WO2000079312A1 - High refractive index compositions for ophthalmic implants - Google Patents

High refractive index compositions for ophthalmic implants Download PDF

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Publication number
WO2000079312A1
WO2000079312A1 PCT/US2000/015464 US0015464W WO0079312A1 WO 2000079312 A1 WO2000079312 A1 WO 2000079312A1 US 0015464 W US0015464 W US 0015464W WO 0079312 A1 WO0079312 A1 WO 0079312A1
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Prior art keywords
acrylate
methacrylate
poly
glass transition
transition temperature
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Application number
PCT/US2000/015464
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French (fr)
Inventor
David P. Vanderbilt
Original Assignee
Bausch & Lomb Surgical, Inc.
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Publication date
Application filed by Bausch & Lomb Surgical, Inc. filed Critical Bausch & Lomb Surgical, Inc.
Priority to AU54643/00A priority Critical patent/AU5464300A/en
Publication of WO2000079312A1 publication Critical patent/WO2000079312A1/en

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    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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 present invention relates to novel ophthalmic lens materials and a method for making and using the same. More particularly, the present invention relates to soft, optically transparent, high refractive index materials particularly suited for use in the production of intraocular lenses, and a method for manufacturing and using the same.
  • intraocular lenses Since the 1940's optical devices in the form of intraocular lenses (lOLs) have been utilized as replacements for diseased or damaged natural ocular lenses. In most cases, an intraocular lens is implanted within an eye at the time of surgically removing the diseased or damaged natural lens, such as for example, in the case of cataracts. For decades, the preferred material for fabricating such intraocular lenses was poly(methyl methacrylate), which is a rigid, glassy polymer.
  • Softer, more flexible lOLs have gained in popularity in more recent years due to their ability to be compressed, folded, rolled or otherwise deformed. Such softer lOLs may be deformed prior to insertion thereof through an incision in the cornea of an eye. Following insertion of the IOL in an eye, the IOL returns to its original pre-deformed shape due to the memory characteristics of the soft
  • high water content hydrogel materials have relatively low refractive indexes, making them less desirable than other materials with respect to minimal incision size.
  • Low refractive index materials require a thicker IOL optic portion to achieve a given refractive power.
  • Silicone materials may have a higher refractive index than high-water content hydrogels, but tend to unfold explosively after being placed in the eye in a folded position. -Explosive unfolding
  • Soft, foldable, high refractive index, low glass transition temperature compositions produced through the copolymerization of one or more high refractive index, low glass transition temperature monomers with one or more low
  • compositions of the present invention comprise two or more monomers polymerized in the presence
  • Another object of the present invention is to provide an IOL material having a high refractive index and low glass transition temperature.
  • Another object of the present invention is to provide an IOL material that has a high refractive index, a low glass transition temperature and is colorless.
  • Another object of the present invention is to provide an IOL material that has a high refractive index, a low glass transition temperature and is transparent.
  • Still another object of the present invention is to provide an IOL material that is relatively simple to manufacture.
  • compositions of the present invention have a balance of high
  • the refractive power of an IOL is a function of the particular lens shape and the refractive index of the material from which the lens is made.
  • An IOL made from a material having a relatively high refractive index may be made to be thinner and yet have the same refractive power as a thicker IOL made from a material having a relatively lower refractive index.
  • the flexibility of an IOL is a function of the particular lens shape and the glass transition temperature of the material from which the lens is made.
  • An IOL made from a material having a relatively low glass transition temperature will be more flexible than the same lens made from a material having a relatively high glass transition temperature.
  • lOLs designed to be rolled or folded for insertion through a small incision are preferably thinner and more flexible.
  • lOLs of the present invention manufactured from the novel compositions disclosed herein may be designed to be thinner because of the unexpectedly high refractive index of the material and may be
  • compositions of the present invention suitable for use in the manufacture
  • the first class of monomer forms a homopolymer having a relatively high refractive index, such as a refractive index of approximately 1.50 or greater, and relatively low glass transition temperature, such as a glass transition temperature of approximately 20 degrees Celsius or less.
  • Suitable homopolymers formed from the first class of monomer have at least one monomer having the structure represented by Formulas 1 through 5 below,
  • Ri is selected from the group consisting of hydrogen and C 1 - 12 alkyl such as for example but not limited to methyl, butyl, heptyl or decyl but preferably hydrogen to promote chain flexibility
  • R 2 is selected from the group consisting of oxygen, sulfur and NR3 but preferably oxygen or sulfur
  • R 3 is selected from the group consisting of hydrogen and C1-6 alkyl such as for example but not limited to methyl, propyl or hexyl
  • R4 is selected from the group consisting of oxygen and sulfur
  • Ar is selected from the group consisting of C ⁇ -36 aryl such as for example but not limited to C6H 5 ( ⁇ henyl), C ⁇ 0 H7(naphthyl), Ci4Hg(anthracyl), Ci 4 Hg(phenanthryl) or an aromatic system having up to eight fused rings but
  • Ci- ⁇ such as for example but not limited to fluorine, chlorine, bromine or iodine, but preferably chlorine or bromine due to high refractive index considerations, Ci- ⁇
  • alkyl such as for example but not limited to methyl, propyl or hexyl but preferably methyl, C ⁇ -- ⁇ alkoxy such as for example but not limited to methoxy, propoxy or hexyloxy but preferably methoxy, C6-25 aryl such as for example but not limited to phenyl, naphthyl or anthracyl but preferably phenyl due to glass transition temperature considerations, and C &.25 substituted aryl containing nitrogen or sulfur such as for example but not limited to pyridine, quinoline, benzoquinoline, isoquinoline, pyrrole, thiophene, imidazole, thiazole, pyrazole, pyrimidine, purine, or carbazole but preferably thiophene and thiazole due to high refractive index considerations; n is an integer greater than or equal to 2, m is an integer greater than 1 and less than 5, and p is an integer greater than or equal to 1 ; whereby the homo
  • Suitable monomers from the first class of monomers described above include for example but are not limited to 2-phenylethyl acrylate, 3-phenylpropyl acrylate, 4-phenylbutyl acrylate, 4-phenylbutyl methacrylate, 5-phenylpentyl acrylate, 5-phenylpentyl methacrylate, 6-phenylhexyl acrylate, 6-phenylhexyl methacrylate, 2-phenyloxyethyl acrylate, 3-phenyloxypropyl acrylate, 2-hydroxy-
  • monomers for use in the present invention include 2-phenylethyl acrylate, 2-
  • the second class of monomer forms a homopolymer having a relatively low refractive index, such as a refractive index less than approximately 1.50, and a relatively high glass transition temperature, such as a glass transition temperature greater than approximately 20 degrees Celsius, the general structure of which is represented by Formula 6 below,
  • Ri is defined the same as for that of Formulas 1 through 5 above; and Rs is selected from the group consisting of hydrogen and C 1 - 4 alkyl such as for example but not limited to methyl, propyl or butyl but preferably methyl due to glass transition temperature considerations; whereby the homopolymer formed from said monomer has a glass transition temperature greater than
  • methacrylate n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 1-methylcyclohexyl methacrylate, bomyl methacrylate,
  • Preferred low refractive index, high glass transition temperature monomers for use in the present invention include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate and glycidyl methacrylate to achieve the unexpectedly high refractive index and unexpectedly low glass transition temperature compositions of the present invention which are both flexible and biocompatible.
  • Glycidyl methacrylate and like monomers are also particularly preferable for use in the present invention for the attachment of surface coatings. Medical devices and/or implants manufactured using compositions of the present invention comprising glycidyl methacrylate and/or like monomers, may be surface coated to alter the surface chemistry thereof if desired.
  • compositions of the present invention are produced by polymerizing approximately 50 mol percent or more of a monomer or monomers from the first class of monomers with approximately 50 mol percent or less of a monomer or monomers from the second class of monomers in the presence of a ⁇ osslinker
  • hydrophilic a hydrophilic compound selected from the group consisting of: a hydrophilic and a hydrophilic group consisting of: a hydrophilic and a hydrophilic group consisting of: a hydrophilic and a hydrophilic
  • compositions of the present invention may also be added during the polymerization of the compositions of the present invention to reduce or eliminate the formation of haze and/or
  • compositions of the present invention include for example, but are not limited to poly(2-phe ⁇ ylethyl acrylate-co-methyl methacrylate), poly(3- phenylpropyl acrylate-co-methyl methacrylate), poly(4-phenylbutyl acrylate-co- methyl methacrylate), poly(4-phenylbutyl methacrylate-co-methyl methacrylate), poly(5-phenylpentyl acrylate-co-methyl methacrylate), poly(5-phenylpentyl methacrylate-co-methyl methacrylate), poly(6-phenyl hexyl acrylate-co-methyl methacrylate), poly(6-phenylhexyl methacrylate-co-methyl methacrylate), poly(2- phenyloxyethyl acrylate-co-methyl methacrylate), poly(3-phenyloxypropyl acrylate-co-methyl methacrylate), poly(2-hydroxy
  • methacrylate-co-methyl methacrylate poly(6-phenyloxyhexyl acrylate-co-methyl methacrylate), poly(6-phenyloxyhexyl methacrylate-co-methyl methacrylate), l poly(2-aminophenylethyl acrylate-cg-methyl methacrylate), poly(3- aminopheny I propyl acrylate-cg-methyl methacrylate), poly(4-aminophenylbutyl
  • phenyloxyhexyl methacrylate-co-isopropyl methacrylate poly(2-phenylthioethyl acrylate-cg-isopropyl methacrylate), poly(3-phenylthiopropyl acrylate-cg-isopropyl methacrylate), poly(4-phenylthiobutyl acrylate-cg-isopropyl methacrylate), poly(4- phenylthiobutyl methacrylate-cg-isopropyl methacrylate), poly(5-phenylthiopentyl acrylate-co-isopropyl methacrylate), poly(5-phenylthiopentyl methacrylate-co- isopropyl methacrylate), poly(6-phenyloxyhexyl acrylate-cg-isopropyl methacrylate), poly(6-phenyloxyhexyl methacrylate-cg-isopropyl
  • phenyl ether methacrylate-cg-glycidyl methacrylate poly(2-phenyloxyethyl acrylate-cg-methyl methacrylate-cg-ethyl methacrylate), poiy(2-phenylethyl acrylate-cg-methyl methacrylate-cg-glycidyl methacrylate) and poly(2- phenylthioethyl acrylate-cg-methyl methacrylate-cg-glycidyl methacrylate).
  • compositions of the present invention include poly(2-phenylethyl acrylate-gg-methyl methacrylate), poly(2-phenylethyl acrylate-cg-methyl methacrylate-cg-glycidyl methacrylate), poly(2-phenylthioethyl acrylate-cg-methyl methacrylate), poly(2-phenyloxyethyl acrylate-cg-methyl methacrylate), poly(2- phenyloxyethyl acrylate-cg-methyl methacrylate-cg-ethyl methacrylate) and poly(phenylthioethyl acrylate-cg-methyl methacrylate-cg-glycidyl methacrylate).
  • compositions of the present invention unexpectedly have high refractive indexes and low glass transition temperatures.
  • One reason such material characteristics are unexpected is due to the relatively low refractive index and relatively high glass transition temperature of a major component thereof, i.e., the second class of monomers.
  • the compositions of the present invention with their high refractive indexes and low glass transition temperatures are desirable for use in the manufacture thinner lOLs.
  • a thin IOL or an IOL having a thin optic is critical in enabling a surgeon to minimize incision size. Keeping the surgical incision size to a minimum reduces
  • a thin IOL is also ⁇ itical
  • lOLs may be placed in the anterior chamber for
  • the preferred materials of the present invention also have the flexibility
  • the glass transition temperature (Tg) of the material is of considerable importance.
  • materials could be synthesized as described herein to have the desired high refractive index and low glass transition temperature because many high refractive index monomers have bulky side-chains which restrict chain mobility and drastically in ⁇ ease the overall glass transition temperature of the copolymer.
  • a ⁇ ylates produce polymers with lower glass transition temperatures than the corresponding methacrylates and are therefor preferred for use as a monomer from the first class of monomers.
  • Suitable ⁇ osslinkers for use in producing the subject compositions include
  • Suitable initiators for use in producing the subject compositions include for example but are not limited to 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4- dimethylvaleronitrile), 2,2'-azobis(methylbutyronitrile), 1 ,1'- azobis(cyanocyclohexane), di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoyl peroxy)hexane, t-butyl peroxyneodecanote, t-butyl peroxy 2-ethylhexanoate, di(4-t-butyl cyclohexyl) peroxydicarbonate, t-
  • Suitable ultraviolet light absorbers which may optionally be used in the manufacture of the subject compositions include for example but are not limited to beta-(4-benzotriazoyl-3-hyd-Oxyphenoxy) ethyl acrylate, 4-(2-a ⁇ yloxyethoxy)- 2-hydroxybenzophenone, 4-methacryloxy-2-hydroxybenzophenone, 2- ⁇ 2'- metha---ryloxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'- methacryoxyethylphenyl)-2H-benzotriazole, 2- ⁇ 3'-tert-Butyl-2'-hydroxy-5'-(3''- methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-(3'-te ⁇ t-Butyl-5'-(3 ,, - dimethylvinylsilylpropoxy)-2'-hydroxyphenyl]-5-methoxybenzotriazole, 2-(
  • Inhibitor-free 2-phenylethyl acrylate (PEA) and methyl methacrylate (MMA) containing 10 parts per million (ppm) methoxyhydroquinone (MEHQ) were combined in the molar ratios tabulated below.
  • Ethylene glycol dimethacrylate (EGDMA) was added in the amount of 0.5 mol % based on total moles of PEA and MMA.
  • 2,2 , -Azobis(isobutyronitrile) (AIBN) and 1,1'-azobis(1- cyclohexanecarbonitrile) (V-40) were added in the amounts of 0.05 mol percent each based on total moles of PEA, MMA and EGDMA.
  • test pieces were removed from each cured sheet and extracted in acetone at room temperature to remove residual monomers. After air-drying at room temperature for several hours, the test pieces were heated in
  • the samples were subsequently held at 37 °C in balanced salt solution (BSS) and the refractive index of each composition was re- determined.
  • BSS balanced salt solution
  • the equilibrium water content (EWC) was determined by [mass of water in the polymer / mass of water-swollen polymer] X 100.
  • a second series of polymer sheets were prepared holding the ⁇ osslinker level constant at 0.5 mol% EGDMA based on total moles of PEA, MMA and glycidyl methacrylate (GMA).
  • a combination of free radical initiators, i.e., AIBN i.e., AIBN
  • PEA/MMA/GMA (mol/mol/mol.
  • a third set of sheets was prepared in the same manner as Example 2
  • PTEA Inhibitor-free phenylthioethyl acrylate
  • MMA Inhibitor-free phenylthioethyl acrylate
  • EGDMA phenylthioethyl acrylate
  • MMA mol/mol
  • AIBN 0.025 mol%
  • V-A0 0.025 mol%
  • PTEA/MMA mol/mol
  • Rl post-extm
  • Rl 37 °C. BSS
  • EWC 37 °C. BSS
  • lOLs manufactured using the compositions of the present invention can be of any design capable of being rolled or folded into a small ⁇ oss section that can fit through a relatively small incision, i.e., 4.0 mm or less.
