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WO2003066707A1 - Silicone souple a indice de refraction eleve - Google Patents

Silicone souple a indice de refraction eleve Download PDF

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Publication number
WO2003066707A1
WO2003066707A1 PCT/NL2003/000090 NL0300090W WO03066707A1 WO 2003066707 A1 WO2003066707 A1 WO 2003066707A1 NL 0300090 W NL0300090 W NL 0300090W WO 03066707 A1 WO03066707 A1 WO 03066707A1
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WO
WIPO (PCT)
Prior art keywords
refractive index
radicals
polymer
groups
polysiloxane
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Ceased
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PCT/NL2003/000090
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English (en)
Inventor
Miriam Adrienne Lambertina Verbruggen
Eelco Christoffer Brian Van Der Flier
Theodorus Adrianus Cornelius Flipsen
Hendrik Smit
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Ophtec BV
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Ophtec BV
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Priority claimed from EP02075566A external-priority patent/EP1334991A1/fr
Application filed by Ophtec BV filed Critical Ophtec BV
Priority to JP2003566074A priority Critical patent/JP2005516702A/ja
Priority to AU2003207419A priority patent/AU2003207419A1/en
Priority to CA2475468A priority patent/CA2475468C/fr
Priority to EP03705495A priority patent/EP1472305A1/fr
Publication of WO2003066707A1 publication Critical patent/WO2003066707A1/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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/16—Materials or treatment for tissue regeneration for reconstruction of eye parts, e.g. intraocular lens, cornea

Definitions

  • the invention relates to a silicone material with a high refractive index. More particularly, it relates to a flexible silicone material with a high refractive index for use as an intra-ocular lens material, to intra-ocular lenses prepared from high refractive index polysiloxanes and to methods for their preparation.
  • Prosthetic implant lenses are widely used to replace natural lenses that are affected by cataract. Cataract is the leading cause of blindness in the industrialized and developing world. The standard medical procedure for treatment is to remove the natural cloudy lens by elective cataract surgery and replace it with an intra-ocular lens.
  • materials for intra-ocular lenses should be clear, highly transparent and should allow for the manufacturing of lenses with high refractive indices.
  • An intra-ocular lens with a high refractive index has the advantage that it can be thinner at the same dioptric power as an intra-ocular lens with lower refractive index.
  • co- polymers of polysiloxane and polymethacrylates may be prepared.
  • sulphur compounds can be introduced into the siloxane polymer. But despite these modifications, the refractive index of silicone materials is still limited, and a thin lens thereof does not provide much optical power.
  • refractive index modifying groups such as cyclo-alkyl groups or aromatic groups, optionally combined with phenyl groups (JP2000017176) or phenol groups (US 5,541,278)
  • conventional co-polymers for intra-ocular lenses consist of dimethylsiloxane-phenylmethylsiloxane co-polymers or dimethylsiloxane- diphenylsiloxane co-polymers as described in e.g. US 5,147,396, JP10305092, EP 0335312, WO 93/21245, WO 95/17460, US 5,444,106 and US 5,236,970.
  • silicone materials with higher refractive index can be obtained by increasing the phenyl content of silicone (co)polymers.
  • a polydimethyl siloxane / methylphenyl siloxane co-polymer has a refractive index of 1.462 (Gu & Zhou, Eur. Polymer J. 34, pp. 1727-33 [1998]).
  • a principal disadvantage is associated with the reduced flexibility or elongation of cross-linked networks of such modified polymers.
  • the presence of phenyl groups attached to the alternating silicon-oxygen backbone of the siloxane causes the (co)polymer to become relatively stiff and, despite their potential dioptric power, the suitability of such polymers as a material for intra-ocular lenses is greatly reduced.
  • the introduction of aromatic groups, such as phenyl groups, in polysiloxane increases the glass transition temperature, or Tg, of the polymer, making it more hard and brittle and less flexible over a wider temperature range. This renders the material more vulnerable to cracking or breaking during folding and reduces the suitability of phenylated polysiloxanes as a material for intra-ocular lenses because such lenses must be folded and inserted through a self-sealing incision.
  • a well-known remedy to the problem of vulnerability to cracking is to reinforce the lens and improve its mechanical properties by combining the polymer with a solid filler material.
  • finely powdered silica is used as a filler material for this purpose.
  • This filler material has a refractive index of 1.46. Since differences in the refractive index of the filler material and the polymer are not allowable in an optical lens, the maximum refractive index of a lens containing such filler material is ultimately 1.46.
  • silicone as an intra-ocular lens implant material and particularly the development of silicone with the enhanced material characteristics that would support broadening of such use is determined, at large, by the maximum attainable refractive index of the material and its associated flexibility.
  • the glass transition temperature of the material must be reduced.
  • One method of reducing the glass transition temperature of phenyl-modified polysiloxanes is to link the phenyl-groups to the silicon-oxygen backbone by alkanediyl-bridges. Such modification of polysiloxanes is known from US 4,780,510 wherein a hydride/vinyl reaction pair is used.
  • the refractive index of siloxane polymers is increased considerably without compromising the mechanical properties of the material, when refractive index modifying groups are bonded to the siloxane backbone via an alkanediyl-bridge in a clustered configuration.
  • refractive index modifying groups are bonded to the siloxane backbone via an alkanediyl-bridge in a clustered configuration.
  • a high refractive index polysiloxane (co)polymer is obtained of which the mechanical properties are minimally affected.
  • the advantageous material characteristics of silicone prepared therewith are essentially maintained.
  • the polysiloxanes may be prepared by one of two routes: i) via an addition reaction between clustered configurations of refractive index modifying groups and cyclic siloxane monomers followed by one of several methods of polymerization to obtain a (co)polymer, also termed the monomer- route hereinbelow, or (ii) via an addition reaction between clustered configurations of refractive index modifying groups and a (co)polymer (pre- polymer), also termed the polymer-route hereinbelow.
