U.S. patent application number 10/848262 was filed with the patent office on 2004-10-28 for high refractive index aromatic-based silyl monomers.
Invention is credited to Kunzler, Jay F., Ozark, Richard M., Salamone, Joseph C., Seelye, David E., Vanderbilt, David P..
Application Number | 20040215032 10/848262 |
Document ID | / |
Family ID | 21706715 |
Filed Date | 2004-10-28 |
United States Patent
Application |
20040215032 |
Kind Code |
A1 |
Salamone, Joseph C. ; et
al. |
October 28, 2004 |
High refractive index aromatic-based silyl monomers
Abstract
Optically transparent, relatively high refractive index
polymeric compositions and ophthalmic devices such as intraocular
lenses, contact lenses and corneal inlays made therefrom are
described herein. The preferred polymeric compositions are produced
through the polymerization of one or more aromatic-based silyl
monomers or the copolymerization of one or more aromatic-based
silyl monomers with one or more aromatic or non-aromatic
non-siloxy-based monomers, hydrophobic monomers or hydrophilic
monomers.
Inventors: |
Salamone, Joseph C.; (Boca
Raton, FL) ; Kunzler, Jay F.; (Canadaigua, NY)
; Ozark, Richard M.; (Solvay, NY) ; Seelye, David
E.; (North Chili, NY) ; Vanderbilt, David P.;
(Webster, NY) |
Correspondence
Address: |
RITA D. VACCA
BAUSCH & LOMB INCORPORATED
ONE BAUSCH & LOMB PLACE
ROCHESTER
NY
14604-2701
US
|
Family ID: |
21706715 |
Appl. No.: |
10/848262 |
Filed: |
May 18, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10848262 |
May 18, 2004 |
|
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10003616 |
Nov 2, 2001 |
|
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6762271 |
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Current U.S.
Class: |
556/437 ;
556/418 |
Current CPC
Class: |
Y10S 623/907 20130101;
C07F 7/081 20130101; Y10S 623/905 20130101 |
Class at
Publication: |
556/437 ;
556/418 |
International
Class: |
C07F 007/04; C07F
007/08 |
Claims
1. Aromatic-based silyl monomers having a structure represented by
4wherein R is a polymerizable group; X is selected from the group
consisting of C.sub.1-10 alkyl, C.sub.1-10 alkyloxy, C.sub.6-36
aryl and C.sub.6-36 aryloxy; and the R.sub.1 groups may be the same
or different selected from the group consisting of C.sub.1-10
alkyl, C.sub.1-20 cycloalkyl, C.sub.6-36 aryl, C.sub.6-36 aryl
ether, C.sub.6-36 heterocycle, C.sub.6-36 heterocycle with one or
more substituents, C.sub.1-10 alkyl ether and C.sub.6-36
aryloxy.
2. A polymeric composition produced through the polymerization of
one or more monomers of claim 1.
3. A polymeric composition produced through the copolymerization of
one or more monomers of claim 1 with one or more aromatic or
non-aromatic non-siloxy-based monomers.
4. A polymeric composition produced through the copolymerization of
one or more monomers of claim 1 with one or more hydrophilic
monomers.
5. A polymeric composition produced through the copolymerization of
one or more monomers of claim 1 with one or more hydrophobic
monomers.
6. A method of producing aromatic-based silyl monomers having a
structure represented by 5wherein R is a polymerizable group; X is
selected from the group consisting of C.sub.1-10 alkylene,
C.sub.1-10 alkyleneoxy. C.sub.6-36 arylene and C.sub.6-36
aryleneoxy; and the R.sub.1 groups may be the same or different
selected from the group consisting of C.sub.1-10 alkyl, C.sub.1-20
cycloalkyl, C.sub.6-36 aryl, C.sub.6-36 aryl ether, C.sub.6-36
heterocycle, C.sub.6-36 heterocycle with one or more substituents,
C.sub.1-10 alkyl ether and C.sub.6-36 aryloxy, with at least one
R.sub.1 group being other than a methyl group; and with at least
one of said monomers having at least one non-phenyl R.sub.1 group,
comprising: combining an aromatic alkylsilane with a catalyst to
form a product; and combining said product with acetic acid
followed by an addition of acryloyl chloride.
