018-06-04 2021-01-22 信越化学工业株式会社 聚硅氧烷单体及其制造方法
CN116948351A (zh) * 2023-06-08 2023-10-27 江苏视科新材料股份有限公司 一种硅水凝胶材料的制备方法

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Cited By (10)

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Publication number Priority date Publication date Assignee Title
WO2012128740A1 (fr) * 2011-03-18 2012-09-27 Essilor International (Compagnie Generale D'optique) Procédé de préparation de revêtements durs durcissables par uv antistatiques, sur des articles optiques
CN103429650A (zh) * 2011-03-18 2013-12-04 埃西勒国际通用光学公司 用于在光学物品上制备抗静电的可紫外光固化的硬质涂层的方法
CN103429650B (zh) * 2011-03-18 2015-07-01 埃西勒国际通用光学公司 用于在光学物品上制备抗静电的可紫外光固化的硬质涂层的方法
EA023845B1 (ru) * 2011-03-18 2016-07-29 Эссилор Энтернасьональ (Компани Женераль Д'Оптик) Фотоотверждаемая композиция, способ ее получения и способ получения антистатических уф-отверждаемых твёрдых покрытий на оптических изделиях
CN112262160A (zh) * 2018-06-04 2021-01-22 信越化学工业株式会社 聚硅氧烷单体及其制造方法
CN109021174A (zh) * 2018-08-29 2018-12-18 华南理工大学 含氟胆碱类离子液体接枝“干荔枝型”聚合物微球的制备方法及应用
WO2020049177A1 (fr) 2018-09-06 2020-03-12 Biomodics Aps Dispositif tubulaire médical
CN109814182A (zh) * 2019-03-15 2019-05-28 中国工程物理研究院激光聚变研究中心 一种提高高功率激光系统传输管道内壁抗杂散光损伤阈值的方法
CN110964282A (zh) * 2019-12-23 2020-04-07 江阴市华盛印刷有限公司 一种ep/pmma-ipn环压增强剂及其制备方法
CN116948351A (zh) * 2023-06-08 2023-10-27 江苏视科新材料股份有限公司 一种硅水凝胶材料的制备方法

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