  • the present invention therefore provides a high refractive index (cyclic) siloxane monomer comprising a clustered configuration of refractive index modifying groups chemically bonded to the siloxane backbone via an alkanediyl-bridge such that one alkanediyl-bridge binds at least two refractive index modifying groups to said backbone.
  • the present invention also provides a high refractive index siloxane (co)polymer, comprising a clustered configuration of refractive index modifying groups chemically bonded to the polysiloxane backbone via an alkanediyl- bridge such that one alkanediyl-bridge binds at least two refractive index modifying groups to said backbone.
  • the attainable refractive indices of the new high refractive index polysiloxane (co)polymer material may reach such high values, that copolymerizing with conventional and even unmodified polysiloxanes is possible or even necessary for use in an intraocular lens while maintaining a relatively high refractive index in the resulting (co)polymer. Additionally high refractive index polysiloxane (co)polymer material may directly be obtained.
  • the (co)polymers of the invention exhibit high molecular weights so that after cross-linking the resulting material is strong and flexible.
  • the material attains these mechanical properties, whilst having a high refractive index, due to the fact that the refractive index modifying groups are bonded to the backbone of the siloxane in a clustered configuration via alkanediyl-bridges, such that one alkanediyl-bridge binds at least two refractive index modifying groups to said backbone.
  • the polymers of the invention are essentially not crosslinked so that processing and handling thereof in the manufacture of intra-ocular lenses is possible.
  • the number of unreacted crosslinkable groups that remain in the polymer upon its preparation is so small that these groups substantially completely disappear during and after cross-linking of the polymer. This is necessary to obtain a biocompatible material.
  • high refractive index silicone materials of good mechanical strength and with a large possible range of values for the refractive index can be obtained, i.e. both very high and reduced.
  • Such silicone materials constitute an excellent material for, e.g., intra-ocular lenses.
  • the present invention provides for intra-ocular lenses comprising a high refractive index polysiloxane (co)polymer, said high refractive index polysiloxane (co)polymer comprising a clustered configuration of refractive index modifying groups chemically bonded to the polysiloxane backbone via an alkanediyl-bridge such that one alkanediyl-bridge binds at least two refractive index modifying groups to said backbone.
  • Such an intra-ocular lens may attain high refractive index values whilst being flexible enough to be folded.
  • the present invention also provides methods for the preparation of high refractive index siloxane monomers and siloxane (co)polymers according to the invention, methods for preparing high refractive index siloxane (co)polymers therewith.
  • Said methods for the preparation of high refractive index siloxane (co)polymers are relatively easy to control and do not lead to large batch-to- batch quality variations. These methods and the materials resulting thereof are required for the mass manufacturing of intra-ocular lenses. Therefore, the present invention also provides methods for the preparation of intra-ocular lenses.
  • Figure 1 represents a cyclic siloxane that may be used as a monomeric precursor for the preparation of a high refractive index siloxane (co)polymer according to the invention.
  • Figure 2 represents the clustered configuration wherein the refractive index modifying groups are positioned in the high refractive index siloxane (co)polymers of the present invention and identifies the polysiloxane backbone, the alkanediyl-bridge, the carrier component (X) and the refractive index modifying groups (Y).
  • Figure 3A represents an embodiment of the present invention wherein an addition reaction between triphenylsilane and trivinyl pentamethyl cyclo tetrasiloxane and the resulting high refractive index siloxane (co)polymer is illustrated.
  • Figure 3B represents an embodiment of the present invention wherein an addition reaction between triphenylsilane and a divinyl hexamethyl tetrasiloxane polymer and the resulting high refractive index siloxane (co)pofymer is illustrated.
  • alkyl group refers to a straight chain or a branched-chain alkyl radical containing from 1 to 20, preferably from 1 to 10, more preferable from 1 to 3, carbon atoms.
  • the alkyl radical may be optionally substituted with one or more substituents that comprise of elements such as oxygen, nitrogen, sulphur, halogen (Cl, Br, I, F), hydrogen and phosphorus and may comprise alkoxy, hydroxy, amino, nitro or cyano.
  • (cyclo)alkyl group refers to an alkyl radical or a cyclic alkyl radical.
  • the latter includes saturated or partially saturated monocyclic, bicyclic or tricyclic alkyl radicals wherein each cyclic moiety contains 3 to 8, preferably 4 to 8, carbon atoms.
  • radicals include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso- amyl, hexyl, octyl, cyclopentyl, cyclopentenyl, cyclohexenyl, and cyclohexyl and are understood to include (cyclo)alkyl groups optionally substituted with substituents that comprise of elements such as oxygen, nitrogen, sulphur, halogen, hydrogen and phosphorous and may comprise alkyl, alkoxy, hydroxy, amino, nitro or cyano.
  • aromatic group refers to the monocyclic and polycyclic aromatic hydrocarbons, or arenes, and their substitution products such as benzene, naphthalene, toluene as well as to the hetero-aromatic, or aromatic heterocyclic structures, such as thiophene and pyridine.
  • aryl group refers to radicals comprising an aromatic or hetero- aromatic ring system derived from arenes by removal of a hydrogen atom from a ring carbon atom, such as a phenyl, naphtyl or anthracene radical which may optionally carry one or more substituents that comprise of elements such as oxygen, nitrogen, sulphur, halogen (Cl, Br, I, F), hydrogen and phosphorous and may comprise alkyl, alkoxy, hydroxy, amino, nitro or cyano.
  • radicals examples include phenyl, p-tolyl, 4-methoxyphenyl, 4-(tert-butoxy) phenyl, 4-chlorophenyl, 4-hydroxyphenyl, 1-naphtyl, and 2-naphtyl. It is to be noted that fused and connected rings, as well as 5, 6, 7 or 8 membered rings, such as cyclopentadienyl, imidazolyl, thiophenyl, thienyl, etc. are included.
  • aryl groups will be understood to include the arene-derived bivalent arylene groups, such as o-phenylene and the arynes, such as benzyne.