  • lOLs can be of a one-piece or multipiece design, and comprise optic and haptic portions.
  • the optic portion is that portion which serves as the lens and the haptic portions are attached to the optic portion to hold the optic portion in proper alignment within an eye.
  • the haptic portions may be integrally formed with the optic
  • the subject lOLs may be manufactured to have the optic portion and the
  • haptic portions made of the same or different materials.
  • haptic portions made of the same or different materials.
  • the optic portion and the haptic portions are made of the same high-refractive index, low glass transition temperature composition.
  • the optic portion and the haptic portions may also be manufactured from different compositions and/or different formulations of the same composition as des ⁇ ibed in detail in U.S. Patent Numbers 5, 217,491 and 5,326,506, each incorporated herein in their entirety by reference.
  • the material is either cast in molds of the desired shape or cast in the form of rods and lathed into disks. These disks are then machined at low temperatures below the glass transition temperature into lOLs. The lOLs whether molded or machined are then cleaned, polished, packaged and sterilized by customary methods known to those skilled in the art.
  • the materials of the present invention are also suitable for use as other ophthalmic devices such as contact lenses, keratoprostheses, capsular bag extension rings, comeal inlays, corneal rings or like devices.
  • lOLs manufactured using the unique materials of the present invention are used as customary in the field of ophthalmology. In a surgical procedure, an incision is placed in the cornea of an eye, most commonly the natural lens of the eye is removed and the IOL manufactured from materials of the present invention is inserted into the posterior chamber or lens capsule of the eye prior to closing

Abstract

Optically transparent, high refractive index, low glass transition temperature compositions and intraocular lenses fabricated therefrom are described herein. The preferred compositions have a refractive index of approximately 1.45 or greater and a glass transition temperature of approximately 20 degrees Celsius or less.

Description

HIGH REFRACTIVE INDEX COMPOSITIONS FOR OPHTHALMIC IMPLANTS
FIELD OF THE INVENTION
The present invention relates to novel ophthalmic lens materials and a method for making and using the same. More particularly, the present invention relates to soft, optically transparent, high refractive index materials particularly suited for use in the production of intraocular lenses, and a method for manufacturing and using the same.
BACKGROUND OF THE INVENTION
Since the 1940's optical devices in the form of intraocular lenses (lOLs) have been utilized as replacements for diseased or damaged natural ocular lenses. In most cases, an intraocular lens is implanted within an eye at the time of surgically removing the diseased or damaged natural lens, such as for example, in the case of cataracts. For decades, the preferred material for fabricating such intraocular lenses was poly(methyl methacrylate), which is a rigid, glassy polymer.
Softer, more flexible lOLs have gained in popularity in more recent years due to their ability to be compressed, folded, rolled or otherwise deformed. Such softer lOLs may be deformed prior to insertion thereof through an incision in the cornea of an eye. Following insertion of the IOL in an eye, the IOL returns to its original pre-deformed shape due to the memory characteristics of the soft
A material. Softer, more flexible lOLs as just described may be implanted into an
eye through an incision that is much smaller, i.e., less than 4.0 mm, than that necessary for more rigid lOLs, i.e., 5.5 to 7.0 mm. A larger incision is necessary
for more rigid lOLs because the lens must be inserted through an incision in the cornea slightly larger than the diameter of the inflexible IOL optic portion. Accordingly, more rigid lOLs have become less popular in the market since larger incisions have been found to be associated with an increased incidence of postoperative complications, such as induced astigmatism.
With recent advances in small-incision cataract surgery, increased emphasis has been placed on developing soft, foldable materials suitable for use in artificial lOLs. In general, these materials fall into one of three categories: hydrogels, silicones and low glass transition temperature acrylics.
In general, high water content hydrogel materials have relatively low refractive indexes, making them less desirable than other materials with respect to minimal incision size. Low refractive index materials require a thicker IOL optic portion to achieve a given refractive power. Silicone materials may have a higher refractive index than high-water content hydrogels, but tend to unfold explosively after being placed in the eye in a folded position. -Explosive unfolding
can potentially damage the corneal endotheiium and/or rupture the natural lens
capsule and associated zonules. Low glass transition temperature acrylic
materials are desirable because they typically have a high refractive index and
unfold more slowly and more controllably than silicone materials. Unfortunately,
low glass transition temperature acrylic materials, which contain little or no water
1 initially, may absorb pockets of water in vivo causing light reflections or "glistenings". Furthermore, it may be difficult to achieve ideal folding and
unfolding characteristics due to the temperature sensitivity of some acrylic
polymers.
U.S. Patent No. 5,433,746 issued July 18, 1995 teaches of particular high refractive index, low glass transition temperature acrylic compositions synthesized by polymerizing with a αosslinker certain high refractive index, low glass transition temperature monomers with certain high refractive index, high glass transition temperature monomers.
U.S. Patent No. 5,359,021 issued October 25, 1994 teaches of particular high refractive index, low glass transition temperature compositions synthesized by polymerizing with a crosslinker certain high refractive index, high glass transition temperature monomers with certain low refractive index, low glass transition temperature monomers.
SUMMARY OF THE INVENTION
Soft, foldable, high refractive index, low glass transition temperature compositions produced through the copolymerization of one or more high refractive index, low glass transition temperature monomers with one or more low
refractive index, high glass transition temperature monomers having
unexpectedly high refractive indexes and unexpectedly low glass transition
temperatures particularly suited for use as intraocular lenses (lOLs), or other
ophthalmic devices such as for example but not limited to contact lenses, keratoprostheses and corneal rings or inlays, have now been discovered. The high refractive index, low glass transition temperature compositions of the present invention comprise two or more monomers polymerized in the presence
of a crosslinker, an initiator and optionally an ultraviolet light absorber.
Accordingly, it is an object of the present invention to provide a biocompatible IOL material having a high refractive index and low glass transition temperature.
Another object of the present invention is to provide an IOL material having a high refractive index and low glass transition temperature.
Another object of the present invention is to provide an IOL material that has a high refractive index, a low glass transition temperature and is colorless.
Another object of the present invention is to provide an IOL material that has a high refractive index, a low glass transition temperature and is transparent.
Still another object of the present invention is to provide an IOL material that is relatively simple to manufacture.
These and other objectives and advantages of the present invention, some of which are specifically described and others that are not, will become apparent from the detailed description and claims that follow. DETAILED DESCRIPTION OF THE INVENTION
The unique compositions of the present invention have a balance of high
refractive index and low glass transition temperature to achieve desirable characteristics for use in the manufacture of ophthalmic devices such as
intraocular lenses (lOLs). The refractive power of an IOL is a function of the particular lens shape and the refractive index of the material from which the lens is made. An IOL made from a material having a relatively high refractive index may be made to be thinner and yet have the same refractive power as a thicker IOL made from a material having a relatively lower refractive index. Likewise, the flexibility of an IOL is a function of the particular lens shape and the glass transition temperature of the material from which the lens is made. An IOL made from a material having a relatively low glass transition temperature will be more flexible than the same lens made from a material having a relatively high glass transition temperature. Glass transition temperatures of less than 20 degrees Celsius are required to enable folding of the lOLs in the operating room. lOLs designed to be rolled or folded for insertion through a small incision are preferably thinner and more flexible. lOLs of the present invention manufactured from the novel compositions disclosed herein may be designed to be thinner because of the unexpectedly high refractive index of the material and may be
folded or rolled for insertion due to the unexpectedly low glass transition temperature of the material.
Compositions of the present invention suitable for use in the manufacture
of intraocular implants are comprised using copolymers from two different
-r classes of acrylic monomers. The first class of monomer forms a homopolymer having a relatively high refractive index, such as a refractive index of approximately 1.50 or greater, and relatively low glass transition temperature, such as a glass transition temperature of approximately 20 degrees Celsius or less. Suitable homopolymers formed from the first class of monomer have at least one monomer having the structure represented by Formulas 1 through 5 below,
O
II
Figure imgf000007_0001
C
Formula 1
O
II
Ri - C - — C — π U .. t (LIi l i2) ,\n D K_2 A ΔTr
//
C
Formula 2
0
II
Figure imgf000007_0002
Formula 3
£ 0 w
-C C O— [CH2CH(OH)CH2R ]P Ar ,or
11
Formula 4
Figure imgf000008_0001
Formula 5
wherein Ri is selected from the group consisting of hydrogen and C1-12 alkyl such as for example but not limited to methyl, butyl, heptyl or decyl but preferably hydrogen to promote chain flexibility; R2 is selected from the group consisting of oxygen, sulfur and NR3 but preferably oxygen or sulfur; R3 is selected from the group consisting of hydrogen and C1-6 alkyl such as for example but not limited to methyl, propyl or hexyl; R4 is selected from the group consisting of oxygen and sulfur; Ar is selected from the group consisting of Cβ-36 aryl such as for example but not limited to C6H5(ρhenyl), Cι0H7(naphthyl), Ci4Hg(anthracyl), Ci4Hg(phenanthryl) or an aromatic system having up to eight fused rings but
preferably phenyl or naphthyl due to glass transition temperature considerations,
and C«β substituted aryl wherein one or more carbons are substituted with the same or different substituents selected from the group consisting of halogens
such as for example but not limited to fluorine, chlorine, bromine or iodine, but preferably chlorine or bromine due to high refractive index considerations, Ci-β
alkyl such as for example but not limited to methyl, propyl or hexyl but preferably methyl, Cι--β alkoxy such as for example but not limited to methoxy, propoxy or hexyloxy but preferably methoxy, C6-25 aryl such as for example but not limited to phenyl, naphthyl or anthracyl but preferably phenyl due to glass transition temperature considerations, and C &.25 substituted aryl containing nitrogen or sulfur such as for example but not limited to pyridine, quinoline, benzoquinoline, isoquinoline, pyrrole, thiophene, imidazole, thiazole, pyrazole, pyrimidine, purine, or carbazole but preferably thiophene and thiazole due to high refractive index considerations; n is an integer greater than or equal to 2, m is an integer greater than 1 and less than 5, and p is an integer greater than or equal to 1 ; whereby the homopolymer formed from the selected monomer has a glass transition temperature of approximately 20 degrees Celsius or less and a refractive index of approximately 1.50 or greater.
Suitable monomers from the first class of monomers described above include for example but are not limited to 2-phenylethyl acrylate, 3-phenylpropyl acrylate, 4-phenylbutyl acrylate, 4-phenylbutyl methacrylate, 5-phenylpentyl acrylate, 5-phenylpentyl methacrylate, 6-phenylhexyl acrylate, 6-phenylhexyl methacrylate, 2-phenyloxyethyl acrylate, 3-phenyloxypropyl acrylate, 2-hydroxy-
3-phenoxypropyl acrylate, 4-phenyloxybutyl acrylate, 4-phenyloxybutyl
methacrylate, 5-phenyloxypentyl acrylate, 5-phenyloxypentyl methacrylate, 6- phenyloxyhexyl acrylate, 6-phenyloxyhexyl methacrylate, 2-phenylthioethyl
acrylate, 3-phenylthiopropyl acrylate, 4-phenylthiobutyl acrylate, 4- phenylthiobutyl methacrylate, 5-phenylthiopentyl acrylate, 5-phenylthiopentyl methacrylate, 6-phenyloxyhexyl acrylate, 6-phenyloxyhex l methacrylate, 2-
aminophenylethyl acrylate, 3-aminophenylpropyl acrylate, 4-aminophenylbutyl acrylate, 4-aminophenylbutyl methacrylate, 5-aminophenylpentyl acrylate, 5- aminophenylpentyl methacrylate, 6-aminophenylhexyl acrylate, 6- aminophenylhexyl methacrylate, (N-methyl)aminophenylethyl acrylate, 2- naphthylethyl acrylate, 3-naphthylpropyl acrylate, 4-naphthylbutyl acrylate, 5- naphthylpentyl acrylate, 6-naphthylhexyl acrylate, 2-naphthyloxyethyl acrylate, 3- naphthyloxypropyl acrylate, 4-naphthyloxybutyl acrylate, 5-naphthyloxypentyl acrylate, 6-naphthyloxyhexyl acrylate, 2-naphthylthioethyl acrylate, 3- naphthylthiopropyl acrylate, 4-naphthylthiobutyl acrylate, 5-naphthylpentyl acrylate, 6-naphthylhexyl acrylate, poly(ethylene oxide) phenyl ether acrylate, poly( ethylene oxide) phenyl ether methacrylate, poly(trimethylene oxide) phenyl ether acrylate, poly(trimethylene oxide) phenyl ether methacrylate, poly(ethylene sulfide) phenyl ether acrylate, poly(ethylene sulfide) phenyl ether methacrylate, poly(trimethylene sulfide) phenyl ether acrylate, poly(trimethylene sulfide) phenyl ether methacrylate, poly(propylene oxide) phenyl ether acrylate, poly(propylene oxide) phenyl ether methacrylate, poly(propylene sulfide) phenyl ether acrylate and poly(propylene sulfide) phenyl ether methacrylate.
Preferred high refractive index, low glass transition temperature
monomers for use in the present invention include 2-phenylethyl acrylate, 2-
phenyloxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate and 2- phenylthioethyl acrylate to achieve the unexpectedly high refractive index and i unexpectedly low glass transition temperature compositions of the present
invention which are both flexible and biocompatible.
The second class of monomer forms a homopolymer having a relatively low refractive index, such as a refractive index less than approximately 1.50, and a relatively high glass transition temperature, such as a glass transition temperature greater than approximately 20 degrees Celsius, the general structure of which is represented by Formula 6 below,
O
-C Rs
II c
Formula 6 wherein Ri is defined the same as for that of Formulas 1 through 5 above; and Rs is selected from the group consisting of hydrogen and C1-4 alkyl such as for example but not limited to methyl, propyl or butyl but preferably methyl due to glass transition temperature considerations; whereby the homopolymer formed from said monomer has a glass transition temperature greater than
approximately 20 degrees Celsius and a refractive index less than approximately 1.50.
Suitable monomers from the second class of monomers described above
include for example, but are not limited to methyl methacrylate, ethyl
methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 1-methylcyclohexyl methacrylate, bomyl methacrylate,
isobornyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, methoxymethyl methacrylate, ethoxymethyl methacrylate, cyclohexyloxymethyl methacrylate, 1-ethoxyethyl methacrylate, 2-ethoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate and glycerol methacrylate.
Preferred low refractive index, high glass transition temperature monomers for use in the present invention include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate and glycidyl methacrylate to achieve the unexpectedly high refractive index and unexpectedly low glass transition temperature compositions of the present invention which are both flexible and biocompatible. Glycidyl methacrylate and like monomers are also particularly preferable for use in the present invention for the attachment of surface coatings. Medical devices and/or implants manufactured using compositions of the present invention comprising glycidyl methacrylate and/or like monomers, may be surface coated to alter the surface chemistry thereof if desired.
Compositions of the present invention are produced by polymerizing approximately 50 mol percent or more of a monomer or monomers from the first class of monomers with approximately 50 mol percent or less of a monomer or monomers from the second class of monomers in the presence of a αosslinker
and an initiator as described in more detail below. Optionally, a hydrophilic
II monomer may also be added during the polymerization of the compositions of the present invention to reduce or eliminate the formation of haze and/or
"glistenings".