7. A method of producing the polymeric compositions of claim 3
wherein said one or more aromatic or non-aromatic non-siloxy-based
monomers is selected from the group consisting of 2-phenyoxyethyl
methacrylate, 3,3-diphenylpropyl methacrylate,
N,N-dimethylacrylamide, methyl methacrylate, 2-(1-naphthylethyl)
methacrylate, glycol methacrylate, 3-phenylpropyl acrylate and
2-(2-naphthylethyl) methacrylate.
8. A method of producing the polymeric compositions of claim 4
wherein said one or more hydrophilic monomers is selected from the
group consisting of N,N-dimethylacrylamide and methyl
methacrylate.
9. A method of producing the polymeric compositions of claim 5
wherein said one or more hydrophobic monomers is selected from the
group consisting of 2-ethylhexyl methacrylate,
3-methacryloyloxypropyl-diphenyl- methylsilane and 2-phenyloxyethyl
methacrylate.
10. A method of producing ophthalmic devices from the polymeric
compositions of claim 2, 3, 4 or 5 comprising: casting one or more
polymeric compositions in the form of a rod; lathing or machining
said rod into disks; and lathing or machining said disks into
ophthalmic devices.
11. A method of producing ophthalmic devices from the polymeric
compositions of claim 2, 3, 4 or 5 comprising: pouring one or more
polymeric compositions into a mold prior to curing; curing said one
or more polymeric compositions; and removing said one or more
polymeric compositions form said mold following curing thereof.
12. A method of using ophthalmic devices of claim 10 or 11
comprising: making an incision in the cornea of an eye; and
implanting said ophthalmic device within the eye.
13. The method of claim 10, 11 or 12 wherein said ophthalmic device
is an intraocular lens or a corneal inlay.
14. The method of claim 10 or 11 wherein said ophthalmic device is
a contact lens.
15. A polymeric composition produced through the polymerization of
one or more monomers of claim 1 with one or more strengthening
agents.
16. A polymeric composition produced through the copolymerization
of one or more monomers of claim 1 with one or more aromatic or
non-aromatic non-siloxy-based monomers and one or more
strengthening agents.
17. A polymeric composition produced through the copolymerization
of one or more monomers of claim 1 with one or more hydrophilic
monomers and one or more strengthening agents.
18. A polymeric composition produced through the copolymerization
of one or more monomers of claim 1 with one or more hydrophobic
monomers and one or more strengthening agents.
19. The polymeric composition of claim 15, 16, 17 or 18 wherein
said one or more strenghthening agents are selected from the group
consisting of cycloalkyl acrylates and methacrylates.
20. A polymeric composition produced through the polymerization of
one or more monomers of claim 1 with one or more crosslinking
agents.
21. A polymeric composition produced through the copolymerization
of one or more monomers of claim 1 with one or more aromatic or
non-aromatic non-siloxy-based monomers and one or more crosslinking
agents.
22. A polymeric composition produced through the copolymerization
of one or more monomers of claim 1 with one or more hydrophilic
monomers and one or more crosslinking agents.
23. A polymeric composition produced through the copolymerization
of one or more monomers of claim 1 with one or more hydrophobic
monomers and one or more crosslinking agents.
24. The polymeric composition of claim 20, 21, 22 or 23 wherein
said one or more crosslinking agents are selected from the group
consisting of diacrylates and dimethacrylates of triethylene
glycol, butylene glycol, neopentyl glycol, hexane-1,6-diol,
thio-diethylene glycol and ethylene glycol, trimethylolpropane
triacrylate, N,N'-dihydroxyethylene bisacrylamide, diallyl
phthalate, triallyl cyanurate, divinylbenzene; ethylene glycol
divinyl ether, N,N-methylene-bis-(meth)acrylamide, sulfonated
divinylbenzene and divinylsulfone.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to monomers useful in the
manufacture of biocompatible medical devices. More particularly,
the present invention relates to aromatic-based silyl monomers
capable of polymerization alone or copolymerization with other
monomers. Upon polymerization or copolymerization, the subject
monomers form polymeric compositions having desirable physical
characteristics and refractive indices useful in the manufacture of
ophthalmic devices.