  • arylalkyl group means an alkyl radical as defined above in which one hydrogen atom is replaced by an aryl radical as defined above, such as benzyl, or 2-phenylethyl.
  • Allyl refers to propene radicals (CH 2 )2CH.
  • a high refractive index siloxane (co)polymer according to the invention may be prepared by chemically modifying a monomeric cyclic siloxane precursor through a vinyl/hydride addition reaction with a carrier component (X in figure 2) containing at least two refractive index modifying groups (Y in figure 2) in the presence of an addition reaction catalyst and (co)polymerizing the modified monomeric siloxane precursor.
  • a carrier component X in figure 2
  • Y in figure 2 containing at least two refractive index modifying groups
  • Use may be made of monomeric cyclic siloxane precursors that contain reactive groups such as hydride groups or vinyl groups as a precursor material for a high refractive index siloxane (co)polymer .
  • Such precursors are commercially available (e.g. Petrarch® product line, United Chemical Technologies, Inc., Bristol, Pennsylvania, USA) and support well controlled addition reactions according to the invention.
  • a monomeric cyclic siloxane precursor that is used in embodiments of the present invention may include three or more, preferably 3 to 6, more preferably 3 or 4 silicon atoms alternated with oxygen atoms in a cyclic structure such as presented in figure 1.
  • n is preferably 0, 1, 2 or 3, more preferably 0 or 1;
  • R is independently alkyl, vinyl or hydride;
  • Ri is hydride or, in an alternative embodiment, vinyl.
  • a monomeric cyclic siloxane precursor according to the invention may comprise from 1 to 12, preferable from 2 to 6, more preferable from 2 to 4 reactive groups in the form of vinyl or hydride groups.
  • a carrier component (X) can advantageously be bonded to a silicon atom of the precursor through a vinyl/hydride addition reaction, such as a hydrosilylation reaction.
  • the precursor may contain one or more hydride groups bonded to silicon atoms of the cyclic siloxane, in which case the carrier component would comprise a reactive vinyl group.
  • a precursor monomer comprising one or more reactive vinyl groups bonded to the silicon atoms of the cyclic siloxane to which the carrier component with the refractive index modifying groups (Y) can effectively be bonded.
  • the carrier component would preferably comprise a vinyl reactive hydride group.
  • the position and distribution of the reactive groups in a precursor monomer is not critical.
  • One or more carrier components (X) containing at least two refractive index modifying groups (Y) can be bonded to each precursor monomer.
  • a cyclic siloxane precursor is modified via an alkanediyl-bridge with only one carrier component (X) containing at least two refractive index modifying groups (Y) attached thereto.
  • several or all of the silicon atoms in a cyclic siloxane precursor molecule may have bonded two carrier components (X), each carrying at least two refractive index modifying groups (Y), via alkanediyl-bridges.
  • the number of carrier components bonded to the precursor monomers may be selected such that a desired refractive index in the eventual polysiloxane material is obtained.
  • the present invention therefore also provides a monomeric cyclosiloxane comprising a clustered configuration of refractive index modifying groups chemically bonded to the siloxane backbone via an alkanediyl-bridge such that one alkanediyl-bridge binds at least two refractive index modifying groups to said backbone.
  • a monomeric cyclosiloxane is very useful in preparing a (co)polymer of the present invention.
  • cyclic hydride-containing siloxane monomeric precursors cyclic vinyl- containing siloxane precursors, such as pentavinyl pentamethyl cyclo pentasiloxane, can be used in embodiments of the present invention.
  • Particularly useful precursors are tetrahydro tetramethyl cyclosiloxane and tetravinyl tetramethyl cyclo tetrasiloxane.
  • a carrier component containing at least two refractive index modifying groups is reacted with a monomeric cyclic siloxane precursor as described (figure 3A).
  • the bonding of the carrier component (X) containing at least two refractive index modifying groups (Y) results in a situation wherein it is separated or spaced apart from the silicon atom to which it is most directly bonded.
  • Such spacing can very advantageously be accomplished by using an alkanediyl-bridge between the carrier component and the silicon atom.
  • a very useful reaction pair is therefore formed by an hydride/vinyl reaction pair, whereby one member of said reaction pair is present on the monomeric cyclic siloxane precursor and the other member of said reaction pair is present on the carrier component that contains the refractive index modifying groups, because such a reaction results in an alkanediyl-bridge, in particular an ethanediyl-bridge.
  • An alternative reaction pair may comprise a hydride/allyl reaction pair, which also results in an alkanediyl-bridge, in particular a propanediyl-bridge.
  • refractive index modifying groups can be used. Both cyclic, straight chain and branched chain hydrocarbons are suitable. Preferably, aromatic groups, aryl groups, arylalkyl groups, cycloalkyl groups and/or branched alkyl groups are used as refractive index modifying groups (Y) in embodiments of the present invention. More preferably, phenyl groups are used as refractive index modifying groups.
  • One carrier component (X) may carry two or more, preferably three, refractive index modifying groups (Y).
  • the carrier component (X) may comprise a single or multi-atom structure.
  • the carrier component (X) may suitably comprise a silicon atom to which the refractive index modifying groups (Y) are bonded, in which case the silicon atom serves as the central atom of a clustered configuration of refractive index modifying groups.
  • other atoms may also be comprised by the carrier component (X). Instead of silicon, phosphorus, nitrogen, germanium or carbon may for example be used as the central atom of a clustered configuration of refractive index modifying groups.
  • the choice for the carrier component (X) is not critical as long as at least two refractive index modifying groups (Y) can be bonded thereto and as long as it can be attached to a silicon atom of a cyclic siloxane via an alkanediyl-bridge.
  • the carrier component is bonded to a cyclic siloxane monomer with the refractive index modifying groups already attached to the carrier component.
  • a clustered configuration of refractive index modifying groups according to the invention therefore preferably comprises a carrier component (X) with the refractive index modifying groups (Y) already attached.
