Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02478151 2004-09-24
FLUOROSULFONE-SILICONE ~IYDROGEL,
CONTACT LENS MATERIALS, OPTICAL MEDICAL DEVICES
AND COMPOSITIONS THEREOF
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to bis(perfluoroalkylsulfonyl)amidoalkyl ester
monomers of
acrylic or methacrylic acids and bis(alkylsulfonyl) amidoethyl ester monomers
of acrylic and
methacrylic acid, which are used to copolymerize with other comonomers such as
2-hydroxy 3-
pentamethyldisiloxanylpropyl methacrylate and 2-pentamethyldisiloxanyl 3-
hydroxypropyl
methacrylate to produce polymers for the purpose of manufacturing various
types of contact
lenses and other optical devices, including optical medical devices. In
particular, one important
use of the materials made from the invention is the manufacture of corneal
contact lenses.
2. Description of the Related Art
In recent years, hydrophilic corneal lenses have become more and more popular
in the
United States, Canada, and throughout the world. In an attempt to create
contact lenses which
are comfortable, oxygen permeable, and essentially clean from deposits, it
requires incorporation
of the longer fluorocarbon chain component in order to make the surface of the
lens slick --
permitting easy movement on the eye without any friction and wettable to
accomplish necessary
-1-
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n .2Aa.',A7~...:::.. , 21M."7.:'N:m.~ _C
a~.Y......(N.,ry.,.:..:9&T.tdA'.~~'.,»:"S..fi.7Ad8d.a~'A~'t%w.~e.;e-
:F.:.kv~if';('.,d.,.,.NA1H"~F~:~Xfi'if4';.Z.r"'Y:lt3%.:~..~'
't,~i~'~4&:YSA~T..~'.~ F% ~'~'
CA 02478151 2004-09-24
comfort for the patient.
Previous hydrophilic contact lenses are based on 2-hydroxyethyl methacrylate
(HEMA) or
derivatives thereof which produce reasonable comfort to the patient while they
are clean;
however, when worn for a longer period of time they have a tendency to
accumulate deposits or
debris on the surface of the lens and then require constant cleaning or in
other cases become
disposable. The patient then has to dispose of the contact lenses and get new
ones.
While such materials accumulate proteinaceous matter as deposits on the
surface of the
lens, the lens is impaired to proper transparency; or, if the deposits on the
lens are too large, the
lens could cause abrasion to the wearer's eyes. In recent years lVicolson
describes, in U.S. Patent
#5,789,461 and related counterparts, extended wear hydrophilic. contact lenses
based on
fluoroethers and amido compound. However, as practical experience shows
patients require
longer periods of time for adaptation to use such lenses.
Furthermore, in U.S. patent # 4,095, 877, Stoy teaches how to crosslink
macromolecular
block copolymers using acrylonitrile, formaldehyde, butyraldehyde with
polyisocyanate such as
hexamethylene diisocyanate or m-toluylene diisocyanate, diepoxides and similar
components.
In Harvey III, U.S. Patent #4,711,943, silicone hydrogel contact lens
describes
copolymers made from amidosilicone methacrylates as his invention.
In an earlier Novicky patent, U.S. Patent #4,748,224, he describes silicone-
sulfone contact
lenses as RGP lenses and semi-RGP's. However, it is desirable to invent
contact lenses with
superior comfort from initial placement of the lens on the human eye to
achieve patient
satisfaction and patient desire to use contact lenses.
