WO2012010918A2 - Dispositifs optiques - Google Patents

Dispositifs optiques Download PDF

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Publication number
WO2012010918A2
WO2012010918A2 PCT/HU2011/000077 HU2011000077W WO2012010918A2 WO 2012010918 A2 WO2012010918 A2 WO 2012010918A2 HU 2011000077 W HU2011000077 W HU 2011000077W WO 2012010918 A2 WO2012010918 A2 WO 2012010918A2
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Prior art keywords
general formula
group
same
alkyl
benzoyloxy
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PCT/HU2011/000077
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English (en)
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WO2012010918A3 (fr
Inventor
József Nagy
Péter ÁGOSTON
Erika Pusztai
Nándor TURKEVI-NAGY
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Medicontur Orvostechnikai Kft.
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Publication of WO2012010918A2 publication Critical patent/WO2012010918A2/fr
Publication of WO2012010918A3 publication Critical patent/WO2012010918A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/14—Eye parts, e.g. lenses, corneal implants; Implanting instruments specially adapted therefor; Artificial eyes
    • A61F2/16—Intraocular lenses
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
    • C07C69/614—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety of phenylacetic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/78—Benzoic acid esters
    • 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
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
    • C08F120/68—Esters
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
    • C08F220/68—Esters
    • 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
    • C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a heterocyclic ring containing sulfur
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