Suitable compositions of the present invention include for example, but are not limited to poly(2-pheπylethyl acrylate-co-methyl methacrylate), poly(3- phenylpropyl acrylate-co-methyl methacrylate), poly(4-phenylbutyl acrylate-co- methyl methacrylate), poly(4-phenylbutyl methacrylate-co-methyl methacrylate), poly(5-phenylpentyl acrylate-co-methyl methacrylate), poly(5-phenylpentyl methacrylate-co-methyl methacrylate), poly(6-phenyl hexyl acrylate-co-methyl methacrylate), poly(6-phenylhexyl methacrylate-co-methyl methacrylate), poly(2- phenyloxyethyl acrylate-co-methyl methacrylate), poly(3-phenyloxypropyl acrylate-co-methyl methacrylate), poly(2-hydroxy-3-phenoxypropyl acrylate-co- methyl methacrylate), poly(4-phenyloxybutyl acrylate-co-methyl methacrylate), poly(4-phenyloxybutyl methacrylate-co-methyl methacrylate), poly(5- phenyloxypentyl acrylate-co-methyl methacrylate), poly(5-phenyloxypentyl methacrylate-co-methyl methacrylate), poly(6-phenyloxyhexyl acrylate-cg-methyl methacrylate), poly(6-phenyloxyhexyl methacrylate-co-methyl methacrylate), poly(2-phenylthioethyl acrylate-cg-methyl methacrylate), poly(3-phenylthiopropyl
acrylate-co-methyl methacrylate), poly(4-phenylthiobutyl acrylate-co-methyl methacrylate), poly(4- phenyithiobutyl methacrylate-co-methyl methacrylate), poly(5-phenylthiopentyl acrylate-co-methyl methacrylate), poly(5-phenylthiopentyl
methacrylate-co-methyl methacrylate), poly(6-phenyloxyhexyl acrylate-co-methyl methacrylate), poly(6-phenyloxyhexyl methacrylate-co-methyl methacrylate), l poly(2-aminophenylethyl acrylate-cg-methyl methacrylate), poly(3- aminopheny I propyl acrylate-cg-methyl methacrylate), poly(4-aminophenylbutyl
acrylate-co-methyl methacrylate), poly(4-aminophenylbutyl methacrylate-cg- methyl methacrylate), poly(5-aminophenylpentyl acrylate-cg-methyl methacrylate), poly(5-aminophenylpentyl methacrylate-cg-methyl methacrylate), poly(6-aminophenylhexyl acrylate-co-methyl methacrylate), poly(6- aminophenylhexyl methacrylate-cg-methyl methacrylate), poly[(N- methyl)aminophenylethyl acrylate-cg-methyl methacrylate], poly(2-naphthylethyl acrylate-cg-methyl methacrylate), poly(3-naphthylpropyl acrylate-cg-methyl methacrylate), poly(4-naphthylbutyl acrylate-cg-methyl methacrylate), poly(5- naphthylpentyl acrylate-cg-methyl methacrylate), poly(6-naphthylhexyl acrylate- cg-methyl methacrylate), poly(2-naphthyloxyethy1 acrylate-cg-methyl methacrylate), poly(3-naphthyloxypropyl acrylate-co-methyl methacrylate), poly(4-naphthyloxybutyl acrylate-cg-methyl methacrylate), poly(5- naphthyloxypentyl acrylate-cg-methyl methacrylate), poly(6-naphthyloxyhexyl acrylate-cg-methyl methacrylate), poly(2-naphthylthioethyl acrylate-cg-methyl methacrylate), poly(3-naphthylthiopropyl acrylate-cg-methyl methacrylate), poly(4-naphthylthiobutyl acrylate-cg-methyl methacrylate), poly(5-naphthylpentyl
acrylate-cg-methyl methacrylate), poly(6-naphthylhexyl acrylate-cg-methyl
methacrylate), poly[poly(ethylene oxide) phenyl ether acrylate-cg-methyl
methacrylate], poly[poly(ethylene oxide) phenyl ether methacrylate-cg-methyl
methacrylate], poly(poly(trimethylene oxide) phenyl ether acrylate-cg-methyl
methacrylate], poly[poly(trimethyiene oxide) phenyl ether methacrylate-cg-methyl methacrylate], poly{poly(ethylene sulfide) phenyl ether acrylate-cg-methyl methacrylate], poly[poly(ethylene sulfide) phenyl ether methacrylate-cg-methyl methacrylate], poly[poly(trimethylene sulfide) phenyl ether acrylate-cg-methyl methacrylate], poly(poly(trimethylene sulfide) phenyl ether methacrylate-cg- methyl methacrylate], poly[poly(propylene oxide) phenyl ether acrylate-c -methyl
methacrylate], poly[poly(propylene oxide) phenyl ether methacrylate-cg-methyl methacrylate], poly[poly(propylene sulfide) phenyl ether acrylate-cg-methyl methacrylate], polyfpoly(propylene sulfide) phenyl ether methacrylate-cg-methyl methacrylate], poly(2-phenylethyl acrylate-cg-ethyl methacrylate), poly(3- phenylpropyl acrylate-cg-ethyl methacrylate), poly(4-phenylbutyl acrylate-cg-ethyl methacrylate), poly(4-phenylbutyl methacrylate-cg-ethyl methacrylate), poly(5- phenylpentyl acrylate-cg-ethyl methacrylate), poly(5-phenylpentyl methacrylate- cg-ethyl methacrylate), poly(6-phenylhexyl acrylate-cg-ethyl methacrylate), poly(6-phenylhexyl methacrylate-cg-ethyl methacrylate), poly(2-phenyloxyethyl acrylate-cg-ethyl methacrylate), poly(3-phenyloxypropyl acrylate-cg-ethyl methacrylate), poiy(2-hydroxy-3-phenoxypropyl acrylate-co-ethyl methacrylate), poly(4-phenyloxybutyl acrylate-cg-ethyl methacrylate), poly(4-phenyloxybutyl methacrylate-cg-ethyl methacrylate), poly(5-phenyloxypentyl acrylate-cg-ethyl
methacrylate), poly(5-phenyloxypentyl methacrylate-co-ethyl methacrylate), poly(6-phenyloxyhexyl acrylate-cg-ethyl methacrylate), poly(6-phenyloxyhexyl me-hac-rylate-cg-ethyl methacrylate), poly(2-phenylthioethyl acrylate-co-ethyl
methacrylate), poly(3-phenylthiopropyl acrylate-cg-ethyl methacrylate), poly(4- phenylthiobutyl acrylate-cg-ethyl methacrylate), poly(4- phenylthiobutyl methacrylate-cg-ethyl methacrylate), poly(5-phenylthiopentyl acrylate-cg-ethyl methacrylate), poly(5-phenylthiopentyl methacrylate-cg-ethyl methacrylate),
poly(6-phenyloxyhexyl acrylate-cg-ethyl methacrylate), poly(6-phenyloxyhexyl methacrylate-cg-ethyl methacrylate), poly(2-aminophenylethyl acrylate-cg-ethyl methacrylate), poly(3-aminophenylpropyl acrylate-co-ethyl methacrylate), poly(4- aminophenylbutyl acrylate-cg-ethyl methacrylate), poly(4-aminophenylbutyl methacrylate-cg-ethyl methacrylate), poly(5-aminophenylpentyl acrylate-cg-ethyl methacrylate), poly(5-aminophenylpentyl methacrylate-cg-ethyl methacrylate), poly(6-aminophenylhexyl acrylate-co-ethyl methacrylate), poly(6- amiπophenylhexyl methacrylate-cg-ethyl methacrylate), poly[(N- methyl)aminophenylethyl acrylate-cg-ethyl methacrylate], poly(2-naphthylethyl acrylate-cg-ethyl methacrylate), poly(3-naphthylpropyl acrylate-cg-ethyl methacrylate), poiy(4-naphthylbutyl acrylate-cg-ethyl methacrylate), poly(5- naphthylpentyl acrylate-cg-ethyl methacrylate), poly(6-naphthylhexyl acrylate-co- ethyl methacrylate), poly(2-naphthyloxyethyl acrylate-cg-ethyl methacrylate), poly(3-naphthyloxypropyl acrylate-cg-ethyl methacrylate), poly(4- naphthyloxybutyl acrylate-cg-ethyl methacrylate), poly(5-naphthyloxypentyl acrylate-cg-ethyl methacrylate), poly(6-naphthyloxyhexyl acrylate-cg-ethyl
methacrylate), poly(2-naphthylthioethyl acrylate-cg-ethyl methacrylate), poly(3- naphthylthiopropyf acrylate-cg-ethyl methacrylate), poly(4-naphthylthiobutyl
acrylate-cg-ethyl methacrylate), poly(5-naphthylpentyl acrylate-co-ethyl methacrylate), poly(6-naphthylhexyl acrylate-cg-ethyl methacrylate),
poly[poly(ethylene oxide) phenyl ether acrylate-co-ethyl methacrylate],
IS poly[poly(ethylene oxide) phenyl ether methacrylate-cg-ethyl methacrylate], poly[poly(trimethylene oxide) phenyl ether acrylate-cg-ethyl methacrylate], poly[poly(trimethylene oxide) phenyl ether methacrylate-cg-ethyl methacrylate], poly[poly(ethylene sulfide) phenyl ether acrylate-cg-ethyl methacrylate],
poly[poly(ethylene sulfide) phenyl ether methacrylate-cg-ethyl methacrylate], poly[poly(trimethylene sulfide) phenyl ether acrylate-cg-ethyl methacrylate], poly[poly(trimethylene sulfide) phenyl ether methacrylate-cg-ethyl methacrylate], poly[poly(propylene oxide) phenyl ether acrylate-cg-ethyl methacrylate], poly[poly(propylene oxide) phenyl ether methacrylate-cg-ethyl methacrylate], poly[poly(propylene sulfide) phenyl ether acrylate-cg-ethyl methacrylate], poly[poly(propylene sulfide) phenyl ether methacrylate-cg-ethyl methacrylate], poly(2-phenylethyl acrylate-cg-isopropyl methacrylate), poly(3-phenylpropyl acrylate-cg-isopropyl methacrylate), poly(4-phenyl butyl acrylate-cg-isopropyl methacrylate), poly(4-phenylbutyl methacrylate-cg-isopropyl methacrylate), poly(5-phenylpentyl acrylate-cg-isopropyl methacrylate), poly(5-phenylpentyl methacrylate-cg-isopropyl methacrylate), poly(6-phenylhexyl acrylate-cg- isopropyl methacrylate), poly(6-phenylhexyl methacrylate-cg-isopropyl methacrylate), poly(2-phenyloxyethyl acrylate-cg-isopropyl methacrylate), poly(3-
phenyloxypropyl acrylate-cg-isopropyl methacrylate), poly(2-hydroxy-3-
phenoxypropyl acrylate-cg-isopropyl methacrylate), poly(4-phenyloxybutyl acrylate-cg-isopropyl methacrylate), poly(4-phenyloxybutyl methacrylate-cg-
isopropyl methacrylate), poly(5-phenyloxypentyl acrylate-cg-isopropyl
methacrylate), poly(5-phenyloxypentyl methacrylate-cg-isopropyl methacrylate), poly(6-phenyloxyhexyl acrylate-cg-isopropyl methacrylate), poly(6-
phenyloxyhexyl methacrylate-co-isopropyl methacrylate), poly(2-phenylthioethyl acrylate-cg-isopropyl methacrylate), poly(3-phenylthiopropyl acrylate-cg-isopropyl methacrylate), poly(4-phenylthiobutyl acrylate-cg-isopropyl methacrylate), poly(4- phenylthiobutyl methacrylate-cg-isopropyl methacrylate), poly(5-phenylthiopentyl acrylate-co-isopropyl methacrylate), poly(5-phenylthiopentyl methacrylate-co- isopropyl methacrylate), poly(6-phenyloxyhexyl acrylate-cg-isopropyl methacrylate), poly(6-phenyloxyhexyl methacrylate-cg-isopropyl methacrylate), poly(2-aminophenylethyl acrylate-cg-isopropyl methacrylate), poly(3- aminophenylpropyl acrylate-co-isopropyl methacrylate), poly(4-aminophenylbutyl acrylate-c -isopropyl methacrylate), poly(4-aminophenylbutyl methacrylate-cg- isopropyl methacrylate), poly(5-aminophenylpentyl acrylate-cg-isopropyl methacrylate), poly(5-aminophenylpentyl methacrylate-cg-isopropyl methacrylate), poly(6-aminophenylhexyl acrylate-cg-isopropyl methacrylate), poly(6-aminophenylhexyl methacrylate-cg-isopropyl methacrylate), poly[(N- methyl)aminophenylethyl acrylate-cg-isopropyl methacrylate], poly(2- naphthylethyl acrylate-cgHsopropyl methacrylate), poly(3-naphthylpropyl acrylate- co-isopropyl methacrylate), poly(4-naphthylbutyl acrylate-cg-isopropyl
methacrylate), poly(5-naphthylpentyl acrylate-cg-isopropyl methacrylate), poly(6- naphthylhexyl acrylate-cg-isopropyl methacrylate), poly(2-naphthyloxyethyl acrylate-cg-isopropyl methacrylate), poly(3-naphthyloxypropyl acrylate-cg- isopropyl methacrylate), poly(4-naphthyloxybutyl acrylate-c -isopropyl
methacrylate), poly(5-naphthyloxypentyl acrylate-cg-isopropyl methacrylate), n poly(6-naphthyloxyhexyl acrylate-cg-isopropyl methacrylate), poly(2- naphthylthioethyl acrylate-cg-isopropyl methacrylate), poly(3-naphthylthiopropyl
acrylate-cg-isopropyl methacrylate), poly(4-naphthylthiobutyl acrylate-cg- isopropyl methacrylate), poly(5-naphthylpentyl acrylate-cg-isopropyl methacrylate), poly(6-naphthylhexyl acrylate-cg-isopropyl methacrylate), poly[poly(ethylene oxide) phenyl ether acrylate-cg-isopropyl methacrylate], poly[poly(ethylene oxide) phenyl ether methacrylate-cg-isopropyl methacrylate], poly[poly(trimethylene oxide) phenyl ether acrylate-cg-isopropyl methacrylate], poly[poly(trimethylene oxide) phenyl ether methacrylate-cg-isopropyl methacrylate], poly[poly{ethylene sulfide) phenyl ether acrylate-co-isopropyl methacrylate], poly poly(ethylene sulfide) phenyl ether methacrylate], poly[poly(trimethylene sulfide) phenyl ether acrylate-cg-isopropyl methacrylate], poly[poly(trimethylene sulfide) phenyl ether methacrylate-cg-isopropyl methacrylate], poly[poly(propylene oxide) phenyl ether acrylate-cg-isopropyl methacrylate], poly[poly(propylene oxide) phenyl ether methacrylate-co-isopropyl methacrylate], poly poly(propylene sulfide) phenyl ether acrylate-cg-isopropyl methacrylate], poly[poly(propylene sulfide) phenyl ether methacrylate-cg- isopropyl methacrylate], poly(2-phenylethyl acrylate-cg-t-butyl methacrylate),
poly(3-phenylpropyl acrylate-cg-t-butyl methacrylate), poly(4-phenylbutyl acrylate-cg-t-butyl methacrylate), poly(4-phenylbutyl methacrylate-cg-t-butyl methacrylate), poly(5-phenylpentyl acrylate-cg-t-butyl methacrylate), poly(5- phenylpentyl methacrylate-cg-t-butyl methacrylate), poly(6-phenylhexyl acrylate-
cg-t-butyl methacrylate), poly(6-phenylhexyl methacrylate-cg-t-butyl methacrylate), poly(2-phenyloxyethyl acrylate-cg-t-butyl methacrylate), poly(3-
phenyloxypropyl acrylate-cg-t-butyl methacrylate), poly(2-hydroxy-3-