BACKGROUND OF THE INVENTION
[0002] Since the 1940's ophthalmic devices in the form of
intraocular lens (IOL) implants 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 lens implants was
poly(methyl methacrylate), which is a rigid, glassy polymer.
[0003] Softer, more flexible IOL implants have gained in popularity
in more recent years due to their ability to be compressed, folded,
rolled or otherwise deformed. Such softer IOL implants 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 material. Softer, more flexible IOL
implants 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 IOLs, i.e., 5.5 to 7.0 mm. A larger
incision is necessary for more rigid IOL implants 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 IOL implants 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.
[0004] With recent advances in small-incision cataract surgery,
increased emphasis has been placed on developing soft, foldable
materials suitable for use in artificial IOL implants. In general,
the materials of current commercial IOLs fall into one of three
general categories: silicones, hydrophilic acrylics and hydrophobic
acrylics.
[0005] In general, high water content hydrophilic acrylics, or
"hydrogels," have relatively low refractive indices, 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 endothelium and/or rupture the
natural lens capsule and associated zonules. Low glass transition
temperature hydrophobic 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 hydrophobic acrylic materials, which
contain little or no water 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.
[0006] Because of the noted shortcomings of current polymeric
materials available for use in the manufacture of ophthalmic
implants, there is a need for stable, biocompatible polymeric
materials having desirable physical characteristics and refractive
indices.
SUMMARY OF THE INVENTION
[0007] Soft, foldable, high refractive index, high elongation
polymeric compositions of the present invention are produced
through the polymerization or copolymerization of aromatic-based
silyl monomers. The subject monomers are synthesized through a
multi-step reaction scheme. The polymeric compositions produced
from the silyl monomers have ideal physical properties for the
manufacture of ophthalmic devices. The polymeric compositions of
the present invention are transparent, of relatively high strength
for durability during surgical manipulations, of relatively high
elongation, of relatively high refractive index and are
biocompatible. The subject polymeric compositions are particularly
well suited for use as intraocular lens (IOLs) implants, contact
lenses, keratoprostheses, corneal rings, corneal inlays and the
like.
[0008] Preferred aromatic-based silyl monomers for use in preparing
the polymeric compositions of present invention have the
generalized structure represented by Formula 1 below, 1
[0009] wherein R is a polymerizable group; X is selected from the
group consisting of C.sub.1-10 alkyl, C.sub.1-10 alkyloxy,
C.sub.6-36 aryl and C.sub.6-36 aryloxy; and the R.sub.1 groups may
be the same or different selected from the group consisting of
C.sub.1-10 alkyl, C.sub.1-20 cycloalkyl, C.sub.6-36 aryl,
C.sub.6-36 aryl ether, C.sub.6-36 heterocycle, C.sub.6-36
heterocycle with one or more substituents, C.sub.1-10 alkyl ether
and C.sub.6-36 aryloxy.
[0010] Accordingly, it is an object of the present invention to
provide transparent, polymeric compositions having desirable
physical characteristics for the manufacture of ophthalmic
devices.
[0011] Another object of the present invention is to provide
polymeric compositions of relatively high refractive index.
[0012] Another object of the present invention is to provide
polymeric compositions suitable for use in the manufacture of
intraocular lens implants.
[0013] Another object of the present invention is to provide
polymeric compositions that are biocompatible.
[0014] Another object of the present invention is to provide
polymeric compositions suitable for use as contact lens
materials.
[0015] Still another object of the present invention is to provide
polymeric compositions that are economical to produce.