  • a clustered configuration of refractive index modifying groups (X+Y) according to the invention can suitably be introduced into a cyclic siloxane monomer by using compounds such as triphenylsilane, diphenylsilane, triphenyl dimethyl disiloxane, diphenylalkyl dimethyl disiloxane, all of which will readily react with a vinyl-containing siloxane precursor and wherein carrier and refractive index modifying groups are combined.
  • Also very suitable compounds for introducing a clustered configuration of refractive index modifying groups into a cyclic siloxane monomer are compounds such as triphenyl vinylsilane, diphenylalkyl vinylsilane, phenyldialkyl vinylsilane, triphenyl dimethylvinyl disiloxane, diphenylethene, 3,3,3-triphenyl-l-propene, 3,3-diphenyl-l-propene or any other vinyl reactive polyp henyls, all of which will readily react with a hydride-containing siloxane precursor.
  • Triphenylsilane and triphenyl vinylsilane are preferred compounds by which a clustered configuration of refractive index modifying groups can be introduced in polysiloxane precursors and/or polysiloxanes of the present invention.
  • the person skilled in the art will readily understand from the above which alternative compounds may be used for introducing a clustered configuration of refractive index modifying groups into a cyclic siloxane monomer.
  • a method for preparing a high refractive index siloxane (co)polymer of the invention comprises the steps of a) chemically modifying a cyclic siloxane by performing an addition reaction in the presence of an addition reaction catalyst which reaction links to the siloxane backbone of said cyclic siloxane a clustered configuration of refractive index modifying groups via an alkanediyl- bridge such that at least two of said refractive index modifying groups are bound to said backbone via a single alkanediyl-bridge and b) facilitating subsequent polymerization of the resulting reaction products thereby obtaining the high refractive index siloxane (co)polymer.
  • addition reactions to polysiloxanes it is possible to perform addition reactions to polysiloxanes (see figure 3B).
  • solvents such as methanol or toluene may facilitate lowering the viscosity of the preparation. Due to the solvent-associated dilution of reactive groups present in the reaction mixture, and the resulting reduced reaction rate, reaction temperatures may be elevated and/or longer reaction periods may be used.
  • addition reactions to polysiloxanes are very suitable in methods of the present invention, they generally require more proper control of reaction conditions than addition reactions to cyclic monomers as described above. Additionally, the reaction efficiency, i.e. the degree to which the addition reaction has occurred is generally less than in addition reactions to cyclic monomers.
  • a polymeric material of the invention with a high value for the refractive index may also be prepared by using the addition reaction to the monomeric cyclo siloxanes as described above.
  • the molecular weight of the individual molecules of polysiloxane polymers of the invention is generally better controllable when clustered configurations of refractive index modifying groups are added to siloxane (co)polymers with predetermined molecular weight. The higher molecular weight, obtainable by this embodiment, favours the strength of the resulting crosslinked high refractive index polymer.
  • the fraction of the polymeric material modified, the molecular weight of the polymer and the amount and the distribution of reacted groups in the eventual polymer and therefore the refractive index as well as the mechanical properties of the eventual material may be properly controlled by the person skilled in the art based on the description provided herein.
  • a suitable siloxane (co)polymer in combination with a carrier group.
  • reactive groups on the polysiloxane may be suitably selected.
  • a very suitable (co)polymer is for example a combination of dimethylsiloxane and vinylmethylsiloxane.
  • the starting (co)polymer should be of high molecular weight so that cross-linking of the modified (co)polymer results in a strong, yet flexible network.
  • the solvent is dried and purified by distillation prior to use.
  • the reactive groups such as vinyl groups
  • cyclosiloxane s e.g. octamethyl cyclo tetrasiloxane and tetravinyl tetramethyl cyclo tetrasiloxaan.
  • the percentage or amount of reactive groups, such as vinyl groups, in the copolymer used in the polymer route for preparing a high refractive index polysiloxane of the invention is preferably optimized.
  • the amount of reactive groups is preferably adequately high to allow sufficient refractive index modifying groups (e.g. triphenylsilane groups) to be bonded during the modification (addition) reaction (sufficient herein referring to the desired refractive index).
  • the amount of reactive groups is preferably low enough to result in an almost complete modification reaction, i.e. such as to result in a low amount of unreacted groups left in the polymer that allow appropriate cross-linking of the polymer molecules in a cross-linking reaction.
  • the duration of a reaction at a certain reaction-temperature may be optimized to allow for remaining reactive groups in the co-polymer suitable for performing a cross-linking reaction therebetween.
  • the reactive groups of the precursor can be subjected to an addition reaction in a very controlled manner.
  • reaction parameters such as time, temperature and addition reaction catalyst concentration
  • An advantage of the addition reaction to cyclic monomers of the present invention is that the product resulting from the addition reaction (wherein the cyclic monomers are modified through the addition of carrier compounds with refractive index modifying groups) can be purified more easily than viscous polysiloxanes produced by methods of the prior art.
  • a very small number of unreacted reactive groups usually remain. Under these circumstances, co-polymerization may for example require the incorporation of extra vinylsiloxane units to reach the amount of free vinyl groups advantageous for proper cross-linking at high molecular weights of the polymer (usually about 1-5 mole %).
  • polysiloxanes with refractive index modifying groups prepared by methods of the prior art usually possess free unreacted reactive groups in uneven distribution or to an uncontrolled extent, , which hampers effective control of both the cross-linking reaction and the addition reaction. Therefore, the inventors have found that in order for it to be suitable for use in an intra-ocular lens, a polysiloxane comprising a clustered configuration of refractive index modifying groups chemically bonded to the polysiloxane backbone via an alkanediyl-bridge may be prepared by first completing the addition reaction between the clustered configurations of refractive index modifying groups and the polysiloxane polymer, and then cross-linking the resulting polymer to obtain a high refractive index silicone material, whereby the amount of unreacted reactive groups is substantially reduced over methods of the prior art and whereby no undesired side-reactions occur such as premature gelling as a result of the presence of high levels of unreacted reactive groups.