phenoxypropyl acrylate-cg-t-butyl methacrylate), poly(4-phenyloxybutyl acrylate- cg-t-butyl methacrylate), poly(4-phenyloxybutyl methacrylate-cg-t-butyl methacrylate), poly(5-phenyloxypentyl acrylate-cg-t-butyl methacrylate), poly(5- phenyloxypentyl methacrylate-cg-t-butyl methacrylate), poly(6-phenyloxyhexyl acrylate-cg-t-butyl methacrylate), poiy(6-phenyloxyhexyl methacrylate-cg-t-butyl methacrylate), poly(2-phenylthioethyl acrylate-cg-t-butyl methacrylate), poly(3- phenylthiopropyi acrylate-cg-t-butyl methacrylate), poly(4-phenylthiobutyl acrylate-cg-t-butyl methacrylate), poly(4- phenylthiobutyl methacrylate-cg-t-butyl methacrylate), poly(5-phenylthiopentyl acrylate-cg-t-butyl methacrylate), poly(5- phenylthiopentyl methacrylate-cg-t-butyl methacrylate), poly(6-phenyloxyhexyl acrylate-cg-t-butyl methacrylate), poly(6-phenyloxyhexyl methacrylate-cg-t-butyl methacrylate), poly(2-aminophenylethyl acrylate-cg-t-butyl methacrylate), poly(3- aminophenylpropyl acrylate-co-t-butyl methacrylate), poly(4-aminophenylbutyl acrylate-cg-t-butyl methacrylate), poly(4-aminophenylbutyl methacrylate-cg-t- butyl methacrylate), poly(5-aminophenylpentyl acrylate-cg-t-butyl methacrylate), poly(5-aminophenylpentyl methacrylate-cg-t-butyl methacrylate), poly(6- aminophenylhexyl acrylate-cg-t-butyl methacrylate), poly(6-aminophenylhexyl
methacrylate-cg-t-butyl methacrylate), poly[(N-methyl)aminophenylethyl acrylate-
cg-t-butyl methacrylate], poly(2-naphthylethyl acrylate-cg-t-butyl methacrylate), poly(3-naphthylpropyl acrylate-cg-t-butyl methacryiate), poly(4-naphthylbutyl
acrylate-co-t-butyl methacrylate), poly(5-naphthylpentyl acrylate-cg-t-butyl
/ methacrylate), poly(6-naphthylhexyl acrylate-cg-t-butyl methacrylate), poly(2- naphthyloxyethyl acrylate-cg-t-butyl methacrylate), poly(3-naphthyloxypropyl
acrylate-cg-t-butyl methacrylate), poly(4-naphthyloxybutyl acrylate-cg-t-butyl methacrylate), poly(5-naphthyloxypentyl acrylate-cg-t-butyl methacrylate), poly(6- naphthyloxyhexyl acrylate-cg-t-butyl methacrylate), poly(2-naphthylthioethyl acrylate-cg-t-butyl methacrylate), poiy(3-naphthylthiopropyl acrylate-cg-t-butyl methacrylate), poly(4-naphthylthiobutyl acrylate-cg-t-butyl methacrylate), poly(5- naphthylpentyl acrylate-cg-t-butyl methacrylate), poly(6-naρhthylhexyl acrylate- cg-t-butyl methacrylate), poly[poly(ethylene oxide) phenyl ether acrylate-cg-t- butyl methacrylate], poly[poly(ethylene oxide) phenyl ether methacrylate-cg-t- butyl methacrylate], poly[poly(trimethylene oxide) phenyl ether acrylate-cg-t-butyl methacrylate], poly[poly(trime-hylene oxide) phenyl ether methacrylate-cg-t-butyl methacrylate], polyfpoly(ethylene sulfide) phenyl ether acrylate-cg-t-butyl methacrylate], poly{poly(ethylene sulfide) phenyl ether methacrylate-cg-t-butyl methacrylate], poly[poly(trimethylene sulfide) phenyl ether acrylate-cg-t-butyl methacrylate], poly(poly(trimethylene sulfide) phenyl ether methacrylate-cg-t- butyl methacrylate], poly[poly(propylene oxide) phenyl ether acrylate-cg-t-butyl methacrylate], poly[poly(propylene oxide) phenyl ether methacrylate-cg-t-butyl methacrylate], poly[poly(propylene sulfide) phenyl ether acrylate-cg-t-butyl
methacrylate], poly[poly(propylene sulfide) phenyl ether methacrylate-cg-t-butyl
methacrylate], poly(2-phenylethyl acrylate-cg-glycidyl methacrylate), poly(3- phenylpropyl acrylate-cg-glycidyl methacrylate), poly(4-phenylbutyl acrylate-cg-
glycidyl methacrylate), poly (4-phenylbutyl methacrylate-cg-glycidyl methacrylate), poly(5-phenylpentyl acrylate-cg-glycidyl methacrylate), poly(5-phenylpentyl methacrylate-cg-glycidyl methacrylate), poly(6-phenylhexyl acrylate-cg-glycidyl methacrylate), poly(6-phenylhexyl methacrylate-cg-glycidyl methacrylate) , poly(2-phenyloxyethyl acrylate-cg-glycidyl methacrylate), poly(3-phenyloxypropyl acrylate-co-glycidyl methacrylate), poly(2-hydroxy-3-phenoxypropyl acrylate-cg- glycidyl methacrylate), poiy(4-phenyloxybutyl acrylate-gg-glycidyl methacrylate), poly(4-phenyloxybutyl methacrylate-cg-glycidyl methacrylate), poly(5- phenyloxypentyl acrylate-cg-glycidyl methacrylate), poly(5-phenyloxypentyl methacrylate-cg-glycidyl methacrylate), poly(6-phenyloxyhexyl acrylate-cg- glycidyl methacrylate), poly(6-phenyloxyhexyl methacrylate-cg-glycidyl methacrylate), poly(2-phenylthioethyl acrylate-cg-glycidyl methacrylate), poly(3- phenylthiopropyl acrylate-cg-glycidyl methacrylate), poly(4-phenylthiobutyl acrylate-cg-glycidyl methacrylate), poly (4- phenylthiobutyl methacrylate-cg- glycidyl methacrylate), poly(5-phenylthiopentyl acrylate-cg-glycidyl methacrylate), poly(5-phenylthiopentyl methacrylate-cg-glycidyl methacrylate), poly(6- phenyloxyhexyl acrylate-cg-glycidyl methacrylate), poly(6-phenyloxyhexyl methacrylate-cg-glycidyl methacrylate), poly(2-aminophenylethyl acrylate-cg- glycidyl methacrylate), poly(3-aminophenylpropyl acrylate-cg-glycidyl methacrylate), poly(4-aminophenylbutyl acrylate-co-glycidyl methacrylate), poly(4-aminophenylbutyl methacrylate-cg-glycidyl methacrylate), poly(5- a inophenylpentyl acrylate-cg-glycidyl methacrylate), poly(5-aminophenylpentyl methacrylate-cg-glycidyl methacrylate), poly(6-aminophenylhexyl acrylate-cg- glycidyl methacrylate), poly(6-aminophenylhexyl methacrylate-cg-glycidyl methacrylate), poly[(N-methyl)aminophenylethyl acrylate-co-glycidyl
methacrylate], poly(2-naphthylethyl acrylate-cg-glycidyl methacrylate), poly(3-
naphthylpropyl acrylate-cg-glycidyl methacrylate), poly(4-naphthylbutyl acrylate- cg-glycidyl methacrylate), poly(5-naphthylpentyl acrylate-co-glycidyl methacrylate), poly(6-naphthylhexyl acrylate-cg-glycidyl methacrylate), poly(2- naphthyloxyethyl acrylate-cg-glycidyl methacrylate), poly(3-naphthyloxypropyl acrylate-c -glycidyl methacrylate), poly(4-naphthyloxybutyl acrylate-cg-glycidyl methacrylate), poly(5-naphthyloxypentyl acrylate-cg-glycidyl methacrylate), poly(6-naphthyloxyhexyl acrylate-cg-glycidyl methacrylate), poly(2- naphthylthioethyl acrylate-cg-glycidyl methacrylate), poly(3-naphthylthiopropyl acrylate-cg-glycidyl methacrylate), poly(4-naphthylthiobutyl acrylate-co-glycidyl methacrylate), poly(5-naphthylpentyl acrylate-cg-glyddyl methacrylate), poly(6- naphthylhexyl acrylate-cg-glycidyl methacrylate), poly[poly(ethylene oxide) phenyl ether acrylate-cg-glycidyl methacrylate], poly[poly(ethylene oxide) phenyl ether methacrylate-cg-glycidyl methacrylate], poly[poly(trimethylene oxide) phenyl ether acrylate-co-glycidyl methacrylate], poly[poly(trimethylene oxide) phenyl ether methacrylate-cg-glycidyl methacrylate], poly[poly(ethylene sulfide) phenyl ether acrylate-co-glycidyl methacrylate], poly[poly(ethylene sulfide) phenyl ether methacrylate-cg-glycidyl methacrylate], poly[poly(trimethylene sulfide)
phenyl ether acrylate-cg-glycidyl methacrylate], poly[poly(trimethylene sulfide)
phenyl ether methacrylate-cg-glycidyl methacrylate], poly[poly(propylene oxide) phenyl ether acrylate-cg-glycidyl methacrylate], poly[poly(propylene oxide)
phenyl ether methacrylate-cg-glycidyl methacrylate], poly[poly(propylene sulfide) phenyl ether acrylate-co-glycidyl methacrylate], poly(poly(propylene sulfide)
phenyl ether methacrylate-cg-glycidyl methacrylate), poly(2-phenyloxyethyl acrylate-cg-methyl methacrylate-cg-ethyl methacrylate), poiy(2-phenylethyl acrylate-cg-methyl methacrylate-cg-glycidyl methacrylate) and poly(2- phenylthioethyl acrylate-cg-methyl methacrylate-cg-glycidyl methacrylate).
Preferred compositions of the present invention include poly(2-phenylethyl acrylate-gg-methyl methacrylate), poly(2-phenylethyl acrylate-cg-methyl methacrylate-cg-glycidyl methacrylate), poly(2-phenylthioethyl acrylate-cg-methyl methacrylate), poly(2-phenyloxyethyl acrylate-cg-methyl methacrylate), poly(2- phenyloxyethyl acrylate-cg-methyl methacrylate-cg-ethyl methacrylate) and poly(phenylthioethyl acrylate-cg-methyl methacrylate-cg-glycidyl methacrylate).
The compositions of the present invention unexpectedly have high refractive indexes and low glass transition temperatures. One reason such material characteristics are unexpected is due to the relatively low refractive index and relatively high glass transition temperature of a major component thereof, i.e., the second class of monomers. The compositions of the present invention with their high refractive indexes and low glass transition temperatures are desirable for use in the manufacture thinner lOLs.
A thin IOL or an IOL having a thin optic is critical in enabling a surgeon to minimize incision size. Keeping the surgical incision size to a minimum reduces
intraoperative trauma and postoperative complications. A thin IOL is also αitical
for accommodating certain anatomical locations in the eye such as the anterior
chamber and the ciliary sulcus. lOLs may be placed in the anterior chamber for
>3 inαeasing visual acuity in both aphakic and phakic eyes and placed in the ciliary sulcus for inαeasing visual acuity in phakic eyes.
The preferred materials of the present invention also have the flexibility
required to allow implants manufactured from the same to be folded or deformed so as to be introduced into an eye through the smallest possible incision. As noted above, to achieve this flexibility characteristic, the glass transition temperature (Tg) of the material is of considerable importance. A glass transition temperature of approximately 20 degrees Celsius or less measured by differential scanning calorimetry at approximately 10 degrees Celsius per minute and determined at the midpoint of the transition of the heat flux curve, must be achieved in the subject materials to be acceptable for purposes of desirable folding of the implant . It is also unexpected that materials could be synthesized as described herein to have the desired high refractive index and low glass transition temperature because many high refractive index monomers have bulky side-chains which restrict chain mobility and drastically inαease the overall glass transition temperature of the copolymer. As a general rule, aαylates produce polymers with lower glass transition temperatures than the corresponding methacrylates and are therefor preferred for use as a monomer from the first class of monomers.
Suitable αosslinkers for use in producing the subject compositions include
for example but are not limited to ethylene glycol dimethacrylate, diethylene
glycol dimethacrylate, triethylene glycol dimethacrylate and poiy(ethylene glycol) dimethacrylate wherein ethylene glycol dimethacrylate is preferred. Suitable initiators for use in producing the subject compositions include for example but are not limited to 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4- dimethylvaleronitrile), 2,2'-azobis(methylbutyronitrile), 1 ,1'- azobis(cyanocyclohexane), di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoyl peroxy)hexane, t-butyl peroxyneodecanote, t-butyl peroxy 2-ethylhexanoate, di(4-t-butyl cyclohexyl) peroxydicarbonate, t-butyl peroxypivalate, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-pentanedione peroxide, di(n-propyl) peroxydicarbonate, t- amyl peroxyneodecanoate and t-butyl peroxyacetate wherein 2,2'- azobis(isobutyronitrile) is preferred.
Suitable ultraviolet light absorbers which may optionally be used in the manufacture of the subject compositions include for example but are not limited to beta-(4-benzotriazoyl-3-hyd-Oxyphenoxy) ethyl acrylate, 4-(2-aαyloxyethoxy)- 2-hydroxybenzophenone, 4-methacryloxy-2-hydroxybenzophenone, 2-{2'- metha---ryloxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'- methacryoxyethylphenyl)-2H-benzotriazole, 2-{3'-tert-Butyl-2'-hydroxy-5'-(3''- methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-(3'-te^t-Butyl-5'-(3,,- dimethylvinylsilylpropoxy)-2'-hydroxyphenyl]-5-methoxybenzotriazole, 2-(3'-Allyl- 2'-hydroxy-5'-methylphenyl)benzotriazole, 2-f3'-tert-Butyl-2'-hydroxy-5'-
(3"methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole, and 2-t3'-tert-Butyl-
2'-hydroxy-5'-{3,'-methacryloyloxypropoxy)phenyl]-5-chlorober-zotriazole wherein beta-(4-benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate is the preferred ultraviolet light absorber. f The subject compositions having a refractive index of approximately 1.50 or greater and a glass transition temperature of approximately 20 degrees Celsius or less are described in still greater detail in the examples that follow.