[0016] 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
[0017] The present invention relates to novel aromatic-based silyl
monomers synthesized through a three-step reaction scheme. The
subject aromatic-based silyl monomers are useful in the production
of biocompatible polymeric compositions. The subject polymeric
compositions have particularly desirable physical properties. The
subject polymeric compositions have a relatively high refractive
index of approximately 1.45 or greater and relatively high
elongation of approximately 100 percent or greater. Accordingly,
the subject polymeric compositions are ideal for use in the
manufacture of ophthalmic devices. The aromatic-based silyl
monomers of the present invention are generally represented by
Formula 1 below: 2
[0018] wherein R is a polymerizable group selected from the group
consisting of methacrylate, acrylate, acrylamido, methacrylamido,
styryl, itaconate, fumaroyl, vinyl, vinyloxy, vinyl carbamate and
vinyl carbonate; X is selected from the group consisting of
C.sub.1-10 alkyl such as for example but not limited to methyl,
propyl or heptyl, C.sub.1-10 alkyloxy such as for example but not
limited to ethyloxy, butyloxy or octyloxy, C.sub.6-36 aryl such as
for example but not limited to phenyl or naphthyl and C.sub.6-36
aryloxy such as for example but not limited to phenyloxy or
naphthyloxy; and the R.sub.1 groups may be the same or different
selected from the group consisting of C.sub.1-10 alkyl such as for
example but not limited to methyl, propyl or pentyl but preferably
propyl for increased stability, C.sub.1-20 cycloalkyl such as for
example but not limited to cyclohexyl or cycloheptyl, C.sub.6-36
aryl such as for example but not limited to phenyl or naphthyl,
C.sub.6-36 aryl ether such as for example but not limited to phenyl
ether or naphthyl ether, C.sub.6-36 heterocycle such as for example
but not limited to pyridine, quinoline, furan or thiophene but
preferably pyridine to increase refractive index, C.sub.6-36
heterocycle such as those described above with one or more
substituents such as for example but not limited to chlorine,
fluorine, amine, amide, ketone or C.sub.1-3 alkyl such as for
example methyl or propyl, C.sub.6-36 aryloxy such as for example
but not limited to phenyloxy or naphthyloxy and C.sub.1-10 alkyl
ethers such as for example methyl ether or propyl ether.
[0019] Examples of aromatic-based silyl monomers of the present
invention include for example but are not limited to
1-methacryloyloxypropyldimethy- lphenylsilane,
1-methacryloyloxypropyldiphenylmethylsilane and
1-methacryloyloxypropyltriphenylsilane.
[0020] Aromatic-based silyl monomers of the present invention may
be synthesized through a three-step reaction scheme as represented
in Scheme 1 below: 3
[0021] One or more aromatic-based silyl monomers of the present
invention produced as described above may be polymerized alone or
copolymerized with other monomers. One or more of the subject silyl
monomers may be copolymerized with one or more aromatic or
non-aromatic non-siloxy-based monomers, hydrophobic monomers,
hydrophilic monomers or a combination thereof to produce polymeric
compositions of the present invention.
[0022] Examples of aromatic and non-aromatic non-siloxy-based
monomers useful for copolymerization with one or more
aromatic-based silyl monomers of the present invention include for
example but are not limited to 2-phenyoxyethyl methacrylate,
3,3-diphenylpropyl methacrylate, N,N-dimethylacrylamide, methyl
methacrylate, 2-(1-naphthylethyl) methacrylate, glycol
methacrylate, 3-phenylpropyl acrylate and 2-(2-naphthylethyl)
methacrylate but preferably 2-(1-naphthylethyl) methacrylate for
increased refractive index.
[0023] Examples of hydrophobic monomers useful for copolymerization
with one or more aromatic-based silyl monomers of the present
invention include for example but are not limited to 2-ethylhexyl
methacrylate, 3-methacryloyloxypropyldiphenylmethylsilane and
2-phenyloxyethyl methacrylate but preferably
3-methacryloyloxypropyldiphenylmethylsilane for increased
refractive index.