  • reaction results in an uniform distribution of reactive index modifying groups. Further, the reaction may take place at relatively low temperatures and relatively shorter reaction times compared to addition to a polymer, whereby the incidence of undesired cross- linking between reactive groups of the individual precursors is reduced.
  • (Co)polymerization catalyst are used when a process for the preparation of a polysiloxane according to the invention is performed with certain combinations of cyclic siloxane monomers and siloxane monomer modified with clustered configurations of refractive index modifying groups.
  • the high refractive index siloxane (co)polymer or alternatively the siloxane oligomers or monomers are an aspect of the present invention.
  • the terms "modified monomer”, “siloxane (co)polymer” or “polymer” with reference to the product resulting from the modification reaction of monomeric cyclic siloxanes as herein described, is herein defined as the reaction product of an addition reaction wherein cyclic siloxane monomers are modified with clustered configurations of refractive index modifying groups in any state.
  • a reaction mixture for performing an addition reaction preferably comprises a cyclic siloxane and clustered configurations of refractive index modifying groups in a molar ratio of about 10: 1 to about 1:10, more preferably of about 1:1 to about 1:10, even more preferably of about 1:4.
  • Such a reaction mixture further preferably comprises an addition reaction catalyst in an amount depending on the type of catalyst, but in the case of platinum divinyl tetramethyl disiloxane an amount of about 1-200 ppm, preferably of about 10 ppm can be used.
  • a reaction mixture may comprise additives such as vinyl or hydride reactive UV-blockers. It is advantageous to exclude air from the reaction mixture.
  • the reaction preferably takes place under an inert atmosphere, such as a nitrogen atmosphere.
  • Suitable reaction conditions include a reaction temperature of about 30- 150 °C, preferably about 70 - 100 °C and most preferably about 90 °C.
  • the mixture is preferably stirred at the reaction temperature and the reaction is allowed to take place for a period of about 6 - 168 hours, preferably 72 — 120 hours.
  • the reaction can be stopped at 50-99 % of the maximum level of additions.
  • a particularly suitable method for the preparation of a high refractive index siloxane (co)polymer of the invention comprises the modification of the cyclic siloxane precursor tetravinyl tetramethyl cyclo tetrasiloxane with triphenylsilane, which is exemplified in example 1.
  • a schematic representation of the modification of trivinyl pentamethyl tetrasiloxane with triphenylsilane is illustrated in figure 3A.
  • any catalyst for hydrosilylation such as platinum group metal components or Speiers catalyst can be used.
  • Karstedt catalyst platinum divinyl tetramethyl disiloxane
  • An alternative reaction route for the preparation of a high refractive index siloxane (co)polymer of the invention is formed by producing the clustered configuration of refractive index modifying groups as a Grignard- reagent and contacting this reagent with a cyclic hydride-containing siloxane precursor. Such a method is well known in the art.
  • a high refractive index siloxane (co)polymer may be prepared according to a preferred method of the invention by performing the addition reaction to a cyclic siloxane monomer and copolymerizing this monomer with other cyclic siloxane monomers (termed co-monomers hereinafter) or with other (low refractive index) polysiloxanes to obtain (co)polymers of a specific refractive index or with increased flexibility, increased mechanical strength or with a variety of functional groups (e.g. cross-linking enhancing groups such as vinyl or hydride groups in Pt-catalyzed systems or alkoxy groups).
  • functional groups e.g. cross-linking enhancing groups such as vinyl or hydride groups in Pt-catalyzed systems or alkoxy groups.
  • the crosslink density can then be low and an elastic material with sufficient strength for the use in foldable intraocular lenses is obtained.
  • transparent materials with a tensile strength of 1 MPa (minimum) and an elongation at break of 50 % (minimum) should be obtained.
  • the refractive index modifying groups are introduced into the (co)polymer before crosslinking takes place for both the monomer and polymer routes of synthesis.
  • the high refractive index (co)polymers can be purified before further use.
  • the uncrosslinked polymers of this invention can be used for injection moulding.
  • high refractive index siloxane (co)polymers can be derived from high refractive index siloxane (co)polymers or monomers according to the invention in one of several ways.
  • a high refractive index siloxane (co)polymer or monomer can be mixed with other polysiloxanes, in the presence of a (co-)polymerization catalyst (and optionally a solvent), and allowed to co-polymerize thereby forming a high refractive index polysiloxane (co)polymer.
  • a high refractive index polysiloxane can be prepared by preparing a (co)polymer or modified monomer according to the invention and reacting said (co)polymer or modified monomer with a cyclic siloxane co-monomer in the presence of a (co)polymerization catalyst.
  • Co-monomers may or may not comprise refractive index modifying groups themselves. They may or may not comprise reactive groups, such as hydride or vinyl groups.
  • One method for preparing a (co)polymer according to the invention may comprise the purification of a triphenyl modified siloxane monomer by stirring it in boiling methanol and recovering it by precipitation and decanting the boiling methanol.
  • the resulting white paste can be dried in a vacuum oven until a transparent material is obtained. At room temperature such material may appear as a glassy solid.
  • This material can then be mixed with octamethyl cyclo tetrasiloxane and a small amount of tetravinyl tetramethyl cyclo tetrasiloxane.
  • a (co-)polymerization catalyst such as potassium silanolate dissolved in purified, dried dimethyl sulfoxide (DMSO) can be added, preferably 10 6 to 10 5 mole of potassium silanolate per gram of mixture is used.
  • the mixture is reacted at a reaction temperature of between 10 - 200 °C, but preferably 150 - 200 °C under inert atmosphere (nitrogen). Reaction then may preferably take place under an inert atmosphere for a duration of between 1 - 400 hours, until a transparent viscous material is formed.