EXAMPLE 1- Compositions of PEA/M A:
Inhibitor-free 2-phenylethyl acrylate (PEA) and methyl methacrylate (MMA) containing 10 parts per million (ppm) methoxyhydroquinone (MEHQ) were combined in the molar ratios tabulated below. Ethylene glycol dimethacrylate (EGDMA) was added in the amount of 0.5 mol % based on total moles of PEA and MMA. 2,2,-Azobis(isobutyronitrile) (AIBN) and 1,1'-azobis(1- cyclohexanecarbonitrile) (V-40) were added in the amounts of 0.05 mol percent each based on total moles of PEA, MMA and EGDMA.
Each solution was cast between glass plates covered with Bytac™ film (Norton, Akron, Ohio) having a 1/16 inch gasket of Buna-N™ nitrile rubber (McMaster-Carr, Chicago, Illinois) rubber to separate the plates. The molds were
cured in an 80 °C oven for 3.5 hours, followed by a 120 °C post-cure for 21.5
hours. Rectangular test pieces were removed from each cured sheet and extracted in acetone at room temperature to remove residual monomers. After air-drying at room temperature for several hours, the test pieces were heated in
an oven at 60 °C for 24 hours to remove residual acetone. The refractive index
of each composition was measured on an Abbe Mark™ II refractometer (Reichert-Jung, Model 10480, Reichert Scientific Instruments, Buffalo, NY) at
ambient temperature. The samples were subsequently held at 37 °C in balanced salt solution (BSS) and the refractive index of each composition was re- determined. The equilibrium water content (EWC) was determined by [mass of water in the polymer / mass of water-swollen polymer] X 100.
PEA/MMA, mol/mol Rl (post-extrπ) RK37 °C. BSS) EWC (37 °C. BSS)
100/0 1.551 1.550 1.2%
90/10 1.547 1.546 1.0%
80/20 1.544 1.543 1.3%
70/30 1.540 1.538 1.7%
60/40 1.535 1.534 1.2%
50/50 1.522 1.527 1.4%
EXAMPLE 2- Compositions of PEA/MMA/GMA - 0.5 mol% EGDMA:
A second series of polymer sheets were prepared holding the αosslinker level constant at 0.5 mol% EGDMA based on total moles of PEA, MMA and glycidyl methacrylate (GMA). A combination of free radical initiators, i.e., AIBN
(0.075 mol%) and V-40 (0.025 mol%) were used. Oven cure conditions were 60
°C for 18 hours and 115 °C for 24 hours. Tensile bars conforming to American
Society for Testing and Materials (ASTM) D 1708-84 were stamped from each
demolded sheet and extracted with acetone per Example 1. The dried tensile
specimens were parted on an Instron™ Model 4501 material testing system (Instron, Corporation, Canton, MA) under ambient conditions at a αosshead speed of 1 inch/minute. Refractive index measurements were made at room temperature in air and after exposure to balanced salt solution (BSS) for 7 days
at 37 °C. The equilibrium water contents (EWCs) of the samples were
determined gravimetrically as desαibed in Example 1 above.
PEA/MMA/GMA (mol/mol/mol.
Property 95/4/1 90/9/1 85/14/1 80/19/1
Tensile strength, psi 127 ± 43 204 ± 43 212 ± 29 215 ± 32
Elongation @ break, % 527 ± 71 546 ± 50 542 ± 28 490 ± 26
Initial modulus, psi 33 ± 5 38 + 6 37 ± 4 44 ± 8
Toughness, psi 237 ± 75 436 ± 88 389 ± 57 351 ± 55
Rl (post-acetone extrn) 1.549 1.548 1.546 1.544
RI (37 °C, BSS) 1.549 1.547 1.546 1.543
EWC (37 °C, BSS) 0.6% 0.6% 0.7% 0.6%
EXAMPLE 3- Compositions of PEA/MMA/GMA - 90/9/1:
A third set of sheets was prepared in the same manner as Example 2
holding the molar ratio of PEA/MMA/GMA at 90/9/1, while varying the amount of EGDMA from 1.0 mol% to 3.0 mol% based on total moles of PEA, MMA and GMA Tensile properties, refractive index and equilibrium water content were
determined as in Example 2.
Mol% EGDMA
Property 1.0 1.5 2.0 2.5 3.0
Tensile strength, psi 202 ±43 183 ±43 185 ±39 207 ±37 209 ±26
Elongation @ break, % 358 + 27 268 + 28 212 + 22 180 ±14 151 ±14
Initial modulus, psi 63 ±10 72 ±5 94 ±11 117 ±11 141 ±10
Toughness, psi 294 ±52 213 ±46 171 ±38 161 ±31 141 ±20
Rl (post-acetone extrn) 1.549 1.549 1.549 1.549 1.549 RI(37°C, BSS) 1.547 1.547 1.547 1.547 1.547
EWC (37 °C, BSS) 0.4% 0.4% 0.4% 0.4% 0.5%
EXAMPLE 4- Compositions of PTEA/MMA:
Inhibitor-free phenylthioethyl acrylate (PTEA) and MMA were combined with 0.5 mol% EGDMA and 0.075 mol% AIBN and 0.025 mol% V-A0 in the manner of Example 1. PTEA/MMA (mol/mol) Rl (post-extm) Rl (37 °C. BSS) EWC (37 °C. BSS)
100/0 1.595 1.595 0.4%
90/10 1.590 1.589 0.5%
80/20 1.584 1.583 0.5%
70/30 1.577 1.577 0.6%
60/40 1.571 1.570 0.7%
EXAMPLE 5- Compositions of PTEA/MMA/GMA- 0.5 mol% EGDMA:
A series of PTEA/MMA/GMA sheets were cast holding the EGDMA level constant at 0.5 mol% per Example 2. AIBN (0.1 mol%) was used to initiate cure
(60 °C, 18 hours; 115 °C, 24 hours). Testing was performed as described in
-Example 2.
2- 0 PTEA MMA/GMA (mol/mol/mol)
Property 95/4/1 90/9/1 85/14/1 80/19/1 75/24/1
Tensile strength, psi 64 ± 17 86 ± 15 88 ± 24 153 ± 26 209 ± 15
Elongation@break,% 368 ± 54 415 ± 27 371 ± 43 412 ± 37 446 ± 15
Initial modulus, psi 26 ± 3 28 ± 3 32 ± 3 42 ± 5 51 ± 5
Toughness, psi 111 ± 32 156 ± 27 146 ± 41 297 ± 49 391 ± 28
Rl (post-acetone extrn) 1.593 1.591 1.588 1.585 1.581
RI(37 °C, BSS) 1.592 1.589 1.586 1.583 1.580
EWC (37 °C, BSS) 0.5% 0.5% 0.6% 0.6% 0.6%
EXAMPLE 6- Compositions of PTEA/MMA/GMA - 90/9/1 :
A series of PTEA/MMA/GMA sheets were cast at a molar ratio of 90/9/1 while varying the EDGMA content between 1.0 and 3.0%. The castings were cured, extracted and tested in the manner of Example 5. Mol% EGDMA
Property 10 5 0 2,5 3 )
Tensile strength, psi 105+20 100+9 90+6 91 +6 100+12
Elongation @ break, % 244+41 175+18 125+17 101 +7 86+9
Initial modulus, psi 51+2 63+4 82+4 97+8 121+8
Toughness, psi 148+42 103+16 70+8 57+6 52+10
Rl (post-acetone extrn) 1.590 1.590 1.590 1.590 1.590
RI (37 °C, BSS) 1.589 1.589 1.588 1.588 1.588
EWC (37 °C, BSS) 0.4 0.4 0.5 0.5 0.5
lOLs manufactured using the compositions of the present invention can be of any design capable of being rolled or folded into a small αoss section that can fit through a relatively small incision, i.e., 4.0 mm or less. For example, lOLs can be of a one-piece or multipiece design, and comprise optic and haptic portions. The optic portion is that portion which serves as the lens and the haptic portions are attached to the optic portion to hold the optic portion in proper alignment within an eye. The haptic portions may be integrally formed with the optic
portion in a one-piece design or attached by staking, adhesives or other methods known to those skilled in the art in a multipiece design.
The subject lOLs may be manufactured to have the optic portion and the
haptic portions made of the same or different materials. Preferably, in
accordance with the present invention, the optic portion and the haptic portions are made of the same high-refractive index, low glass transition temperature composition. However, the optic portion and the haptic portions may also be manufactured from different compositions and/or different formulations of the same composition as desαibed in detail in U.S. Patent Numbers 5, 217,491 and 5,326,506, each incorporated herein in their entirety by reference. Once the particular composition is selected, the material is either cast in molds of the desired shape or cast in the form of rods and lathed into disks. These disks are then machined at low temperatures below the glass transition temperature into lOLs. The lOLs whether molded or machined are then cleaned, polished, packaged and sterilized by customary methods known to those skilled in the art.
In addition to lOLs, the materials of the present invention are also suitable for use as other ophthalmic devices such as contact lenses, keratoprostheses, capsular bag extension rings, comeal inlays, corneal rings or like devices. lOLs manufactured using the unique materials of the present invention are used as customary in the field of ophthalmology. In a surgical procedure, an incision is placed in the cornea of an eye, most commonly the natural lens of the eye is removed and the IOL manufactured from materials of the present invention is inserted into the posterior chamber or lens capsule of the eye prior to closing
the incision.
While there is shown and desαibed herein certain specific structures and compositions of the present invention, it will be manifest to those skilled in the art
that various modifications may be made without departing from the spirit and
scope of the underlying inventive concept and that the same is not limited to particular structures herein shown and desαibed except insofar as indicated by the scope of the appended claims.
1

Claims

I claim:
1. A composition comprising: a high refractive index, low glass transition temperature monomer; a low refractive index, high glass transition temperature monomer; a αosslinker, and an initiator; whereby said composition has a refractive index of approximately 1.50 or greater and a glass transition temperature of approximately 20 degrees
Celsius or lower.
2. The composition of claim 1 wherein said composition includes an ultraviolet light absorbing material.
3. The composition of claim 1 wherein said composition includes an ultraviolet light absorbing material selected from the group consisting of beta-(4- benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate, 4-(2-acryloxyethoxy)-2- hydroxybenzophenone, 4-methaαyloxy-2-hydroxybenzophenone, 2-(2'-
methaαyloxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'- methaαyoxyethylphenyl)-2H-benzotriazole, 2-[3,-tert-Butyl-2'-hydroxy-5'-(3''-
methacyloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-(3'-tert-Butyl-5,-{3-
dimethylvinylsilylpropoxy)-2'-hydroxyphenyl]-5-methoxybenzotriazole, 2-{3'- Allyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[3'-tert-Butyl-2'-hydroxy-5'- (3"-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole and 2-[3'-tert-
Butyl-2'-hydroxy-5'-(3"-methacryloyloxypropoxy)phenyl]-5- chlorobenzotriazole.
4. The composition of claim 1 wherein said composition includes beta-(4- benzotriazoyl-3-hydroxyphenoxy) ethyl acrylate as an ultraviolet light absorbing material.
5. The composition of claim 1 wherein said initiator is selected from the group consisting of 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4- dimethylvaleronitrile), 2,2'-azobis(methylbutyronitrile), 1,1'- azobis(cyanocyclohexane), di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t- butylperoxyneodecanote, t-butyl peroxy 2-ethylhexanoate, di(4-t-butyl cyclohexyl) peroxydicarbonate, t-butyl peroxypivalate, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-pentanedione peroxide, di(n- propyl)peroxydicarbonate, t-amyl peroxyneodecanoate and t-butyl peroxyacetate.
6. The composition of claim 1 wherein said initiator is 2,2'- azobis(isobutyronitrile).
7. The composition of claim 1 wherein said αosslinker is selected from the
group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and poly(ethylene glycol) dimethacrylate.
8. The composition of claim 1 wherein said αosslinker is ethylene glycol dimethacrylate.
9. The composition of claim 1 wherein said high refractive index, low glass transition temperature monomer has a structure represented by one of the formulas
O
II
Figure imgf000038_0001
Figure imgf000038_0002
c
//
Figure imgf000038_0003
C
? o
II
R, C C 0- [CH2CH(0H)CH2F-4]p Ar , or
C
O
/I
Rl c c o- [CH2CH(CH3)R ]P Ar
W
wherein Ri is selected from the group consisting of hydrogen and C1-12 alkyl; R2 is selected from the group consisting of oxygen, sulfur and NR3; R3 is selected from the group consisting of hydrogen and C1-6 alkyl; R* is selected from the group consisting of oxygen and sulfur; Ar is selected from the group consisting of C&-36 aryl and Cs-3β substituted aryl wherein one or more carbons are substituted with the same or different substituents selected from the group
consisting of halogens, C.-β alkyl, C1-6 alkoxy, Cs-25 aryl and Cβ-25 substituted aryl containing nitrogen or sulfur; n is an integer greater than or equal to 2; m is an integer greater than 1 and less than 5; and p is an integer greater than or equal to 1 ; whereby the homopolymer formed from the selected monomer has a glass
transition temperature of approximately 20 degrees Celsius or less and a
refractive index of approximately 1.50 or greater.
0. The composition of claim 1 wherein said high refractive index, low glass transition temperature monomer is selected from the group consisting of 2- phenylethyl acrylate, 3-phenylpropyl acrylate, 4-phenylbutyl acrylate, 4- phenylbutyl methacrylate, 5-phenylpentyl acrylate, 5-phenylpentyl methacrylate, 6-phenylhexyl acrylate, 6-phenylhexyl methacrylate, 2- phenyloxyethyl acrylate, 3-phenyloxypropyl acrylate, 2-hydroxy-3- phenoxypropyl acrylate, 4-phenyloxybutyl aαylate, 4-phenyloxybutyl methacrylate, 5-phenyloxypentyl acrylate, 5-phenyloxypentyl methacrylate, 6- phenyloxyhexyl acrylate, 6-phenyloxyhexyl methacrylate, 2-phenylthioethyl acrylate, 3-phenylthiopropyl acrylate, 4-phenylthiobutyl aαylate, 4- phenylthiobutyl methacrylate, 5-phenylthiopentyl aαylate, 5-phenylthiopentyl methacrylate, 6-phenyloxyhexyl acrylate, 6-phenyloxyhexyl methacrylate, 2- aminophenylethyl acrylate, 3-aminophenylpropyl acrylate, 4-aminophenylbutyl acrylate, 4-aminophenylbutyl methacrylate, 5-aminophenylpentyl acrylate, 5- aminophenylpentyl methacrylate, 6-aminophenylhexyl aαylate, 6- aminophenylhexyl methacrylate, (N-methyl)aminophenylethyl acrylate, 2- naphthylethyl acrylate, 3-naphthylpropyl acrylate, 4-naphthylbutyl acrylate, 5- naphthylpentyl acrylate, 6-naphthylhexyl acrylate, 2-naphthyloxyethyl acrylate, 3-naphthyloxypropyl acrylate, 4-naphthyloxybutyl acrylate, 5- naphthyloxypentyl acrylate, 6-naphthyloxyhexyl acrylate, 2-naphthylthioethyl
acrylate, 3-naphthylthiopropyl acrylate, 4-naphthylthiobutyl acrylate, 5-
naphthylpentyl acrylate, 6-naphthylhexyl acrylate, poly(ethylene oxide) phenyl
ether acrylate, poly(ethylene oxide) phenyl ether methacrylate, poly(trimethylene oxide) phenyl ether acrylate, poly(trimethylene oxide) phenyl ether methacrylate, poly(ethylene sulfide) phenyl ether acrylate, poly( ethylene sulfide) phenyl ether methacrylate, poly(trimethylene sulfide) phenyl ether acrylate, poly(trimethylene sulfide) phenyl ether methacrylate, poly(propylene oxide) phenyl ether acrylate, poly(propylene oxide) phenyl ether methacrylate, poly(propylene sulfide) phenyl ether acrylate and poly(propylene sulfide) phenyl ether methacrylate.