[0024] Examples of hydrophilic monomers useful for copolymerization
with one or more aromatic-based silyl monomers of the present
invention include for example but are not limited to
N,N-dimethylacrylamide and methyl methacrylate but preferably
N,N-dimethylacrylamide for increased hydrophilicity.
[0025] The physical and mechanical properties of copolymers
produced from formulations based on 3-phenylpropyl acrylate (PPA),
N,N-dimethylacrylamide (DMA),
3-acryloyloxypropyldiphenylmethylsilane (APDMS) and methyl
methacrylate (MMA) with are set forth below in Table 1.
1TABLE 1 Mechanical and Physical Property Results of formulations
based on PPA, DMA and APDMS (initiator Irgacure .TM. 819 at 0.5%
(Ciba-Geigy, Basel, Switzerland) and UV blocker at 0.25% for all
formulations) Mod Tear % % Composition W/W % R.I. (g/mm.sup.2)
(g/mm) % Elong. Rec. H.sub.2O PPA/DMA/APDMS/ 75/25/0/20/1 1.5349
5.1 Hex/Eg/819 75/25/0/20/2 1.5364 55 24 197 88 6.5 75/25/0/20/3 86
5.0 65/25/10/20/1 1.5396 50 47 338 80 4.5 65/25/10/20/2 1.5442 81
54 228 77 5 65/25/10/20/3 1.5448 143 57 178 72 5.7 55/25/20/20/1
1.5409 94 79 332 70 5.5 55/25/20/20/2 1.5429 141 77 232 64 4.8
55/25/20/20/3 1.5422 196 83 184 60 5 Hex = Hexanol Eg = EGDMA =
Ethyleneglycol dimethacrylate 819 = Irgacure .TM. 819
[0026] No water content, low water content of less than 15 percent
water content by volume and high water content "hydrogels" of 15
percent or higher water content by volume polymeric compositions of
the present invention having ideal physical characteristics for use
in the manufacture of ophthalmic devices are described herein. In
the production of such polymeric compositions of the present
invention, one or more silyl monomers of the present invention may
be polymerized or copolymerized to form crosslinked
three-dimensional networks. However, one or more crosslinking
agents may be added in quantities less than 10 percent weight per
volume (W/V) to the silyl monomer(s), if desired, prior to
polymerization or copolymerization thereof.
[0027] Examples of suitable crosslinking agents include but are not
limited to diacrylates and dimethacrylates of triethylene glycol,
butylene glycol, neopentyl glycol, hexane-1,6-diol, thio-diethylene
glycol and ethylene glycol, trimethylolpropane triacrylate,
N,N'-dihydroxyethylene bisacrylamide, diallyl phthalate, triallyl
cyanurate, divinylbenzene; ethylene glycol divinyl ether,
N,N'-methylene-bis-(meth)acrylamide, sulfonated divinylbenzene and
divinylsulfone.
[0028] Although not required, silyl monomers within the scope of
the present invention may optionally have one or more strengthening
agents added thereto prior to polymerization or copolymerization
thereof, preferably in quantities of less than about 80 weight
percent but more typically from about 20 to about 60 weight
percent.
[0029] Examples of suitable strengthening agents are described in
U.S. Pat. Nos. 4,327,203, 4,355,147 and 5,270,418, each
incorporated herein in its entirety by reference. Specific
examples, not intended to be limiting, of such strengthening agents
include cycloalkyl acrylates and methacrylates, such as for example
tert-butylcyclohexyl methacrylate and isopropylcyclopentyl
acrylate.