  • the reaction time is 96 hours or more to obtain complete randomization of siloxane groups in the co-polymer.
  • potassium silanolate other basic catalysts may be used as (co-)polymerization catalyst, such as potassium hydroxide or sodium hydroxide.
  • DMSO is not essential but increases the reaction rate for potassium salts.
  • Tetravinyl tetramethyl cyclo tetrasiloxane can also be added after copolymerisation of octamethyl cyclo tetrasiloxane and the modified monomer and copolymerised in a the next step at about 100 °C to avoid the formation of gel due to a high concentration of reactive vinylgroups.
  • a clustered configuration of refractive index modifying groups may be reacted with any polysiloxane homo- polymer, more preferably with a siloxane (co)polymer, of high molecular weight.
  • the molecular weight should preferably measure between 5,000 and 1,000,000 g/mole, more preferable between 10,000 and 500,000.
  • an addition reaction of a triphenylsilane, as a clustered configuration of refractive index modifying group, may be performed to a siloxane (co)polymer comprising a limited number of vinyl groups.
  • the number of vinyl groups in the (co)polymer should be chosen such that a modified (co)polymer is obtained that contains a relatively low amount of remaining unreacted vinyl groups, said low amount being essentially completely removable by a suitable cross-linking reaction between said modified (co)polymer and a suitable cross-linker for the preparation of a silicone material.
  • the amount of remaining unreacted vinyl groups before crosslinking should preferably amount to a mole percentage between 1 and 10, most preferably between 2 and 5.
  • the high refractive index (co)polymers of the present invention may be co-polymerized or re-arranged with other high refractive index (co)polymers of the present invention or still other polysiloxanes or cyclo siloxanes to prepare a (co)polymer with a desired refractive index.
  • Co polymers with a refractive index varying from 1.4 to about 1.6 can be produced by co-polymerization of highly phenylated siloxane polymers and siloxane polymers with a lower degree of aromatic substitution or even phenyl- free siloxane polymers using a method described hereinabove.
  • Co-polymers according to the invention have the formula:
  • R1 Si-O- J m L -Si-O- - n S i i-R1 R3 R R
  • R is independently selected from alkyl radicals, substituted alkyl radicals, aryl radicals, substituted aryl radicals, aromatic radicals such as naphtyl radicals, cycloalkyl radicals, arylalkyl radicals, allyl radicals, vinyl and hydride;
  • RI is independently selected from alkyl radicals, substituted alkyl radicals, aryl radicals, substituted aryl radicals, aromatic radicals such as naphtyl radicals, cycloalkyl radicals, arylalkyl radicals, allyl radicals, vinyl and hydride, monovalent hydrocarbon radicals having a multiple bond or substituted equivalents thereof, monovalent hydrocarbon radicals having a siliconhydride group, and triphenylsiloxane groups, but preferably comprises a vinyl or hydride group;
  • R2 is preferably a triphenyl silylalkyl radical, but can be selected from the group of triarylsilyl alkyl radicals, diarylalkyl silylalkyl radicals, aryl dialkylsilyl alkyl radicals, trialkyl alkylsilyl radicals, tricycloalkyl silylalkyl radicals, dicycloalkyl alkylsilyl alkyl radicals, cycloalkyl dialkyl silylalkyl radicals;
  • R3 is independently selected from alkyl radicals, substituted alkyl radicals, aryl radicals, substituted aryl radicals, aromatic radicals such as naphtyl radicals, cycloalkyl radicals, arylalkyl radicals, allyl radicals, vinyl and hydride, but is preferably an alkyl radical, more preferably a methyl radical; m is between 10 and about 2,000,000, preferably between about 100 and about
  • n is between 10 and about 2,000,000, preferably between about 100 and about 500,000 ; most preferably, m and n are values that result in a molecular weight of the polymer that is high enough to result in a strong and flexible material after cross-linking of said polymer.
  • the polymeric resin may further contain endgroups (empirical formula RsSiOo. ⁇ ), and branching points and T-resins (empirical formula RSIO S) and tetra-functional units (empirical formula Si ⁇ 2), structures known to those skilled in the art, to improve material properties for the application involved.
  • endgroups empirical formula RsSiOo. ⁇
  • branching points and T-resins empirical formula RSIO S
  • tetra-functional units empirical formula Si ⁇ 2
  • the polymeric resin may also contain alkylgroups between polysiloxane chains as bridging groups obtainable by e.g. end-linking.
  • unreacted vinyl groups as part of siloxane (co)monomers or (co)polymers, allows cross-linking of the (co)polymer as described earlier.
  • Unreacted vinyl groups may also deliberately be introduced by choosing reaction conditions in such a way that not all reactive groups (such as hydride or vinyl groups) on the precursor monomers have reacted.
  • the presence of such unreacted vinyl groups is then deliberately introduced in a polysiloxane of the invention in order to enable performance of a cross-linking reaction.
  • the performance of additional cross-linking then results in a polymer having good mechanical properties for use in an intra-ocular lens.
  • any siloxane (co)polymer with hydride groups or with vinyl groups can be used in a method of the present invention, depending on the composition of the polymer that is to be cross-linked.
  • co- polymers of methyl hydrosiloxane and phenyl methylsiloxane, co-polymers of methyl hydrosiloxane and diphenylsiloxane, and co-polymers of methyl vinylsiloxane and phenyl methylsiloxane and/or combinations of such compounds can be used.
  • monomeric crosslinkers such as e.g.
  • cross-linking reagent 1,1,3,3- tetramethyl disiloxane
  • cross-linking reagent 1,1,3,3- tetramethyl disiloxane
  • Alternative cross- linking systems can also be used.
  • Functional groups that contribute to cross-linking can be introduced in the (co)polymer. Examples are alkoxy, acetoxy, ketoxime, amine, (meth)acrylate and epoxy functional siloxane (co)polymers.
  • (Meth)acrylate containing units such as acryloxypropyl can undergo UN - and visible light cross-linking when suitable photo-initiators are present.