Definitions

  • the invention concerns optical devices; especially intraocular lens made from high refractive index polymers prepared from hydroxyalkyl acrylates and methacrylates containing aromatic groups and carbonyl groups.
  • the invention also relates to the starting monomers, the polymers prepared; the application of the same for the manufacture of optical devices and the products derived therefrom.
  • plastic lenses are implanted in the eye, wherein an incision is made and the plastic lens is inserted through the incision.
  • the rigid polymethyl methacrylate lenses previously used have been replaced with soft lenses, which are thin and flexible enough to be inserted into the eye through a smaller incision, in a folded state, where they unfold and take their place.
  • Intraocular lens types and their properties are described in several references. A good overview of the topic is provided by, for example, U.S. Patent No. 7,387,642 or U.S. Patent No. 6,635,732.
  • the refractive power of the lens depends on the shape and the material of which it is made, the higher the refractive index of a material is, the thinner lens can be used to provide the same refractive power. Therefore, said requirements are met by a polymer that is soft and has a high refractive index. However, it is important that the polymer lens material should be biocompatible.
  • U.S. Pat. No. 5,290,892 discloses a solution according to which acrylates and methacrylates containing aromatic groups, especially phenyl ethyl acrylate (PEA) and phenyl ethyl methacrylate (PEMA), were used as a copolymer material for the preparation of IOL lenses.
  • PPA phenyl ethyl acrylate
  • PEMA phenyl ethyl methacrylate
  • the phenyl group provides the high refractive index of about 1.5 to 1.6.
  • the soft IOL lens is always composed of a copolymer prepared from different monomers, especially PEA/PEMA system, i.e. it is a multi-phase system, the composition of which cannot be given with perfect accuracy, which affects the constancy of physical properties as well.
  • the starting acrylate or methacrylate monomer used to prepare the intraocular lens contains both aromatic and carbonyl groups.
  • the invention is based on this recognition.
  • the invention relates to a biocompatible, hydrophobic, soft, high refractive index intraocular lens, wherein an aikane diol derivative is used as a starting monomer, which contains an aryl or aralkyl carboxylic acid ester group on one end, and an acrylic or methacrylic acid ester group to ensure polymerization on the other end.
  • the invention relates to the above starting compounds, the process for the preparation of the same, the polymers prepared therefrom and the use of the compounds for the preparation of optical devices, particularly intraocular lenses.
  • the invention also covers the preparation of intraocular lenses.
  • the common abbreviation (IOL) is used herein to refer to an intraocular lens.
  • the hydrophobic, soft, biocompatible, high- refractive index intraocular lens according to the invention is prepared from aikane diol derivatives containing an aryl or aralkyl carboxylic acid ester on one end and an acrylic or methacrylic acid ester on the other end.
  • Ar represents a substituted aromatic group, preferably a phenyl, biphenylyl, naphthyl, thienyl, furyl, pyrrolyl group, the substituent is one or more hydroxyl, alkyl, alkoxy, alkoxycarbonyl, amino, nitro groups, a halogen atom, wherein the alkyl group may be straight or branched and has 1 to 6 carbon atoms;
  • n is an integer of 2, 3, 4, 5 10;
  • f is an integer of 0, 1 , 2, 3 10;
  • X represents a hydrogen atom or a methyl group
  • Ri , R2, R3, 4 are the same or different and independently represent a hydrogen or halogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl or a carboxyl group.
  • Ar preferably represents an unsubstituted phenyl, thienyl, furyl or pyrrolyl group, particularly preferably a phenyl group, f preferably represents 0, 1 or 2, particularly preferably 0, n is preferably 2, 3 or 4, particularly preferably 2, whereas Ri, R 2 , R3, R4 each preferably represent a hydrogen atom.
  • Preferred compounds are thus the co-(co-phenylalkanoyloxy)alkyl acrylates, the ⁇ -( ⁇ - phenylalkanoyloxy)alkyl methacrylates, the co-[co-(thiophene-2-yl)alkanoyloxy]alkyl acrylates, the (o-[o)-(thiophene-2-yl)alkanoyloxy]alkyl methacrylates, the o-[co-(furan-2-yl)- alkanoyloxy]alkyl acrylates, the (o-[eo-(furan-2-yl)alkanoyloxy]alkyl methacrylates.
  • Furyl derivatives included in the compounds of the general formula (I) are described in U.S. Pat. No. 4,663,41 1. The compounds are used as binders or in the manufacture of coatings.
  • Example 1 1 of WO03/018648 describes a thienyl derivative [2-(thiophene-2-ylcarbonyl)ethyl methacrylate] belonging to compounds of the general formula (I), as the precursor of electrically conductive block copolymers. The said document does not contain any indication as to whether the compounds would be suitable for the preparation of intraocular lenses.
  • WO02/077044 discloses hydrophilic monomers comprising polyether chains, which are different from the hydrophobic compounds according to our invention, for the preparation of contact lenses and IOL lenses.