11. The composition of claim 1 wherein said high refractive index, low glass transition temperature monomer is 2-hydroxy-3-phenoxypropyl acrylate.
12. The composition of claim 1 wherein said low refractive index, high glass transition temperature monomer has a structure represented by the formula
O
R.-C- Rs l\
C
wherein Ri is selected from the group consisting of hydrogen and C1-12 alkyl; and R5 is selected from the group consisting of hydrogen and Cι--» alkyl; whereby the homopolymer formed from said monomer has a glass transition temperature greater than approximately 20 degrees Celsius and a refractive index less than approximately 1.50. O
13. The composition of claim 1 wherein said low refractive index, high glass transition temperature monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methaαylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 1 - methylcyclohexyl methaαylate, bornyl methacrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, methoxymethyl methacrylate, ethoxymethyl methacrylate, cydohexyloxymethyl methacrylate, 1 -ethoxyethyl methacrylate, 2-ethoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, glyddyl methacrylate and glycerol methacrylate.
14. The composition of daim 1 wherein said high refractive index, low glass transition temperature monomer and said low refractive index, high glass transition temperature monomer are present in a ratio of approximately 1:1 , respectively.
15. The composition of daim 1 wherein said high refractive index, low glass transition temperature monomer and said low refractive index, high glass
transition temperature monomer are present in a ratio of approximately 4:1 , respectively.
V
16. A composition poly(2-phenylethyl acrylate-cg-methyl methacrylate).
17. A composition poly(2-phenylethyl acrylate-gg-methyl methacrylate-cg- glyddyl methacrylate).
18. A composition poly(phenylthioethyl acrylate-co-methyl methacrylate).
19. A composition poly(phenylthioethyl acrylate-cg-methyl methacrylate-co- glyddyl methacrylate).
20. A composition poly(phenylthioethyl acrylate-cg-glycidyl methacrylate).
21. A medical device manufactured from a composition comprising: a high refractive index, low glass transition temperature monomer; a low refractive index, high glass transition temperature monomer; a αosslinker; and an initiator; whereby said composition has a refractive index of approximately 1.50 or greater and a glass transition temperature of approximately 20 degrees Celsius or lower.
22. The medical device of daim 21 wherein said composition indudes an ultraviolet light absorbing material.
23. The medical device of daim 21 wherein said composition indudes an ultraviolet light absorbing material selected from the group consisting of beta-
(4-benzotriazoyl-3-hydroxyphenoxy) ethyl acrylate, 4-(2-acryloxyethoxy)-2- hydroxybenzophenone, 4-methacryioxy-2-hydroxybenzophenone, 2-(2'- methaαyloxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'- methacryoxyethylphenyl)-2H-benzotriazole, 2-[3'-tert-Butyl-2'-hydroxy-5'-(3"- methacyloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-(3'-tert-Butyl-5'-{3- dimethylvinylsiiylpropoxy)-2'-hydroxyphenyl]-5-methoxybenzotriazole, 2-{3'- Allyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[3'-tert-Butyl-2'-hydroxy-5'- (3"-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole and 2-[3'-tert- Butyl-Z-hydroxy-S S'-methaαyloyloxypropoxyJphenylJ-S- chlorobenzotriazole.
24. The medical device of daim 21 wherein said composition includes beta-(4- benzotriazoyl-3-hydroxyphenoxy) ethyl acrylate as an ultraviolet light absorbing material.
25. The medical device of daim 21 wherein said initiator is selected from the
group consisting of 2,2'-azobis(isobutyronitrile)) 2,2'-azobis(2,4- dimethylvaleronitrile), 2,2'-azobis(methyibutyronitrile), 1 ,1'-
azobis(cyanocydohexane), di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl
peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t-
Hi butylperoxyneodecanote, t-butyl peroxy 2-ethylhexanoate, di(4-t-butyl cyclohexyl) peroxydicarbonate, t-butyl peroxypivalate, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-pentanedione peroxide, di(n- propyl)peroxydicarbonate, t-amyl peroxyneodecanoate and t-butyl peroxyacetate.
26. The medical device of daim 21 wherein said initiator is 2,2'- azobis(isobutyronitrile).
27. The medical device of daim 21 wherein said αosslinker is selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and poly(ethylene glycol) dimethacrylate.
28. The medical device of daim 21 wherein said αosslinker is ethylene glycol dimethacrylate.
29. The medical device of daim 21 wherein said high refractive index, low glass transition temperature monomer has a structure represented by one of the formulas
Figure imgf000045_0001
fl O
C- 0 - (CH2)„ R2 — Ar ,
\
Figure imgf000046_0001
o O- [CH2CH(OH)CH2 R ]P Ar , or
Figure imgf000046_0002
O
II R C C 0- [CH2CH(CH3)R4]p Ar
C
wherein Ri is selected from the group consisting of hydrogen and C1-12 alkyl; R2 is selected from the group consisting of oxygen, sulfur and NR3; R3 is
selected from the group consisting of hydrogen and Cι-β alkyl; R4 is selected from the group consisting of oxygen and sulfur; Ar is selected from the group consisting of C6-3-5 aryl and C& β substituted aryl wherein one or more carbons
are substituted with the same or different substituents selected from the group consisting of halogens, Cι-β alkyl, C1-6 alkoxy, Cβ-∑s aryl and C6-2S substituted aryl containing nitrogen or sulfur; n is an integer greater than or equal to 2; m is an integer greater than 1 and less than 5; and p is an integer greater than
or equal to 1 ; whereby the homopolymer formed from the selected monomer has a glass transition temperature of approximately 20 degrees Celsius or less and a refractive index of approximately 1.50 or greater.
30. The medical device of daim 21 wherein said high refractive index, low glass transition temperature monomer is selected from the group consisting of 2- phenylethyl acrylate, 3-phenylpropyl acrylate, 4-phenylbutyl acrylate, 4- phenylbutyl methaαylate, 5-phenylpentyl aαylate, 5-phenylpentyl methaαylate, 6-phenylhexyl aαylate, 6-phenylhexyl methaαylate, 2- phenyloxyethyl acrylate, 3-phenyloxypropyl acrylate, 2-hydroxy-3- phenoxypropyl acrylate, 4-phenyloxybutyl acrylate, 4-phenyloxybutyl methacrylate, 5-phenyloxypentyl acrylate, 5-phenyloxypentyl methacrylate, 6- phenyloxyhexyl acrylate, 6-phenyloxyhexyl methacrylate, 2-phenylthioethyl acrylate, 3-phenylthiopropyl acrylate, 4- phenylthiobutyl acrylate, 4- phenylthiobutyl methacrylate, 5-phenylthiopentyl acrylate, 5-phenylthiopentyl methacrylate, 6-phenyloxyhexyl acrylate, 6-phenyloxyhexyl methacrylate, 2-
aminophenylethyl aαylate, 3-aminophenylpropyl aαylate, 4-aminophenylbutyl acrylate, 4-aminophenylbutyl methacrylate, 5-aminophenylpentyl acrylate, 5-
aminophenylpentyl methacrylate, 6-aminophenylhexyl aαylate, 6- aminophenylhexyl methacrylate, (N-methyl)aminophenylethyl acrylate, 2-
naphthylethyl acrylate, 3-naphthylpropyl acrylate, 4-naphthylbutyl acrylate, 5- naphthylpentyl acrylate, 6-naphthylhexyl acrylate, 2-naphthyloxyethyl acrylate, 3- naphthyloxypropyl acrylate, 4-naphthyloxybutyl acrylate, 5- naphthyloxypentyl acrylate, 6-naphthyloxyhexyl acrylate, 2-naphthylthioethyl acrylate, 3-naphthylthiopropyl acrylate, 4-naphthylthiobutyl acrylate, 5- naphthylpentyl acrylate, 6-naphthylhexyl acrylate, poly(ethylene oxide) phenyl ether acrylate, poly(ethylene oxide) phenyl ether methacrylate, poly(trimethylene oxide) phenyl ether acrylate, poly(trimethylene oxide) phenyl ether methaαylate, poly(ethylene sulfide) phenyl ether acrylate, poly(ethylene sulfide) phenyl ether methacrylate, poly(trimethylene sulfide) phenyl ether aαylate, poly(trimethylene sulfide) phenyl ether methacrylate, poly(propylene oxide) phenyl ether acrylate, poly(propylene oxide) phenyl ether methacrylate, poly(propylene sulfide) phenyl ether acrylate and poly(propylene sulfide) phenyl ether methacrylate.
31. The medical device of daim 21 wherein said high refractive index, low glass transition temperature monomer is 2-hydroxy-3-phenoxypropyl acrylate.
32. The medical device of daim 21 wherein said low refractive index, high glass
transition temperature monomer has a structure represented by the formula
I O
II R,— C — C O Rs
// C wherein Ri is selected from the group consisting of hydrogen and C1-.2 alkyl; and R5 is selected from the group consisting of hydrogen, C1- alkyl; whereby the homopolymer formed from said monomer has a glass transition temperature greater than approximately 20 degrees Celsius and a refractive index less than approximately 1.50.
33. The medical device of daim 21 wherein said low refractive index, high glass transition temperature monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, cydohexyl methacrylate, 1 - methylcyclohexyl methacrylate, bomyl methacrylate, isobomyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, methoxymethyl methacrylate, ethoxymethyl methacrylate, cydohexyloxymethyl methacrylate, -ethoxyethyl methacrylate, 2-ethoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, glyddyl methacrylate and glycerol methacrylate.
W
34. The medical device of daim 21 wherein said high refractive index, low glass transition temperature monomer and said low refractive index, high glass
transition temperature monomer are present in a ratio of 1:1, respedively.
35. The medical device of daim 21 wherein said high refractive index, low glass transition temperature monomer and said low refractive index, high glass transition temperature monomer are present in a ratio of 4:1, respectively.
36. The medical device of daim 21 wherein said high refractive index, low glass transition temperature monomer is 2-phenylethyl acrylate and said low refractive index, high glass transition temperature monomer is methyl methacrylate.
37. The medical device of daim 21 wherein said high refractive index, low glass transition temperature monomer is 2-phenylthioethyl acrylate and said low refractive index, high glass transition temperature monomer is methyl methacrylate.
38. The medical device of daim 21 wherein said high refractive index, low glass transition temperature monomer is 2-hydroxy-3-phenoxypropyl acrylate and said low refractive index, high glass transition temperature monomer is methyl methacrylate.
39. The medical device of daim 21 wherein said high refractive index, low glass transition temperature monomer is 2-phenylethyl acrylate and said low refractive index, high glass transition temperature monomer is methyl methacrylate.
40. An intraocular lens manufactured from a composition comprising: a high refractive index, low glass transition temperature monomer; a low refractive index, high glass transition temperature monomer; a αosslinker; and an initiator; whereby said composition has a refractive index of approximately 1.50 or greater and a glass transition temperature of approximately 20 degrees Celsius or less.
41. The intraocular lens of daim 40 wherein said composition includes an ultraviolet light absorbing material.
42. The intraocular lens of claim 40 wherein said composition indudes an ultraviolet light absorbing material selected from the group consisting of beta- (4-benzotriazoyl-3-hydroxyphenoxy) ethyl acrylate, 4-(2-aαyloxyethoxy)-2- hydroxybenzophenone, 4-methacryloxy-2-hydroxybenzophenone, 2-(2'- methacryloxy-5'-methylphenyl)benzotriazole, 2-{2'-hydroxy-5'- methacryoxyethylphenyl)-2H-benzotriazole, 2-[3,-tert-Butyl-2'-hydroxy-5'-(3''- methacyloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-(3'-tert-Butyl-5,-(3- dimethylvinylsilylpropoxy)-2'-hydroxyphenyl]-5-methoxybenzotriazole, 2-(3'-
Allyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[3'-tert-Butyl-2'-hydroxy-5'- (3"-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole and 2-[3'-tert- Butyl^'-hydroxy-S'-fS'-methaayloyloxypropoxyJphenylj-S- chlorobenzotriazole.
43. The intraocular lens of claim 40 wherein said composition includes beta-(4- benzotriazoyl-3-hydroxyphenoxy) ethyl acrylate as an ultraviolet light absorbing material.
44. The intraocular lens of claim 40 wherein said initiator is selected from the group consisting of 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4- dimethylvaleronitrile), 2,2'-azobis(methylbutyronitrile), 1 ,1'- azobis(cyanocydohexane), di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t- butylperoxyneodecanote, t-butyl peroxy 2-ethylhexanoate, di(4-t-butyl cyclohexyl) peroxydicarbonate, t-butyl peroxypivalate, decanoyl peroxide,
lauroyl peroxide, benzoyl peroxide, 2,4-pentanedione peroxide, di(n- propyl)peroxydicarbonate, t-amyl peroxyneodecanoate and t-butyl peroxyacetate.
45. The intraocular lens of claim 40 wherein said initiator is 2,2'- azobis(isobutyronitrile).
46. The intraocular lens of claim 40 wherein said crosslinker is selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and poly(ethylene glycol) dimethacrylate.
47. The intraocular lens of claim 40 wherein said αosslinker is ethylene glycol dimethacrylate.
48. The intraocular lens of claim 40 wherein said high refractive index, low glass transition temperature monomer is represented by one of the formulas
Figure imgf000053_0001
C
O li
R, — c C 0- (CH2)n R2 — Ar , C
R, c — C //-O°-[(CH2)mR ]P Ar j
C
4 o
II
C — 0 - [CH2CH(OH)CH2 R- ]P Ar , or w
Figure imgf000054_0001
wherein Ri is selected from the group consisting of hydrogen and C1-12 alkyl; R2 is selected from the group consisting of oxygen, sulfur and NR3; 3 is selected from the group consisting of hydrogen and Ci-β alkyl; R is selected from the group consisting of oxygen and sulfur; Ar is selected from the group consisting of Ce β aryl and Cβ-aβ substituted aryl wherein one or more carbons are substituted with the same or different substituents seleded from the group consisting of halogens, C1-6 alkyl, C1-6 alkoxy, Cβ-25 aryl and Ce-25 substituted aryl containing nitrogen or sulfur; n is an integer greater than or equal to 2; m is an integer greater than 1 and less than 5; and p is an integer greater than or equal to 1 ; whereby the homopolymer formed from the selected monomer has a glass
transition temperature of approximately 20 degrees Celsius or less and a
refractive index of approximately 1.50 or greater.