  • Epoxy-modified siloxane units e.g. can undergo electron beam curing.
  • Cross-linking preferably should not proceed too rapidly at room temperature.
  • cross-linking inhibitors such as 1,2,3,4-tetramethyl-l, 2,3,4- tetravinyl-cyclotetrasiloxane may be used. Such inhibitors may be added to the reaction mixture of the addition reaction in amounts of 0.01 - 10 wt. % based on the weight of the polymer.
  • additives such as UN-blocking agents or other additives such as dyes may be administered to the reaction mixtures.
  • vinyl functional or hydride functional benzotriazol vinyl functional or hydride functional 2- hydroxy benzophenones, allyl benzophenones (monoallyl benzophenone) and vinyl functional or hydride functional benzotriazoles may be used in amounts of 0.01 - 5 wt. % based on the weight of the polymer.
  • a high refractive index siloxane (co)polymer or modified monomeric precursor according to the present invention preferably exhibits a refractive index of at least 1.4, more preferably at least 1.65.
  • the refractive index is measured by Abbe-type refractometry.
  • High refractive index siloxane (co)polymers according to the present invention are very suitable for use in a multitude of applications. Especially in those applications where light refraction or optical appearance is important, such as in optical lenses, optical fibers, intra-ocular devices such as intra- ocular lenses for cataract, refractive and reconstruction surgery as well as for occluders and tear duct devices, in contact lenses, ophthalmic applications, glasses, windows, windshields, transparent coatings and in cosmetic products like hair care products the material of the present invention can be beneficially applied.
  • the high refractive index siloxane (co)polymers of the present invention are used for the manufacture of intraocular lenses.
  • Formation of intra-ocular lenses or optics from the high refractive index siloxane (co)polymers of the present invention may be accomplished by liquid injection molding or by cast or compression molding or other types of molding. These processes are well known in the art. Suitable vulcanization temperatures for such processes are between 20- 200 °C.
  • a polymer of the invention is used for the preparation of flexible intra-ocular lenses with high refractive index, preferably by a method known as injection molding, as such a method is cheap and rapid and produces high quality lenses.
  • Tetravinyl tetramethyl cyclo tetrasiloxane and triphenylsilane were mixed in a molar ratio of 1 to 4.
  • An amount of 11 ppm of platinum divinyl tetramethyl disiloxane was added as a 2.5 wt.% solution in xylene. Air was excluded by replacing it with an argon atmosphere and the mixture was heated to 90 °C. The mixture was stirred at the reaction temperature for 96 hours. After 96 hours, a small amount of vinyldiethylmethylsilane or another vinylcontaining silane was added and the mixture was stirred at 90 °C under argon atmosphere for 24 hours.
  • the resulting tetr atrip he nyl silylethane tetramethyl cyclo tetrasiloxane monomer (conversion vinyl groups > 92%) may be allowed to react with other cyclic monomers such as e.g.
  • octamethyl cyclo tetrasiloxane and tetravinyl tetramethyl cyclo tetrasiloxane (or equivalent cyclo siloxanes), or the resulting tetratriphenyl silylethane tetramethyl cyclo tetrasiloxane monomer conversion vinyl groups > 92%) may be co -polymerised with (co)polymers such as polydimethylsiloxane or polydimethyl vinylmethylsiloxane or a combination of e.g. polydimethylsiloxane and tetravinyl tetramethyl cyclo tetrasiloxane monomers.
  • tetravinyl tetramethyl cylo tetrasiloxane was added and reaction allowed to proceed for 4 hours still under nitrogen atmosphere.
  • dichloro dimethylsilane was added as a chain extender or chloro dimethyl vinylsilane was added as an endcapper.
  • trichlorosilanes or dichlorodiphenylsilanes may also be used as chain extenders.
  • the polymer was dried and heated and stirred in air at 90 °C for 2 hours or heated and stirred under argon atmosphere for 2 hours in the presence of divinyl tetramethyl disiloxane or, in parallel experiments in the presence of other vinyl-containing compounds such as 1,4-divinyl tetramethyl disilyle thane and butadiene.
  • the polymer was dried and heated and stirred in air at 90 °C for 2 hours or heated and stirred under argon atmosphere for 2 hours in the presence of divinyl tetramethyl disiloxane or, in parallel experiments in the presence of other vinyl-containing compounds such as 1,4-divinyl tetramethyl disilyle thane and butadiene.
  • IOL intra-ocular lens
  • the (co)polymer of example 1 was divided into two aliquots. To one part, hydride functional cross-linker (tetrakisdimethylsiloxysilane) was added in a ratio of 1:1 hydride groups to vinyl groups in the material after mixing of the two parts. To the other part 10 ppm of platinum divinyl tetramethyl disiloxane was added.
  • hydride functional cross-linker tetrakisdimethylsiloxysilane

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Abstract

La présente invention porte sur un (co)polymère de polysiloxane à indice de réfraction élevé qui comprend des groupes modifiant l'indice de réfraction et qui sont liés chimiquement en une configuration en grappes au squelette de polysiloxane. L'invention porte également sur des procédés de préparation de ces (co)polymères de polysiloxane à indice de réfraction élevé. Le polysiloxane de cette invention est tout à fait approprié pour être utilisé comme matériau dans la production de lentilles intraoculaires.