  • this particular compound and the preparation of this very compound is not presented, since the document discloses a synthesis starting from a polyether (as a first step, oligoether is prepared from 1 ,2-propanediol with propylene oxide, which has about 6 members).
  • Ar' represents a mono- or polysubstituted phenyl, biphenylyl, naphthyl or pyrrolyl group, wherein the substituent is a hydroxyl, alkyl, alkoxy, alkoxycarbonyl, amino, nitro group, a halogen atom, such as chlorine, bromine, fluorine, the alkyl and alkoxy groups have 1 to 6 carbon atoms and may be straight or branched;
  • n' is an integer of 2, 3, 4, 5 10;
  • f is an integer of 0, 1 , 2, 3 10;
  • X' represents a hydrogen atom or a methyl group
  • R]', R 2 ⁇ R3 ' , R4 ' are the same or different and independently represent a hydrogen or halogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl or a carboxyl group.
  • a compound of the general formula Ar-((CRiR 2 ) f -C(0)-0- (CR 3 R4) n -OH, wherein Ar, Ri, R 2 , R 3 , R ⁇ f and n are the same as in the general formula (I), is reacted with a compound of the general formula CH 2 C(X)-C(0)-L; in this latter formula, X is the same as in the general formula (I), L represents a leaving group, for example, a halogen atom, such as chlorine, bromine, fluorine or iodine; the reaction is carried out in the presence of an acid- binding agent, such as triethylamine, in a solvent, for example, an organic solvent, such as diethyl ether, ethyl acetate, acetone or other suitable solvent.
  • an acid- binding agent such as triethylamine
  • the invention also relates to the process for the preparation of compounds of the general formula ( ⁇ ).
  • a further object of the invention is the use of the compounds of the general formula (I) as defined above for the preparation of optical devices such as contact lenses, IOL, especially in the preparation of IOL.
  • the invention also extends to the preparation of polymers from compounds of the general formula (I) as monomers, the prepared polymers and the use thereof for the preparation of optical devices.
  • Monomers of the general formula (I) are suitable on their own for the preparation of homopolymers appropriate for optical devices such as intraocular lenses, but they can also be copolymerized with other known acrylate and methacrylate type monomers in order to prepare two- or three-, possibly multi-component copolymers.
  • Such co-monomers include, but are not limited to the following: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), acrylic acid, methacrylic acid, NN-dimethylacrylamide, N-vinylpyrrolidone, styrene, polyethylene glycol monoacrylate and methacrylate, etc.
  • the invention includes the joint use of compounds of the general formula (I) and such co-monomers for the preparation of optical devices, e.g., contact lenses, IOL, especially IOL.
  • copolymers are prepared from the above monomers with the use of known copolymerizable cross-linking agents. With these, the rheological properties of monomers can be changed.
  • cross-linking agents to be used include, but are not limited to the following: ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, allyl methacrylate, 1 ,3- propanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1 ,4-butanediol diacrylate and dimethacrylate and the like.
  • cross-linking agents preferably ethylene glycol dimethacrylate (EGDMA), 1 ,4-butanediol diacrylate (BDDA) or dimethacrylate (BDDMA) are used.
  • Organic silicone diacrylate and dimethacrylate compounds may also be used as a cross- linking agent, including the following compounds of the general formulae (Ila, lib),
  • X represents a hydrogen atom or a methyl group
  • n is 1 , 2, 3, 4, 5 or 6 and m is 0 or an integer between 1 and 20, and
  • X represents a hydrogen atom or a methyl group and n is 1, 2, 3, 4, 5 or 6, m is 0 or an integer between 1 and 20.
  • Preferred compounds of the general formula (II) include, but are not limited to the following siloxane-based monomers: l ,3-bis(acryloyloxymethyl)- l , l,3,3-tetramethyldisiloxane, 1 ,3-bis(acryloyloxypropyl)- 1 , 1 ,3,3-tetramethyldisiloxane, ⁇ (Tetramethyldisiloxane- 1 ,3-diyl) bis[propane-3, l-diyloxy(2-hydroxypropane-3,l-diyl)] ⁇ diacrylate, etc.
  • auxiliary materials and additives can also be integrated in copolymers used for intraocular lenses. Examples include:
  • Ultraviolet absorbing compounds such as substituted benzophenones like 2- hyroxybenzophenone, 2-(2-hydroxyphenyl)-2H-benzotriazol, or the photostabilizers mentioned in U.S. Patent No. 4,304,895, or the 2-(2-hydroxy-5-acryloyloxyphenyl>2H-benzotriazol or 2-[3-(2- methylallyl>2-hydroxy-5-methylphenyl]-2H-benzotriazol included in U.S. Patent No. 4,528,3 1 1.
  • Colour filter dyes making the lens yellow by filtering the blue light can also be used as an additive.
  • Such dyes are disclosed, for example, in the following documents: U.S. 2003/0078359, U.S. 6,310,215, U.S. 5,662,707, U.S. 5,543,504, U.S. 5,528,322, and U.S. 5,470,932.
  • the said yellow dyes contain active vinyl groups, which are incorporated in the polymer matrix, so they do not dissolve from the lens, and influence the vision through the yellow colour thereof.
  • Examples of the compounds include, but are not limited to, the following: 4-[4-(allyloxycarbonyl)phenylazo]-l- phenyl-3-methylpyrazol-5-on, l-phenyl-3-methyl-4-(4-vinylphenylazo)pyrazol-5-on, l-phenyl-3- methyl-5-oxopyrazol-4-carbaldehyde (MPCA),NN-bis (methaciyloylethyl)-/?-aminoazobenzene.