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CA 02478151 2004-09-24
SUMMARY OF THE INVENTION
The present invention, therefore, is intended to improve performance of
contact lenses on
human eyes. The copolymers of the present invention will give very good
optical-clarity when
hydrated because the copolymers contain a fluorocarbone chain monomer that
reduces surface
tension, that gives very good slick surface of the lens and remains free of
debris or deposits, even
when lenses are worn for longer periods of time. The copolymer plastic, when
hydrated, will have
increased strength over HEMA hydrophilic contact lenses. The copolymer plastic
of the present
invention can be prepared by polymerization in rod form and then processed
into contact lens
blanks and ultimately into contact lenses; or, can be directly cast molded in
specific molds directly
into the shape of contact lenses. The said contact lenses when immersed in
Alcon OPTI-FREE
contact lens solution gives wettable or an hydrophilic contact lens polymer.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A still fixrther face of the invention includes synthesis of the copolymer
plastic which,
when hydrated in saline solution, gives a water content between 0.1% to 40%
that can be used for
other medical devices, such as intra-ocular lenses, lenses for instruments
used for body contact
and health diagnostic instruments.
The present invention includes the following novel monomers:
(1) Bis(perfluoroalkylsulfonyl)amidoethyl methacrylate having the following
formula:
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CF3(CFz)nSOa R
0
~'N-(CHz)m-O- i-C=CHz ( I )
CF3(CFa)nSOa O
where n is an integer from 0 to 16; m is an integer from 1 to 5 and R is a
methyl group or
hydrogen.
(2) (N-perfluoroalkylsulfonyl N'-methylsulfonyl)amidoethyl methacrylate
formula:
CF3(CFz)nSOz O
N-(CHz)m-O-C-C=CIIz (II)
I
CHs{CH2)nSOa R
where n is an integer from 0 to 16; m is an integer from 1 to 5 and R is a
methyl group or
hydrogen.
(3) Bis(methylsulfonyl)amidoalkyl methacrylate having the following formula
CHs{CFIz)»SOa R
I
~N-(CHZ)na-O-C-C=CHz (III)
CHs(CHz)nSOz O
where n is an integer from 0 to 16; m is an integer from 1 to 5 and R is a
methyl group or
hydrogen.
(4) Another useful perfluoroalkylsulfoneamidoethyl methacrylate monomer from
prior
art is: 2-(N-ethylperfluoroalkylsulfonamido)ethylmethacrylate
O O
CHa=C-C-O-(CH2)n N--~-(CFz)m-CF3 (IV)
I I Il
Ri Rz O
wherein R~ and R2, which may be the same or different, are hydrogen, alkyl,
cyclic or phenyl
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CA 02478151 2004-09-24
groups, where n is an integer from 1 to 5 and m is an integer from 0 to 10.
Typical monomers are:
2-(N-ethylperfluoroalkylsulfonylamido)ethyl methacrylate, 2-(N-
ethylperfluoroalkylsulfonyl-
amido)ethyl acrylate or mixtures thereof.
Representative of the hydroxyalkyl monomer of acrylic or methacrylic acid are
those
having to following general formula:
O O
CHZ=C~-O-(CHZ)n-0H and CHa=C~-O-(CHz)n-OH
1 !
CIi3 H
where n is an integer from 1 to 5; 2,3 dihydroxypropyl acrylate and 2,3
dihydroxypropyl
methacrylate or mixtures thereof.
Representative of heteroatom hydrophilic monomer are those having the
following general
formulas:
O CH3
N H
and \~ N-C-C--CHZ
r ,!
CH~HZ CH3 O
N Vinyl 2-pyrrolidinone Dimethylacrylamide
Oxygen permeability monomer is represented by organosiloxanylalkyl ester
monomers of
acrylic and methacrylic acid have the structural formula:
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A X O R
t
A ~i-O --Si-(CHz)n-O~-C=CHZ (I-Si)
Y
m
wherein, X and Y are Ci to C6, alkyl, cyclic or phenyl groups and/or groups of
the following
structure:
A
1
A- -Si-O-
I
A m
m being an integer from 1 to 6, n being an integer from 1 to 3, A is selected
from Ci to C6, alkyl
or phenyl groups, and R is a methyl group or hydrogen.