49. The intraocular lens of claim 40 wherein said high refractive index, low glass
transition temperature monomer is selected from the group consisting of 2- phenylethyl acrylate, 3-phenyipropyl acrylate, 4-phenylbutyl aαylate, 4- phenylbutyl methaαylate, 5-phenylpentyl aαylate, 5-phenylpentyl methaαylate, 6-phenylhexyl aαylate, 6-phenylhexyl methacrylate, 2- phenyloxyethyl acrylate, 3-phenyloxypropyl acrylate, 2-hydroxy-3- phenoxypropyl acrylate, 4-phenyloxybutyl acrylate, 4-phenyloxybutyl methaαylate, 5-phenyloxypentyl aαylate, 5-phenyloxypentyl methacrylate, 6- phenyloxyhexyl acrylate, 6-phenyloxyhexyl methacrylate, 2-phenylthioethyl acrylate, 3-phenylthiopropyl acrylate, 4- phenylthiobutyl aαylate, 4- phenylthiobutyl methacrylate, 5-phenylthiopentyl acrylate, 5-phenyithiopentyl methacrylate, 6-phenyloxyhexyl acrylate, 6-phenyloxyhexyl methacrylate, 2- aminophenylethyl aαylate, 3-aminophenylpropyl acrylate, 4-aminophenylbutyl acrylate, 4-aminophenylbutyl methacrylate, 5-aminophenylpentyl acrylate, 5- aminophenylpentyl methacrylate, 6-aminophenylhexyl acrylate, 6- aminophenylhexyl methacrylate, (N-methyl)aminophenylethyl acrylate, 2- naphthylethyl aαylate, 3-naphthylpropyl acrylate, 4-naphthylbutyl acrylate, 5- naphthylpentyl aαylate, 6-naphthylhexyl aαylate, 2-naphthyloxyethyl acrylate, 3- naphthyloxypropyl aαylate, 4-naphthyloxybutyl acrylate, 5- naphthyloxypentyl acrylate, 6-naphthyloxyhexyl acrylate, 2-naphthylthioethyl acrylate, 3-naphthylthiopropyl acrylate, 4-naphthylthiobutyl acrylate, 5- naphthylpentyl acrylate, 6-naphthylhexyl acrylate, poly(ethylene oxide) phenyl ether acrylate, poly(ethylene oxide) phenyl ether methacrylate,
poly(trimethylene oxide) phenyl ether acrylate, poly(trimethylene oxide)
phenyl ether methacrylate, poly(ethylene sulfide) phenyl ether acrylate,
C poly(ethylene sulfide) phenyl ether methacrylate, poly(trimethylene sulfide)
phenyl ether acrylate, poly(trimethylene sulfide) phenyl ether methacrylate, poly(propylene oxide) phenyl ether acrylate, poly(propylene oxide) phenyl ether methacrylate, poly(propylene sulfide) phenyl ether acrylate and poly(propylene sulfide) phenyl ether methacrylate.
50. The intraocular lens of claim 40 wherein said high refractive index, low glass transition temperature monomer is 2-hydroxy-3-phenoxypropyl acrylate.
51. The intraocular lens of claim 40 wherein said low refractive index, high glass transition temperature monomer is represented by the formula
RrC C O Rs
II c wherein Ri is selected from the group consisting of hydrogen and C1- 2 alkyl; and R5 is selected from the group consisting of hydrogen and C 1- alkyl; whereby the homopolymer formed from said monomer has a glass transition temperature greater than approximately 20 degrees Celsius and a refractive index less than approximately 1.50.
52. The intraocular lens of daim 40 wherein said low refradive index, high glass transition temperature monomer is selected from the group consisting of
methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, cydohexyl methacrylate, 1 - methylcyclohexyl methacrylate, bomyl methacrylate, isobomyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, methoxymethyl
methacrylate, ethoxymethyl methacrylate, cydohexyloxymethyl methacrylate, 1 -ethoxyethyl methacrylate, 2-ethoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, glyddyl methacrylate and glycerol methacrylate.
53. The intraocular lens of daim 40 wherein said high refractive index, low glass transition temperature monomer and said low refractive index, high glass transition temperature monomer are present in a ratio of 1:1, respedively.
54. The intraocular lens of daim 40 wherein said high refradive index, low glass transition temperature monomer and said low refractive index, high glass transition temperature monomer are present in a ratio of 4:1, respedively.
55. The intraocular lens of daim 40 wherein said high refradive index, low glass transition temperature monomer is 2-hydroxy-3-phenoxypropyl acrylate and said low refractive index, high glass transition temperature monomer is methyl methacrylate.
n,
56. The intraocular lens of daim 40 wherein said high refractive index, low glass transition temperature monomer is 2-phenylethyl acrylate and said low
refractive index, high glass transition temperature monomer is methyl methacrylate.
57. The intraocular lens of daim 40 wherein said high refractive index, low glass transition temperature monomer is 2-phenoxyethyl acrylate and said low refractive index, high glass transition temperature monomer is methyl methacrylate.
58. A method of making a composition comprising: polymerizing polymerization materials which indude a high refractive index, low glass transition temperature monomer, a low refractive index, high glass transition temperature monomer, an initiator and a αosslinker; whereby said composition has a refractive index of approximately 1.50 or greater and a glass transition temperature of approximately 20 degrees Celsius or less.
59. The method of daim 58 wherein said polymerization materials indude an ultraviolet light absorbing material.
60. The method of daim 58 wherein said polymerization materials indude an ultraviolet light absorbing material seleded from the group consisting of beta- (4-benzotriazoyl-3-hydroxyphenoxy) ethyl acrylate, 4-<2-acryloxyethoxy)-2- hydroxybenzophenone, 4-methacryloxy-2-hydroxybenzophenone, 2-(2'- methacryloxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'- methaαyoxyethylphenyl)-2H-benzotriazole, 2-[3'-tert-Butyl-2'-hydroxy-5'-(3"- methacyloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-(3'-tert-Butyl-5'-(3- dimethylvinylsilylpropoxy)-2'-hydroxyphenyl]-5-methoxybenzotriazole, 2-(3'- Allyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[3'-tert-Butyl-2'-hydroxy-5'- (3"-methacryloyloxypropoxy)phenyl]-5-methoxybenzotriazole and 2-{3'-tert- Butyl-2'-hydroxy-5'-(3"-methacryloyloxypropoxy)phenyl]-5- chlorobenzotriazole.
61. The method of daim 58 wherein said polymerization materials indude beta- (4-benzotriazoyl-3-hydroxyphenoxy) ethyl acrylate as an ultraviolet light absorbing material.
62. The method of daim 58 wherein said initiator is seleded from the group consisting of 2,2'-azobis{isobutyronitrile), 2,2'-azobis(2,4- dimethylvaleronitrile), 2,2'-azobis(methylbutyronitrile), 1,1'- azobis(cyanocydohexane), di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t- butylperoxyneodecanote, t-butyl peroxy 2-ethylhexanoate, di(4-t-butyl cydohexyl) peroxydicarbonate, t-butyl peroxypivalate, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-pentanedione peroxide, di(n- propyl)peroxydicarbonate, t-amyl peroxyneodecanoate and t-butyl
peroxyacetate.
63. The method of daim 58 wherein said initiator is 2,2'-azobis(isobutyronitrile).
64. The method of daim 58 wherein said αosslinker is selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and poly(ethylene glycol) dimethacrylate.
65. The method of daim 58 wherein said αosslinker is ethylene glycol dimethacrylate.
66. The method of daim 58 wherein said high refractive index, low glass transition temperature monomer is represented by one of the formulas
o
II
Figure imgf000060_0001
c
O II
Figure imgf000060_0002
T O
// Ri C — C- 0- [(CH2)mR4]p Ar j
C
O
\l C O- [CH2CH(OH)CH2 F Jp Ar , or
Figure imgf000061_0001
o
II C O -[CH2CH(CH3)R4]P Ar
Figure imgf000061_0002
wherein Ri is selected from the group consisting of hydrogen and C1-12 alkyl; R2 is seleded from the group consisting of oxygen, sulfur and NR3; R3 is selected from the group consisting of hydrogen and C1-6 alkyl; R* is selected from the group consisting of oxygen and sulfur; Ar is seleded from the group consisting of C«6 aryl and C& e substituted aryl wherein one or more carbons are substituted with the same or different substituents selected from the group
consisting of halogens, C1-6 alkyl, Ci-β alkoxy, C6-25 aryl and Cβ-∑s substituted aryl containing nitrogen or sulfur, n is an integer greater than or equal to 2; m is an integer greater than 1 and less than 5; and p is an integer greater than
or equal to 1 ;
If O whereby the homopolymer formed from the selected monomer has a glass transition temperature of approximately 20 degrees Celsius or less and a refradive index of approximately 1.50 or greater.
67. The method of daim 58 wherein said high refractive index, low glass transition temperature monomer is selected from the group consisting of 2- phenylethyl acrylate, 3-phenylpropyl acrylate, 4-phenylbutyl acrylate, 4- phenylbutyl methacrylate, 5-phenylpentyl acrylate, 5-phenylpentyl methaαylate, 6-phenylhexyl aαylate, 6-phenylhexyl methaαylate, 2- phenyloxyethyl aαylate, 3-phenyloxypropyl acrylate, 2-hydroxy-3- phenoxypropyl acrylate, 4-phenyloxybutyl acrylate, 4-phenyloxybutyl methacrylate, 5-phenyloxypentyl acrylate, 5-phenyloxypentyl methacrylate, 6- phenyloxyhexyl acrylate, 6-phenyloxyhexyl methacrylate, 2-phenylthioethyl acrylate, 3-phenylthiopropyl acrylate, 4- phenylthiobutyl acrylate, 4- phenylthiobutyl methacrylate, 5-phenylthiopentyl acrylate, 5-phenylthiopentyl methacrylate, 6-phenyioxyhexyl acrylate, 6-phenyloxyhexyl methacrylate, 2- aminophenylethyl acrylate, 3-aminophenylpropyl acrylate, 4-aminophenylbutyl acrylate, 4-aminophenylbutyl methacrylate, 5-aminophenylpentyl acrylate, 5- aminophenylpentyl methacrylate, 6-aminophenylhexyl acrylate, 6-
aminophenylhexyl methacrylate, (N-methyl)aminophenylethyl acrylate, 2- naphthylethyl acrylate, 3-naphthylpropyl acrylate, 4-naphthyibutyl acrylate, 5- naphthylpentyl aαylate, 6-naphthylhexyl aαylate, 2-naphthyloxyethyl
acrylate, 3- naphthyloxypropyl aαylate, 4-naphthyloxybutyl acrylate, 5- naphthyloxypentyl acrylate, 6-naphthyloxyhexyl acrylate, 2-naphthylthioethyl acrylate, 3-naphthylthiopropyl acrylate, 4-naphthylthiobutyl acrylate, 5- naphthylpentyl acrylate, 6-naphthylhexyl acrylate, poly(ethylene oxide) phenyl ether acrylate, poly(ethylene oxide) phenyl ether methacrylate, poly(trimethylene oxide) phenyl ether acrylate, poly(trimethylene oxide) phenyl ether methacrylate, poly(ethylene sulfide) phenyl ether acrylate, poly(ethylene sulfide) phenyl ether methacrylate, poly(trimethylene sulfide) phenyl ether acrylate, poly(trimethylene sulfide) phenyl ether methacrylate, poly(propylene oxide) phenyl ether acrylate, poly(propylene oxide) phenyl ether methacrylate, poly(propylene sulfide) phenyl ether acrylate and poly(propylene sulfide) phenyl ether methacrylate.
68. The method of daim 58 wherein said high refractive index, low glass transition temperature monomer is 2-hydroxy-3-phenoxypropyl acrylate.
69. The method of daim 58 wherein said low refractive index, high glass transition temperature monomer is represented by the formula
0
II
Rt C C O Rs
C
wherein Ri is selected from the group consisting of hydrogen and C1-12 alkyl; and R5 is selected from the group consisting of hydrogen and C alkyl;
whereby the homopolymer formed from said monomer has a glass transition temperature greater than approximately 20 degrees Celsius and a refractive
index less than approximately 1.50.
70. The method of daim 58 wherein said low refractive index, high glass transition temperature monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, cydohexyl methacrylate, 1 - methylcydohexyl methacrylate, bornyl methacrylate, isobomyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, methoxymethyl methacrylate, ethoxymethyl methacrylate, cydohexyloxymethyl methacrylate, 1-ethoxyethyl methacrylate, 2-ethoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, glyddyl methaαylate and glycerol methacrylate.
71.The method of daim 58 wherein said high refractive index, low glass transition temperature monomer and said low refractive index, high glass transition temperature monomer are present in a ratio of 1:1, respectively.
72. The method of daim 58 wherein said high refractive index, low glass
transition temperature monomer and said low refradive index, high glass transition temperature monomer are present in a ratio of 4: 1 , respedively.
t,3
73. The method of daim 58 wherein said high refractive index, low glass transition temperature monomer is 2-phenylethyl acrylate and said low refractive index, high glass transition temperature monomer is methyl
methacrylate.
74.. The method of daim 58 wherein said high refractive index, low glass transition temperature monomer is 2-phenoxyethyl acrylate and said low refractive index, high glass transition temperature monomer is methyl methacrylate.
75. A method of making an intraocular lens from a composition comprising: lathing a composition polymerized from polymerization materials induding a high refractive index, low glass transition temperature monomer, a low refractive index, high glass transition temperature monomer, an initiator and a αosslinker, into the form of an intraocular lens; whereby said intraocular lens has a refradive index of approximately 1.50 or greater and a glass transition temperature of approximately 20 degrees Celsius or less.
76. The method of daim 75 wherein said polymerization materials indude an ultraviolet light absorbing material.
77. The method of daim 75wherein said polymerization materials indude an ultraviolet light absorbing material selected from the group consisting of beta- (4-benzotriazoyl-3-hydroxyphenoxy) ethyl acrylate, 4-{2-acryloxyethoxy)-2- hydroxybenzophenone, 4-methacryloxy-2-hydroxybenzophenone, 2-(2'- methaαyloxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-
methacryoxyethylphenyl)-2H-benzotriazole, 2-[3'-tert-Butyl-2'-hydroxy-5'-(3"- methacyloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-(3'-tert-Butyl-5'-(3- dimethylvinylsilylpropoxy)-2'-hydroxyphenyl]-5-methoxybenzotriazole, 2-(3'- Allyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[3'-tert-Butyl-2'-hydroxy-5'- (3"-methaαyloyloxypropoxy)phenyl]-5-methoxybenzotriazole and 2-{3'-tert- Butyl-2'-hydroxy-5'-(3"-methacryloyloxypropoxy)phenyl]-5- chlorobenzotriazole.
78. The method of daim 75 wherein said polymerization materials indude beta- (4-benzotriazoyl-3-hydroxyphenoxy) ethyl acrylate as an ultraviolet light absorbing material.
79. The method of daim 75 wherein said initiator is seleded from the group consisting of 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-
dimethylvaleronitrile), 2,2'-azobis(methylbutyronitrile), 1,1"-
azobis(cyanocydohexane), di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl
peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t- butylperoxyneodecanote, t-butyl peroxy 2-ethylhexanoate, di(4-t-butyl cyclohexyl) peroxydicarbonate, t-butyl peroxypivalate, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-pentanedione peroxide, di(n-
propyl)peroxydicarbonate, t-amyl peroxyneodecanoate and t-butyl peroxyacetate.