PCT/NL2003/000090 2002-02-08 2003-02-07 Silicone souple a indice de refraction eleve Ceased WO2003066707A1 (fr)

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JP2003566074A JP2005516702A (ja) 2002-02-08 2003-02-07 高屈折率の可撓性シリコーン
AU2003207419A AU2003207419A1 (en) 2002-02-08 2003-02-07 High refractive index flexible silicone
CA2475468A CA2475468C (fr) 2002-02-08 2003-02-07 Silicone souple a indice de refraction eleve
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WO2007128051A1 (fr) * 2006-05-03 2007-11-15 Vision Crc Limited Polysiloxanes biologiques
US7551830B2 (en) 2006-02-01 2009-06-23 Dow Corning Corporation Impact resistant optical waveguide and method of manufacture thereof
US7939614B2 (en) * 2004-05-12 2011-05-10 Adeka Corporation Silicon-containing curing composition and heat cured product thereof
US8071697B2 (en) 2005-05-26 2011-12-06 Dow Corning Corporation Silicone encapsulant composition for molding small shapes
US8258502B2 (en) 2006-02-24 2012-09-04 Dow Corning Corporation Light emitting device encapsulated with silicones and curable silicone compositions for preparing the silicones
US8439974B2 (en) 2006-05-03 2013-05-14 Vision Crc Limited Adjusted index of refraction of ocular replacement material
US9486311B2 (en) 2013-02-14 2016-11-08 Shifamed Holdings, Llc Hydrophilic AIOL with bonding
US10133092B2 (en) 2014-06-03 2018-11-20 Tsubota Laboratory, Inc. Myopia prevention device
US10195018B2 (en) 2013-03-21 2019-02-05 Shifamed Holdings, Llc Accommodating intraocular lens
US10350056B2 (en) 2016-12-23 2019-07-16 Shifamed Holdings, Llc Multi-piece accommodating intraocular lenses and methods for making and using same
US10548718B2 (en) 2013-03-21 2020-02-04 Shifamed Holdings, Llc Accommodating intraocular lens
US10736734B2 (en) 2014-08-26 2020-08-11 Shifamed Holdings, Llc Accommodating intraocular lens
US10823982B2 (en) 2014-06-03 2020-11-03 Tsubota Laboratory, Inc. Myopia treatment device
US10987214B2 (en) 2017-05-30 2021-04-27 Shifamed Holdings, Llc Surface treatments for accommodating intraocular lenses and associated methods and devices
US11141263B2 (en) 2015-11-18 2021-10-12 Shifamed Holdings, Llc Multi-piece accommodating intraocular lens
US11266496B2 (en) 2017-06-07 2022-03-08 Shifamed Holdings, Llc Adjustable optical power intraocular lenses
US12167960B2 (en) 2016-12-23 2024-12-17 Shifamed Holdings, Llc Multi-piece accommodating intraocular lenses and methods for making and using same
US12376957B2 (en) 2015-11-18 2025-08-05 Shifamed Holdings, Llc Multi-piece accommodating intraocular lens

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US7939614B2 (en) * 2004-05-12 2011-05-10 Adeka Corporation Silicon-containing curing composition and heat cured product thereof
US8071697B2 (en) 2005-05-26 2011-12-06 Dow Corning Corporation Silicone encapsulant composition for molding small shapes
US7551830B2 (en) 2006-02-01 2009-06-23 Dow Corning Corporation Impact resistant optical waveguide and method of manufacture thereof
US8258502B2 (en) 2006-02-24 2012-09-04 Dow Corning Corporation Light emitting device encapsulated with silicones and curable silicone compositions for preparing the silicones
WO2007128051A1 (fr) * 2006-05-03 2007-11-15 Vision Crc Limited Polysiloxanes biologiques
US8439974B2 (en) 2006-05-03 2013-05-14 Vision Crc Limited Adjusted index of refraction of ocular replacement material
US10709549B2 (en) 2013-02-14 2020-07-14 Shifamed Holdings, Llc Hydrophilic AIOL with bonding
US10350057B2 (en) 2013-02-14 2019-07-16 Shifamed Holdings, Llc Hydrophilic AIOL with bonding
US11540916B2 (en) 2013-02-14 2023-01-03 Shifamed Holdings, Llc Accommodating intraocular lens
US9486311B2 (en) 2013-02-14 2016-11-08 Shifamed Holdings, Llc Hydrophilic AIOL with bonding
US10548718B2 (en) 2013-03-21 2020-02-04 Shifamed Holdings, Llc Accommodating intraocular lens
US10195018B2 (en) 2013-03-21 2019-02-05 Shifamed Holdings, Llc Accommodating intraocular lens
US10823982B2 (en) 2014-06-03 2020-11-03 Tsubota Laboratory, Inc. Myopia treatment device
US10133092B2 (en) 2014-06-03 2018-11-20 Tsubota Laboratory, Inc. Myopia prevention device
US11583390B2 (en) 2014-08-26 2023-02-21 Shifamed Holdings, Llc Accommodating intraocular lens
US10736734B2 (en) 2014-08-26 2020-08-11 Shifamed Holdings, Llc Accommodating intraocular lens
US12251303B2 (en) 2014-08-26 2025-03-18 Shifamed Holdings, Llc Accommodating intraocular lens
US11141263B2 (en) 2015-11-18 2021-10-12 Shifamed Holdings, Llc Multi-piece accommodating intraocular lens
US12376957B2 (en) 2015-11-18 2025-08-05 Shifamed Holdings, Llc Multi-piece accommodating intraocular lens
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US11065109B2 (en) 2016-12-23 2021-07-20 Shifamed Holdings, Llc Multi-piece accommodating intraocular lenses and methods for making and using same
US10350056B2 (en) 2016-12-23 2019-07-16 Shifamed Holdings, Llc Multi-piece accommodating intraocular lenses and methods for making and using same
US12167960B2 (en) 2016-12-23 2024-12-17 Shifamed Holdings, Llc Multi-piece accommodating intraocular lenses and methods for making and using same
US10987214B2 (en) 2017-05-30 2021-04-27 Shifamed Holdings, Llc Surface treatments for accommodating intraocular lenses and associated methods and devices
US11266496B2 (en) 2017-06-07 2022-03-08 Shifamed Holdings, Llc Adjustable optical power intraocular lenses
US12465483B2 (en) 2017-06-07 2025-11-11 Shifamed Holdings, Llc Adjustable optical power intraocular lenses

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AU2003207419A1 (en) 2003-09-02

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