  • the polymer or copolymer forming the raw material of the intraocular lens is prepared by a known polymerization process.
  • the invention also involves the process of preparing polymers from new monomers.
  • the invention applies in particular to a polymer preparation process, wherein a tetrafunctional disiloxane of the general formula (Ila) or (lib) is used as a cross-linking agent; substituents in the formulae are the same as above.
  • Polymerization can be carried out by using free radical initiators, such as thermally decomposing peroxides, azides, or it can be carried out with the use of photoinitiators, for example, UV light, inducing radical polymerization.
  • free radical initiators such as thermally decomposing peroxides, azides
  • photoinitiators for example, UV light, inducing radical polymerization.
  • free radical initiators benzophenone peroxide, peroxycarbonates, bis-(4-/err-butylcyclohexyl) peroxycarbonate, azonitriles, for example, azobisisobutyronitrile.
  • Photoinitiators are generally of benzophenone type.
  • the refractive index of the soft IOL polymers according to the invention is around 1.5, the glass transition temperature thereof corresponds to the given use.
  • the materials used are either prepared by us or purchased from commercial sources.
  • BEA 2-(benzoyloxy)ethyl acrylate or 2-(acryloyloxy)ethyl benzoate
  • EGDMA ethylene glycol dimethacrylate or ethane- l ,2-diyl-bis(2-methacrylate)
  • BDDMA butanediol dimethacrylate or butane- l,4-diyl-bis(2-methacr late)
  • FEA 2-(furan-2-ylcarbonyloxy)ethyl acrylate
  • HEM A hydroxyethyl methacrylate
  • SD A 1 ,3 -bis(acry loyloxymethy 1)- 1 , 1 ,3,3 -tetramethyldisiloxane
  • UV ultraviolet light-absorbing compound
  • a 500-ml four-necked flask equipped with a thermometer, a reflux condenser closed with a CaCl 2 tube, a stirrer and a dropping funnel is charged with 90.0 g (0.7965 mol) of potassium acrylate (which was previously prepared from acrylic acid and potassium carbonate), 2.0 g of hydroquinone and 200 ml of dimethylformamide.
  • the reaction mixture is heated until dissolution and then 77.0 g (0.3333 mol) of (ClCH 2 SiMe 2)2 0, i.e. 1.3-bis(chloromethyl)-l,l,3,3,-tetramethyldisiloxane is slowly added thereto.
  • the reaction mixture is boiled for 6 hours and then the KCl salt formed is filtered over a G3 glass filter. 80% of the solvent is distilled off, the residue is dissolved in 300 ml of diethyl ether, washed four times with distilled water and then dried overnight over CaCl 2. The mixture is filtered, the solvent is distilled off and the residue is distilled under vacuum.
  • a 1500-ml four-necked flask equipped with a thermometer, a reflux condenser closed with a CaCl 2 tube, a stirrer and a dropping funnel is charged with 1000 ml of ethyl acetate, 2.0 g of hydroquinone and 250 g (1 mol) of l ,3-bis(hydroxypropyl)-l,l,3,3-tetramethyldisiloxane.
  • the reaction mixture is cooled to 5 °C; 190 g (2.1 mol) of acryloyl chloride is slowly added thereto and then stirred for 6 hours.
  • the crude product obtained is deinhibited as described in reference example 1.
  • a 250-ml four-necked flask equipped with a thermometer, a reflux condenser closed with a CaCl 2 tube, a stirrer and a dropping funnel is charged with 65.2 g (0.2 mol) of allyl glycidyl ether, 0.4 g hydroquinone, 0.5 ml of concentrated sulphuric acid and 28.8 g (0.4 mol) acrylic acid.
  • the reaction mixture is stirred for 6 hours at a temperature between 70-80 °C and then allowed to cool to room temperature. It is deinhibited as described in reference example 1.
  • n d 25 1.464.
  • a 2-liter apparatus equipped with a stirrer, a dropping funnel, a thermometer, a reflux condenser and a calcium chloride tube is charged with 700 ml of ethyl acetate, 202 g (2 mol) of triethylamine, 62 g (1 mol) of ethylene glycol, under nitrogen stream and 285 g (2 mol) of benzoyl chloride is added dropwise thereto for about 1 hour.
  • the reaction mixture is stirred for 4 hours and allowed to stand overnight.
  • 250 ml of 1 N hydrochloric acid is added thereto, stirred for 10 minutes and the phases are separated.
  • the organic phase is washed twice with 1 N hydrochloric acid solution and then washed neutral with water.
  • the organic phase is then dried over anhydrous calcium chloride, filtered, and the solvent is distilled. 264.2 g of the title compound is obtained, yield 97.9%. After crystallization from methanol, a white, solid material is obtained.
  • a one-liter flask equipped with a magnetic stirrer, a calcium chloride tube and a reflux condenser is charged with 264.2 g (0.978 mol) of melted ethylene dibenzoate prepared according to the previous step, and then 270 g (4.35 mol) of ethylene glycol and 2.0 g of potassium hydroxide are added thereto.
  • the reaction mixture is stirred for 16 hours at 160-170 C in oil bath, thus a homogeneous solution is obtained, which is allowed to cool to room temperature, and then the potassium hydroxide is neutralized with carbon dioxide gas.
  • the desired compound is separated by vacuum distillation. 221.0 g of 2-hydroxyethyl benzoate is obtained, yield 66.6%.