[0030] One or more ultraviolet light absorbers may optionally be
added to the subject silyl monomers prior to polymerization or
copolymerization thereof in quantities typically less than 2
percent W/V. Suitable ultraviolet light absorbers for use in the
present invention include for example but are not limited to
.beta.-(4-benzotriazoyl-3-hydroxyphenoxy)e- thyl acrylate,
4-(2-acryloyloxyethoxy)-2-hydroxybenzophenone,
4-methacryloyloxy-2-hydroxybenzophenone,
2-(2'-methacryloyloxy-5'-methylp- henyl)benzotriazole,
2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-2H-benzo- triazole,
2-[3'-tert-butyl-2'-hydroxy-5'-(3"-methacryloyloxypropyl)phenyl]-
-5-chlorobenzotriazole,
2-(3'-tert-butyl-5'-(3"-dimethylvinylsilylpropoxy)-
-2'-hydroxyphenyl]-5-methoxybenzotriazole,
2-(3'-allyl-2'-hydroxy-5'-methy- lphenyl)benzotriazole,
2-[3'-tert-butyl-2'-hydroxy-5'-(3"-methacryloyloxyp-
ropoxy)phenyl]-5-methoxybenzotriazole, and
2-[3'-tert-butyl-2'-hydroxy-5'--
(3"-methacyloyloxypropoxy)phenyl]-5-chlorobenzotriazole wherein
.beta.-(4-benzotriazoyl-3-hydroxyphenoxy)ethyl acrylate is the
preferred ultraviolet light absorber.
[0031] The silyl monomers of the present invention may be readily
cured in cast shapes, as discussed in more detail below, by one or
more conventional methods. Such methods include for example but are
not limited to ultraviolet light polymerization, visible light
polymerization, microwave polymerization, thermal polymerization,
free radical thermal polymerization or combinations thereof.
[0032] One or more suitable free radical thermal polymerization
initiators may be added to the monomers of the present invention.
Examples of such initiators include for example but are not limited
to organic peroxides, such as acetyl peroxide, lauroyl peroxide,
decanoyl peroxide, stearoyl peroxide, benzoyl peroxide, tert-butyl
peroxypivalate, peroxydicarbonate, and the like. Preferably such an
initiator is employed in a concentration of approximately 0.01 to 1
percent by weight of the total monomer mixture.
[0033] Representative ultraviolet light initiators include those
known in the field such as for example but not limited to benzoin
methyl ether, benzoin ethyl ether, Darocur.TM. 1173, 1164, 2273,
1116, 2959, 3331 (EM Industries) and Irgacur.TM. 651 and 184
(Ciba-Geigy, Basel, Switzerland).
[0034] The polymeric compositions of the present invention are of
relatively high refractive index, relatively high elongation and
relatively high clarity. The polymeric compositions of the present
invention with the desirable physical properties noted above are
particularly useful in the manufacture of ophthalmic devices such
as but not limited to relatively thin, foldable intraocular lens
implants, contact lenses and corneal inlays.
[0035] IOLs having relatively thin optic portions are critical in
enabling a surgeon to minimize surgical incision size. Keeping the
surgical incision size to a minimum reduces intraoperative trauma
and postoperative complications. A relatively thin IOL optic
portion is also critical for accommodating certain anatomical
locations in the eye such as the anterior chamber and the ciliary
sulcus. IOLs may be placed in the anterior chamber for increasing
visual acuity in either aphakic or phakic eyes, or placed in the
ciliary sulcus for increasing visual acuity in phakic eyes.
[0036] The polymeric compositions of the present invention have the
flexibility required to allow implants manufactured from the same
to be folded or deformed for insertion into an eye through the
smallest possible surgical incision, i.e., 3.5 mm or smaller. It is
unexpected that the subject polymeric compositions could possess
the ideal physical properties described herein. The ideal physical
properties of the subject polymeric compositions are unexpected
because high refractive index monomers typically lend to polymers
that have increased crystallinity and decreased clarity, which does
not hold true in the case of the subject polymeric
compositions.
[0037] The subject silyl monomers and polymeric compositions
produced therefrom are described in still greater detail in the
examples that follow.