A second useful group of organosiloxanylalkyl ester monomers of acrylic and
methacrylic
acids are represented by the following formula:
A X OR
t I 11
D- - l i-O- -- ~ -(CHz)n-O-C-C=CHa (II-Si)
A Y
~m
wherein, X and Y are C~ to C6, alkyl or phenyl groups or groups of the
following structure:
,A
D- --Si-O
1
A
m
m being an integer from 1 to 6, n being an integer from 1 to 3, A is selected
from Ci to C6, alkyl
or phenyl groups, R is a methyl group or hydrogen, and D is hydrogen or
hydroxy group.
_m~~: . _ ~~ ~.
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A third useful group of oganosiloxanylalkyl ester monomers of acrylic and
methacrylic
acids are represented by the following structural formula:
X O
CH3-Si-(CHz)n--O-~~ C=CHZ (III-Si)
I I
Y R
wherein, X and Y are groups of the following structure:
A
I
A-- -Si-O-
1
A m
m being an integer from 1 to 5, n is an integer from 1 to 3, whey. a A is
selected from Ci to Cs,
alkyl, cyclic or phenyl groups and R is a methyl group or hydrogen.
The fourth useful organosilicone monomer useful in the present invention is
represented
by the following formula O CHs CHs
1 1
CHz -C-C-O-CHz -CH-CH2 -O Si-O Si-
R OH CHs ~ CHs
h being an integer from 1 to 10
The fifth useful organosilicone monomer in the present invention is
represented by the
following formula:
_...-~. r ,~.,_-~,~,.p.._,.,~..~..~,.,-
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O
CHz=C-C-O-CHz- CH-CH2-OH
I
R O
C
CHz-Si-CHz
r -~--- -,
O
I
CH3-Si-CHs
CH3
Where n is an integer from 0 to 10
The copolymer plastic can be further modified to suppress deposits on the
surface of the
lens by incorporation of the fluorocarbon ester monomers of acrylic and
methacrylic acids,
namely:
perfluoroalkyl ester monomer having the general formula:
R
f
CFs(CF2)n-{CHz)m-O- ~-C=CHz
O
and
R
I
CF3(CFa-CFzO~t-(CHz)m-O- ~ -C=CHz
O
where n is an integer from 0 to 20; m is integer from 1 to 5 and R is hydrogen
or methyl group.
Additional fluorocarbone monomers can also be incorporated into copolymer
plastic of
the present invention, such as:
1H,1H, 7H-Dodecafluoroheptyl acrylate;
_g_
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1H,1H, 7H-Dodecafluroheptyl methacrylate;
1H,1H-Heptafluorobutyl acrylate;
1H,1H-Heptaflurobutyl methacrylate;
Hexafluoroisoropyl acrylate;
Hexafluoroisopropyl methacrylate;
Hexafluoro-2-methylisopropyl acrylate;
2,2,3,3,4,4,5,5-Octafluro-1,6-hexyl diacrylate;
2,2,3,3,4,4,5,5-Octafluoro-1,6-hexyl dimethacrylate;
2,2,3,3,3-Pentafluoropropyl methacrylate;
1H,1H,2H,2H-Perfluorodecyl acrylate;
1H,1H,2H,2H-Perffurodecyl methacrylate;
1H,1H,9H-Perflurononyl acrylate;
1H,1H,9H-Perfluorononyl methacrylate;
1H,1H-Perfluoro-n-octyl acrylate;
1H,1H,2H,2H-Perfluorooctyl acrylate;
mono-1H,1H-Perfluorooctyl itaconate;
1H,1H-Perfluoro-n-octyl methacrylate;
1H,1H,2H,2H-Perfluorooctyl methacrylate;
1H,1H,11H-Perfluoroundecyl acrylate;
1H,1H,11H-Perfluoroundecyl methacrylate;
and alkyl sulfone monomers can also be incorporated.