  • a 2-liter flask equipped with a stirrer, a thermometer, a nitrogen inlet, a dropping funnel and a reflux condenser is charged with 107.0 g (1.06 mol) of triethylamine, 166.0 g (1 mol) of 2- hydroxyethyl benzoate prepared according to the previous step and 600 ml of ethyl acetate.
  • 95.0 g (1.05 mol) of acryloyl chloride is added dropwise to the reaction mixture while cooling in ice, in the meantime the temperature thereof rises to 10 °C, it is stirred for 5 hours at this temperature, then allowed to stand overnight.
  • n D 20 1.5150.
  • a 2-liter four-necked round-bottom flask equipped with a stirrer, a reflux condenser closed with a CaCl 2 tube, a thermometer and a dropping funnel is charged with 1 12.0 g (1.1 mol) of triethylamine, 1 16.0 g (1 mol) of HEA, 600 ml of ethyl acetate and 0.40 g of hydroquinone stabilizer washed in with ethyl acetate.
  • Moist air is displaced with anhydrous nitrogen stream, and the nitrogen stream is maintained until the end of the reaction. Internal space is cooled to +4 °C with outside cooling in ice.
  • the product is deinhibited as described in reference example 1.
  • the process is the same as described in example 2, with the difference that 51 g (0.5 mol) triethylamine, 65 g (0.5 mol) of 2-hydroxyethyl methacrylate, 0.4 g of hydroquinone, 70.3 g (0, 5 mol) of benzoyl chloride and 500 ml of ethyl acetate is used.
  • a 2-liter four-necked round-bottom flask equipped with a stirrer, a reflux condenser closed with a CaC tube, a thermometer and a dropping funnel is charged with 1 12.0 g ( 1.1 mol) of triethylamine, 116.0 g (1 mol) of HEA, 600 ml of ethyl acetate and 0.40 g of hydroquinone stabilizer washed in with ethyl acetate.
  • Moist air is displaced with anhydrous nitrogen stream, and the nitrogen stream is maintained until the end of the reaction. Internal space is cooled to +4 °C with outside cooling in ice.
  • the product is deinhibited as described above.
  • a 2-liter four-necked round-bottom flask equipped with a stirrer, a reflux condenser closed with a CaCl 2 tube, a thermometer and a dropping funnel is charged with 1 12.0 g ( 1.1 mol) of triethylamine, 144.0 g ( 1 mol) of 4-hydroxybutyl acrylate, 600 ml of ethyl acetate and 0.40 g of hydroquinone stabilizer washed in with ethyl acetate.
  • Moist air is displaced with anhydrous nitrogen stream, and the nitrogen stream is maintained until the end of the reaction. Internal space is cooled to +4 °C with outside cooling in ice.
  • the product is deinhibited as described above.
  • a flask is charged with 196 g of BEA and 3 g of EGDMA. 0.3 g of initiator is added thereto, and the mixture is stirred intensively at 25 °C under a stream of nitrogen gas for 30 minutes. The monomer mixture is filled in an apparatus, then polymerized at 60 °C for 12 hours, and post- polymerized at 90 °C for 24 hours.
  • Discs of 13 to 17 mm in diameter and 2 to 3.5 mm thick are formed from the finished polymer sheets.
  • the finished discs are post-treated at 90 °C for 168 hours, then machining the same, lenses and test specimens are made therefrom.
  • the process is the same as described in example 11 , with the difference that 189 g of BEA, 10 g of EGDMA, and 0.3 g of initiator are used.
  • the process is the same as described in example 11, with the difference that 191 g of BEA, 7.9 g of BDDMA-t and 0.6 g of initiator are used.
  • the process is the same as described in example 11, with the difference that 185.8 g of BEA, 14.2 g of SDA, and 0.14 g of initiator are used.
  • the process is the same as described in example 11, with the difference that 85 g of BEA, 106 g of fractionated BA, 1.4 g of UV and 7 g of EGDMA, as well as 0.28 g of initiator are used.
  • Copolymer preparation from BEA with 56% BA and 3.7% EGDMA The process is the same as described in example 1 1 , with the difference that 78 g of BEA, 1 12.7 g of fractionated BA, 1.4 g of UV-t and 7.4 g of EGDMA, as well as 0.3 g of initiator are used.
  • the process is the same as described in example 11, with the difference that 67.7 g of BEA, 122.2 g of fractionated BA, 1.6 g of UV and 8 g of EGDMA, as well as 0.32 g initiator are used.
  • the process is the same as described in example 11, with the difference that 71 g of BEMA, 1 18.8 g of fractionated BA, 1.56 g of UV and 7.8 g of EGDMA, as well as 0.31 g of initiator are used.
  • Discs of 14 to 16 mm in diameter and 3 mm thick were formed from the polymer materials thus prepared, which served as a raw material for the test specimens and the lenses made therefrom. Refractive index and transmittance were determined for the test specimens prepared. Injectability of lenses made with the same geometry from different materials was examined on the lenses prepared.
  • compositions 1 and 2 The composition, physical constants, workability and elasticity of some polymers according to the invention are provided in Tables 1 and 2 below.
  • Machining means turning under cooled conditions.
  • Elasticity is a characteristic feature of injectability in case of a small wound.
  • EGDMA ethane- 1,2-diyl bis(2-methacrylate) SDA l,3-bis(acryloyloxymethyl)-l , 1 ,3,3-tetramethyldisiloxane
  • BDDMA butane- 1,4-diyl bis(2-methacrylate)
  • INN Radical polymerization initiator
  • the BEA-type material itself is suitable as a raw material for IOL lenses.
  • the synthesized polymers were subjected to toxicological tests in accordance with USP 32 ⁇ 88> and it was found that the compounds were not toxic.