EXAMPLE 1
Three-Step Synthesis of 3-acrylovioxypropvdiphenyl-methylsilane
(APDMS)
[0038] Step One: Synthesis of
3-(trimethylsilyloxy)propyldiphenylmethylsil- ane
[0039] In a two liter acid washed round bottom flask equipped with
magnesium stirrer, condenser and dry air tube was placed 100 g of
diphenylmethylsilane, (0.5042 moles), 656.7 g of
trimethylsilylallyl (TMS-allyl) alcohol (5.042 moles) and 1000
.mu.l of Pt catalyst (Aldrich Chemical Co. 47,951-9). The solution
was refluxed for 16 hours, cooled to room temperature and 20 g of
silica gel was added. Stirring was continued for 2 hours. The
mixture was filtered and rotovapped to oil. The oil was vacuum
distilled (boiling point (b.p.) 110-15.degree. C. at 0.1 mm Hg).
Recovered 158 g (GC-97%) yield 95%.
[0040] Step Two: Synthesis of
3-hydroxypropyldiphenylmethylsilane
[0041] In a one liter erylenmeyer flask was placed 161 g of the
product from step one above (0.4901 mole) dissolved in 700 ml of
methanol. To the above was slowly added 35 ml of distilled water
followed by 4 ml of glacial acetic acid. This solution was stirred
for 2 hours. The solution was rotovapped to remove the methanol;
re-dissolved in chloroform, washed with distilled water three
times, dried over magnesium sulfate and filtered. The solution was
rotovapped to a clear oil. Recovered 132 g (GC purity 93%).
[0042] Step Three: Synthesis of
3-acryloyloxypropyldiphenylmethylsilane
[0043] In a two liter round bottom flask equipped with mechanical
stirrer, dropping funnel, thermometer, condenser and N.sub.2
blanket was placed 132 g (0.4758 mole) of the deprotected alcohol,
53.6 g (0.53 moles) of triethylamine and 1000 ml of anhydrous ethyl
acetate. This solution was cooled to 0.degree. C. and 47 g (0.5234
moles) of acryloyl chloride was added dropwise, keeping the
temperature less than 5.degree. C. After the addition was complete,
the reaction was allowed to come to room temperature and stirred
under N.sub.2 overnight. The next morning the solution was washed
three times with cold 2N HCl, one time with brine and one time with
5% NaHCO.sub.3. The resulting solution was dried over MgSO.sub.4,
filtered and rotovapped to a yellow oil. The oil was passed through
a 400 g silica column eluding with 70/30, 50/50 and 30/70
heptane/dichloromethane solutions (2 bed volumes each). After
solvent removal, 59 g of 3-acryloyloxypropyldiphenylmethylsilane
(98.6% by GC) was recovered.
[0044] Synthesis of 2-(1-napthalylethyl)methacrylate
[0045] In a two liter amber colored round bottom flask equipped
with mechanical stirrer, dropping funnel, thermometer, condenser,
and N.sub.2 blanket was placed 50 g (0.2905 mole) of
1-naphthaleneethanol, 31.4 g (0.31 mole) of triethylamine and 1000
ml of ethyl acetate. The above was cooled to less than o.degree. C.
and 31.9 g (0.305 mole) of methacryloyl chloride was added dropwise
keeping the temperature less than 0.degree. C. The reaction was
allowed to come to room temperature and stirred under N.sub.2
overnight. The following morning, the organic layer was washed two
times with 1 N HCl, one time with brine, and two times with 5%
NaHCO.sub.3. The organic layer was dried over MgSO.sub.4, filtered
and rotovapped to an oil, and passed through 200 g of silica gel
eluding with 70/30 heptane/dichloromethane. After solvent removal,
recovered 48 g (GC purity 97%).