80. The method of daim 75 wherein said initiator is 2,2'-azobis(isobutyronitrile) .
81.The method of daim 75 wherein said αosslinker is selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and poly(ethylene glycol) dimethacrylate.
82. The method of daim 75 wherein said αosslinker is ethylene glycol dimethacrylate.
83. The method of daim 75 wherein said high refractive index, low glass transition temperature monomer is represented by one of the formulas
O
II
Figure imgf000067_0001
C
Figure imgf000067_0002
0
//
R, C — C O- [(CH2)mR ]P — Ar
\\ C o
II
R, C C O- [CH2CH(OH)CH2 R4]p Ar , or
W C o
II C — O- [CH2CH(CH3)R4]P Ar
Figure imgf000068_0001
wherein Ri is selected from the group consisting of hydrogen and C1-12 alkyl; R2 is selected from the group consisting of oxygen, sulfur and NR3; R3 is selected from the group consisting of hydrogen and Ci-β alkyl; R is seleded from the group consisting of oxygen and sulfur, Ar is seleded from the group consisting of C6-3-3 aryl and C5-36 substituted aryl wherein one or more carbons are substituted with the same or different substituents seleded from the group
consisting of halogens, Ci-β alkyl, C1-6 alkoxy, Cβ-25 aryl and C&.25 substituted aryl containing nitrogen or sulfur, n is an integer greater than or equal to 2; m is an integer greater than 1 and less than 5; and p is an integer greater than
or equal to 1 ;
π whereby the homopolymer formed from the selected monomer has a glass transition temperature of approximately 20 degrees Celsius or less and a refradive index of approximately 1.50 or greater.
84. The method of daim 75 wherein said high refractive index, low glass transition temperature monomer is selected from the group consisting of 2- phenylethyl acrylate, 3-phenylpropyl acrylate, 4-phenylbutyl acrylate, 4- phenylbutyl methacrylate, 5-phenylpentyl acrylate, 5-phenylpentyl methacrylate, 6-phenylhexyl acrylate, 6-phenylhexyl methacrylate, 2- phenyloxyethyl acrylate, 3-phenyloxypropyl acrylate, 2-hydroxy-3- phenoxypropyl acrylate, 4-phenyioxybutyl aαylate, 4-phenyloxybutyl methacrylate, 5-phenyloxypentyl acrylate, 5-phenyloxypentyl methacrylate, 6- phenyloxyhexyl acrylate, 6-phenyloxyhexyl methacrylate, 2-phenylthioethyl acrylate, 3-phenylthiopropyl acrylate, 4- phenylthiobutyl acrylate, 4- phenylthiobutyl methacrylate, 5-phenylthiopentyl acrylate, 5-phenylthiopentyl methacrylate, 6-phenyloxyhexyl acrylate, 6-phenyloxyhexyl methacrylate, 2- aminophenylethyl acrylate, 3-aminophenylpropyl acrylate, 4-aminophenylbutyl acrylate, 4-aminophenylbutyl methacrylate, 5-aminophenylpentyl acrylate, 5- aminophenylpentyl methacrylate, 6-aminophenylhexyl acrylate, 6- aminophenylhexyl methacrylate, (N-methyl)aminophenylethyl acrylate, 2-
naphthylethyl acrylate, 3-naphthylpropyl acrylate, 4-naphthylbutyl acrylate, 5-
naphthylpentyl acrylate, 6-naphthylhexyl acrylate, 2-naphthyloxyethyl acrylate, 3- naphthyloxypropyl aαylate, 4-naphthyloxybutyl acrylate, 5- naphthyloxypentyl acrylate, 6-naphthyloxyhexyl aαylate, 2-naphthylthioethyl acrylate, 3-naphthylthiopropyl acrylate, 4-naphthylthiobutyl acrylate, 5- naphthylpentyl acrylate, 6-naphthylhexyl acrylate, poly(ethylene oxide) phenyl ether acrylate, poly(ethylene oxide) phenyl ether methacrylate, poly(trimethylene oxide) phenyl ether acrylate, poly(trimethylene oxide) phenyl ether methacrylate, poly(ethylene sulfide) phenyl ether acrylate, poly(ethylene sulfide) phenyl ether methacrylate, poly(trimethylene sulfide) phenyl ether acrylate, poly(trimethylene sulfide) phenyl ether methacrylate, poly(propylene oxide) phenyl ether acrylate, pdy(propylene oxide) phenyl ether methacrylate, poly(propylene sulfide) phenyl ether acrylate and poly(propylene sulfide) phenyl ether methacrylate.
85. The method of daim 75 wherein said high refractive index, low glass transition temperature monomer is 2-hydroxy-3-phenoxypropyl acrylate.
86. The method of daim 75 wherein said low refradive index, high glass transition temperature monomer is represented by the formula
O II RrC C O Rs
II c wherein Ri is selected from the group consisting of hydrogen and C1-12 alkyl; and R5 is selected from the group consisting of hydrogen and C1-4 alkyl; whereby the homopolymer formed from said monomer has a glass transition temperature greater than approximately 20 degrees Celsius and a refractive
index less than approximately 1.50.
87. The method of daim 75 wherein said low refractive index, high glass transition temperature monomer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 1 - methylcyclohexyl methacrylate, bornyl methacrylate, isobomyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydraxypropyl methacrylate, methoxymethyl methacrylate, ethoxymethyl methacrylate, cydohexyloxymethyl methacrylate, 1-ethoxyethyl methacrylate, 2-ethoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, glyddyl methacrylate and glycerol methacrylate.
88. The method of daim 75 wherein said high refractive index, low glass transition temperature monomer and said low refractive index, high glass
transition temperature monomer are present in a ratio of 1:1, respedively.
89. The method of daim 75 wherein said high refractive index, low glass transition temperature monomer and said low refractive index, high glass
transition temperature monomer are present in a ratio of 4:1, respedively.
90. The method of daim 75 wherein said high refractive index, low glass transition temperature monomer is 2-phenylethyl acrylate and said low refractive index, high glass transition temperature monomer is methyl
methacrylate.
91.The method of daim 75 wherein said high refractive index, low glass transition temperature monomer is 2-phenoxyethyl acrylate and said low refractive index, high glass transition temperature monomer is methyl methacrylate.
92. The method of daim 75 wherein said high refractive index, low glass transition temperature monomer is 2-phenylthioethyi acrylate and said low refractive index, high glass transition temperature monomer is methyl methacrylate.
93. The method of daim 75 wherein said high refractive index, low glass transition temperature monomer is 2-hydroxy-3-phenoxypropyl acrylate and said low refractive index, high glass transition temperature monomer is methyl methacrylate.
94. A method of using an intraocular lens manufadured from a composition
polymerized from polymerization materials including a high refractive index,
low glass transition temperature monomer, a low refractive index, high glass transition temperature monomer, an initiator and a αosslinker, having a
refractive index of approximately 1.50 or greater and a glass transition temperature of approximately 20 degrees Celsius or less, comprising: pladng said intraocular lens within an eye through an incision in the cornea of an eye.
95. The method of daim 94 wherein said polymerization materials indude an ultraviolet light absorbing material.
96. The method of daim 94 wherein said polymerization materials indude an ultraviolet light absorbing material selected from the group consisting of beta- (4-benzotriazoyl-3-hydroxyphenoxy) ethyl aαylate, 4-{2-aαyloxyethoxy)-2- hydroxybenzophenone, 4-methaαyloxy-2-hydroxybenzophenone, 2-(2'- methaαyloxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'- methaαyoxyethylphenyl)-2H-benzotriazole, 2-[3'-tert-Butyl-2'-hydroxy-5'-(3β- methacyloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-{3'-tert-Butyl-5'-{3- dimethylvinylsilylpropoxy)-2'-hydroxyphenyl]-5-methoxybenzotriazole, 2-{3'-
Allyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[3'-tert-Butyl-2'-hydroxy-5'- (3"-methaαyloyloxyρropoxy)phenylJ-5-methoxybenzotriazole and 2-[3'-tert-
Butyl-2'-hydroxy-5'-(3"-methacryloyloxypropoxy)phenyl]-5- chlorobenzotriazole.
1>
97. The method of daim 94 wherein said polymerization materials indude beta- (4-benzotriazoyl-3-hydroxyphenoxy) ethyl acrylate as an ultraviolet light absorbing material.
98. The method of daim 94 wherein said initiator is selected from the group consisting of 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4- dimethylvaleronitrile), 2,2'-azobis(methylbutyronitrile), 1,1'- azobis(cyanocydohexane), di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t- butylperoxyneodecanote, t-butyl peroxy 2-ethylhexanoate, di(4-t-butyl cyclohexyl) peroxydicarbonate, t-butyi peroxypivalate, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-pentanedione peroxide, di(n- propyl)peroxydicarbonate, t-amyl peroxyneodecanoate and t-butyl peroxyacetate.
99. The method of daim 94 wherein said initiator is 2,2'-azobis(isobutyronitrile).
100. The method of daim 94 wherein said αosslinker is seleded from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate and poly(ethylene glycol) dimethacrylate.
?;
101. The method of daim 94 wherein said αosslinker is ethylene glycol
dimethacrylate.
102. The method of daim 94 wherein said high refractive index, low glass transition temperature monomer is represented by one of the formulas
O
II
Figure imgf000075_0001
O
II
R, C C 0- (CH2)n R2 — Ar , C
//
Ri C — C-0-[(CH2)mR4]P Ar ,
W C
0
Figure imgf000075_0002
0 w
Ri C C 0- [CH2CH(CH3)F-4]p Ar w c
wherein Ri is seleded from the group consisting of hydrogen and C1-12 alkyl;
R2 is seleded from the group consisting of oxygen, sulfur and NR3; R3 is
1Λ selected from the group consisting of hydrogen and Ci-β alkyl; R-» is selected
from the group consisting of oxygen and sulfur; Ar is selected from the group
consisting of C&-36 aryl and C&-36 substituted aryl wherein one or more carbons are substituted with the same or different substituents seleded from the group
consisting of halogens, Ci-β alkyl, Ci-β alkoxy, Cβ-2s aryl and C$.25 substituted aryl containing nitrogen or sulfur; n is an integer greater than or equal to 2; m is an integer greater than 1 and less than 5; and p is an integer greater than or equal to 1 ; whereby the homopolymer formed from the selected monomer has a glass transition temperature of approximately 20 degrees Ceisius or less and a refractive index of approximately 1.50 or greater.
. The method of daim 94 wherein said high refractive index, low glass transition temperature monomer is selected from the group consisting of 2- phenylethyl aαylate, 3-phenylpropyl acrylate, 4-phenylbutyl aαylate, 4- phenylbutyl methaαylate, 5-phenylpentyl aαylate, 5-phenylpentyl methaαylate, 6-phenylhexyl aαylate, 6-phenylhexyl methaαylate, 2- phenyloxyethyl acrylate, 3-phenyloxypropyl aαylate, 2-hydroxy-3- phenoxypropyl acrylate, 4-phenyloxybutyl acrylate, 4-phenyloxybutyl
methacrylate, 5-phenyloxypentyl acrylate, 5-phenyloxypentyl methacrylate, 6-
phenyloxyhexyl acrylate, 6-phenyloxyhexyl methacrylate, 2-phenylthioethyl
acrylate, 3-phenylthiopropyl acrylate, 4- phenylthiobutyl acrylate, 4- phenylthiobutyl methacrylate, 5-phenylthiopentyl acrylate, 5-phenylthiopentyl methacrylate, 6-phenyloxyhexyl acrylate, 6-phenyloxyhexyl methacrylate, 2-
aminophenylethyl acrylate, 3-aminophenylpropyl acrylate, 4-aminophenylbutyl acrylate, 4-aminophenylbutyl methacrylate, 5-aminophenylpentyl acrylate, 5- aminophenylpentyl methacrylate, 6-aminophenylhexyl acrylate, 6- aminophenylhexyl methacrylate, (N-methyl)aminophenylethyl acrylate, 2- naphthylethyl acrylate, 3-naphthylpropyl acrylate, 4-naphthylbutyl acrylate, 5- naphthylpentyl acrylate, 6-naphthylhexyl acrylate, 2-naphthyloxyethyl acrylate, 3- naphthyloxypropyl acrylate, 4-naphthyloxybutyl acrylate, 5- naphthyloxypentyl acrylate, 6-naphthyloxyhexyl acrylate, 2-naphthylthioethyl acrylate, 3-naphthylthiopropyl acrylate, 4-naphthylthiobutyl acrylate, 5- naphthylpentyl acrylate, 6-naphthylhexyl acrylate, poly(ethylene oxide) phenyl ether acrylate, poly(ethylene oxide) phenyl ether methacrylate, poly(trimethylene oxide) phenyl ether acrylate, poly(trimethylene oxide) phenyl ether methacrylate, poly(ethylene sulfide) phenyl ether acrylate, poly(ethylene sulfide) phenyl ether methacrylate, poly(trimethylene sulfide)
phenyl ether acrylate, poly(trimethylene sulfide) phenyl ether methacrylate, poly(propylene oxide) phenyl ether acrylate, poly(propylene oxide) phenyl ether methacrylate, poly(propylene sulfide) phenyl ether acrylate and poly(propylene sulfide) phenyl ether methacrylate.
. The method of daim 94 wherein said high refradive index, low glass
transition temperature monomer is 2-hydroxy-3-phenoxypropyl acrylate.
%
105. The method of daim 94 wherein said low refradive index, high glass transition temperature monomer is represented by the formula
Figure imgf000078_0001
wherein Ri is selected from the group consisting of hydrogen and C.-12 alkyl; and Rδis selected from the group consisting of hydrogen and C1-4 alkyl; whereby the homopolymer formed from said monomer has a glass transition temperature greater than approximately 20 degrees Celsius and a refractive index less than approximately 1.50.
106. The method of daim 94 wherein said low refractive index, high glass transition temperature monomer is seleded from the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, cydohexyl methacrylate, 1-
methylcyclohexyl methacrylate, bomyl methaαylate, isobornyl methaαylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, methoxymethyl methaαylate, ethoxymethyl methacrylate, cydohexyloxymethyl methacrylate, 1-ethoxyethyl methacrylate, 2-ethoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, gly dyl methaαylate and glycerol methacrylate.
107. The method of daim 94 wherein said high refractive index, low glass transition temperature monomer and said low refractive index, high glass transition temperature monomer are present in a ratio of 1 : 1 , respectively.
108. The method of daim 94 wherein said high refractive index, low glass transition temperature monomer and said low refractive index, high glass transition temperature monomer are present in a ratio of 4:1, respectively.
109. The method of daim 94 wherein said high refractive index, low glass transition temperature monomer is 2-phenylethyl acrylate and said low refractive index, high glass transition temperature monomer is methyl methacrylate.
110. The method of daim 94 wherein said high refractive index, low glass transition temperature monomer is 2-phenoxyethyl acrylate and said low refradive index, high glass transition temperature monomer is methyl methacrylate.
111. The method of daim 94 wherein said high refractive index, low glass transition temperature monomer is 2-phenylthioethyl acrylate and said low refractive index, high glass transition temperature monomer is methyl methaαylate.
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