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  • Veterinary Medicine (AREA)
  • Vascular Medicine (AREA)
  • Biomedical Technology (AREA)
  • Transplantation (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Cardiology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Medical Uses (AREA)

Abstract

L'invention concerne des dispositifs optiques, notamment des lentilles intra-oculaires en polymères à indice de réfraction élevé produits à partir de méthacrylates et d'acrylates hydroxyalkyliques contenant des groupes aromatiques et des groupes carbonyle. L'invention concerne également les monomères de départ, les polymères produits, l'application de ces derniers pour la fabrication de dispositifs optiques et les produits dérivés.
PCT/HU2011/000077 2010-07-21 2011-07-21 Dispositifs optiques WO2012010918A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
HU1000385A HUP1000385A2 (en) 2010-07-21 2010-07-21 Alkane diol derivatives preparation thereof and based on them
HUP1000385 2010-07-21

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WO2012010918A2 true WO2012010918A2 (fr) 2012-01-26
WO2012010918A3 WO2012010918A3 (fr) 2012-03-29

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CN107827918A (zh) * 2017-11-13 2018-03-23 安庆飞凯高分子材料有限公司 一种有机硅丙烯酸酯单体的制备方法
JP2021017427A (ja) * 2019-07-23 2021-02-15 長瀬産業株式会社 ビスハロアルキルシロキサン化合物及びその製造方法、並びに、両末端官能性のシロキサン化合物の製造方法

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WO2002077044A2 (fr) 2001-03-26 2002-10-03 Contamac Ltd Composition polymere
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107827918A (zh) * 2017-11-13 2018-03-23 安庆飞凯高分子材料有限公司 一种有机硅丙烯酸酯单体的制备方法
JP2021017427A (ja) * 2019-07-23 2021-02-15 長瀬産業株式会社 ビスハロアルキルシロキサン化合物及びその製造方法、並びに、両末端官能性のシロキサン化合物の製造方法
JP7350253B2 (ja) 2019-07-23 2023-09-26 長瀬産業株式会社 ビスハロアルキルシロキサン化合物及びその製造方法、並びに、両末端官能性のシロキサン化合物の製造方法

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WO2012010918A3 (fr) 2012-03-29
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