Example 2
[0046] To 65 parts of 3-phenylpropyl acrylate (PPA) was added 25
parts of N,N-dimethylacrylamide, 20 parts of hexanol, 10 parts of
APDMS, 3 parts of ethyleneglycol dimethacrylate and 0.5% of
Irgacure.TM. 819 as the UV photoinitiator and 0.25% of a commercial
triazole UV blocker (Aldrich Chemical Co). The clear solution was
sandwiched between two silanized glass plates using metal gaskets
and exposed to UV radiation for two hours. The resultant films were
released and extracted in isopropanol (IPA) for four hours,
followed by air-drying and a 30 mm vacuum to remove the IPA. The
resultant film was hydrated at room temperature overnight in borate
buffered saline. The clear tack-free films possessed a modulus of
81 g/mm.sup.2, a tear strength of 77 g/mm, a % elongation of 228%,
a water content of 5% and a refractive index of 1.5442.
Example 3
[0047] To 70 parts of APDMS was added 10 parts of
N,N-dimethylacrylamide, 20 parts of hexanol, 1 part of
ethyleneglycol dimethacrylate and 0.5% of Irgacure.TM. 819 as the
UV photoinitiator and 0.25% of a commercial triazole UV blocker
(Aldrich Chemical Co). The clear solution was sandwiched between
two silanized glass plates using metal gaskets and exposed to UV
radiation for two hours. The resultant films were released and
extracted in IPA for four hours, followed by air-drying and a 30 mm
vacuum to remove the IPA. The resultant film was hydrated at room
temperature overnight in borate buffered saline. The clear
tack-free films possessed a modulus of 161 g/mm.sup.2, a tear
strength of 64 g/mm, a % elongation of 183%, a water content of
10.5% and a refractive index of 1.517.
[0048] Ophthalmic devices such as but not limited to IOLs
manufactured using the polymeric compositions of the present
invention can be of any design capable of being rolled or folded
for implantation through a relatively small surgical incision,
i.e., 3.5 mm or less. For example, ophthalmic devices such as IOLs
typically comprise an optic portion and one or more haptic
portions. The optic portion reflects light onto the retina and the
permanently attached haptic portions 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.
[0049] The subject ophthalmic devices, such as for example IOLs,
may be manufactured to have an optic portion and haptic portions
made of the same or differing materials. Preferably, in accordance
with the present invention, both the optic portion and the haptic
portions of the IOLs are made of one or more polymeric compositions
of the present invention. Alternatively however, the IOL optic
portion and haptic portions may be manufactured from differing
materials and/or differing polymeric compositions of the present
invention, such as described in U.S. Pat. Nos. 5,217,491 and
5,326,506, each incorporated herein in its entirety by reference.
Once the particular material or materials are selected, the same is
either cast in molds of the desired shape or cast in the form of
rods and lathed or machined into disks. If cast in the form of rods
and lathed or machined into disks, the disks are lathed or machined
into IOLs at low temperatures below the glass transition
temperature(s) of the material(s). The IOLs, whether molded or
machined/lathed, are then cleaned, polished, packaged and
sterilized by customary methods known to those skilled in the
art.
[0050] In addition to IOLs, the polymeric compositions of the
present invention are also suitable for use in the manufacture of
other ophthalmic devices such as but not limited to contact lenses,
keratoprostheses, capsular bag extension rings, corneal inlays,
corneal rings or like devices.
[0051] IOLs manufactured using the unique polymeric compositions of
the present invention are used as customary in the field of
ophthalmology. For example, in a surgical procedure, an incision is
placed in the cornea of an eye. Most commonly, through the corneal
incision the natural lens of the eye is removed (aphakic
application) such as in the case of a cataractous natural lens. An
IOL is then inserted into the anterior chamber, posterior chamber
or lens capsule of the eye prior to closing the incision. However,
the subject ophthalmic devices may be used in accordance with other
surgical procedures known to those skilled in the field of
ophthalmology.
[0052] While there is shown and described herein monomers and
polymeric compositions, methods of producing the monomers and
polymeric compositions, methods of producing ophthalmic devices
using the polymeric compositions and methods of using ophthalmic
devices manufactured from the polymeric compositions, all in
accordance with 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. The present invention is likewise not intended to be
limited to particular devices described herein except insofar as
indicated by the scope of the appended claims.
* * * * *