-9-
.~ .n_.~..~..,
CA 02478151 2004-09-24
The preferable monomers are:
methyl vinyl sulfone,
methyl styrene sulfone,
ethyl vinyl sulfone,
ethyl styrene sulfone,
propyl vinyl sulfone,
propyl styrene sulfone,
phenyl vinyl sulfone,
phenyl styrene sulfone,
cyclohexyl vinyl sulfone,
cyclohexyl styrene sulfone,
pentyl vinyl sulfone,
pentyl styrene sulfone,
butyl vinyl sulfone,
butyl styrene sulfone,
phenoxyethyl vinyl sulfone,
phenoxyethyl styrene sulfone,
divinyl sulfone,
methacryloxyethyl methyl sulfone,
methacryloxyethyl ethyl sulfone,
methacryloxyethyl propyl sulfone
methacryloxyethyl butyl sulfone,
-10-
CA 02478151 2004-09-24
methacryloxyethyl phenyl sulfone,
methacryloxyethyl pentyl sulfone,
methacryloxyethyl styrene sulfone, or mixtures thereof.
The copolymer plastic material can also be modified by adding amounts of alkyl
or cyclic
ester monomer of acrylic or methacrylic acids; preferably, methyl
methacrylate, methyl acrylate,
ethyl methacrylate, ethyl acrylate, cyclohexyl methacrylate, 2-
hydroxycyclohexyl methacrylate,
propyl methacrylate and propyl acrylate.
The hydrophilic contact lens material can be further modified to achieve
better hydration
of the lens by the addition of methacrylic acid or acrylic acid and a small
amount of cross-linking
agent to improve overall performance of the contact lenses. Representative
cross-linking agents
are ethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate,
triethyleneglycol
dimethacrylate, triethyleneglycol diacrylate, tetraethyleneglycol diacrylate,
divinyl benzene, divinyl
sulfone, trimethylolpropane trimethacrylate and mixtures thereof.
The preferred composition of the present invention comprises of
( a ) from about 1 to 60 weight percent of ethylenically unsaturated of bis
(perfluoroalkylsulfone)amidoethyl ester monomers of acrylic or methacrylic
acid and bis
(alkylsulfone)amidoethyl esters monomers of acrylic and methacrylic acid or
mixtures thereof;
( b ) from about 1 to 50 weight percent of ethylenically unsaturated
hydroxyalkyl
monomer of acrylic or methacrylic acid or mixtures thereof;
( c ) from about 5 to 70 weight percent organosilicone monomer;
( d ) from 2 to 40 weight percent of unsaturated wettability agemt monomers or
mixtures
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t
CA 02478151 2004-09-24
thereof;
( a ) from about 0.1 to 8 weight percent of acrylic or methacrylic acid or
mixtures thereof;
( f ) from about 0.1 to 10 weight percent of cross-linking agent monomers
(preferably,
ethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate,
triethyleneglycol dimethacrylate,
tetraethyleneglycol dimethacrylate or mixtures thereof;
( g ) from about 1 to 20 weight percent of alkyl or cyclic esters monomer of
methacrylie
acid and acrylic acid;
(h) from about 1 to 20 weight percent of perfluoroalkyl ester monomer of
acrylic and
methacrylic acids or mixtures thereof;
(i) from about 1 to 20 weight percent of additional cross-linking agent such
as
diisocyanates preferably 2-isocyanatoethyl methacrylate; 1,2
diisocyanatopropane, 1,4
diisocyanatobenzene, m-toluylene diisocyanate, 1,5 diisocyanato 1-
carboxypenatane and other
isocyanates can also be useful, and from 1 to 25 weight percent of silicone
surfactant based on
polyethylene on polypropylene glycol or mixture thereof.
The polymerization of the oxygen permeable wettable contact lens material is
disclosed in
the prior art using free-radical polymerization techniques such a.s disclosed
in Novicky U.S. Patent
#4, 86 l, 850.
Examples 1-3 illustrate the preparation of new organosulfoneamide ester
monomers of
acrylic and methacrylic acid.
-12-
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~,~n:.<..»~u~F~.. ~s~~~R$:g:>._~lb,MPX'a6cpy ,:ea . ~z.ka,fA' ,~ ~' . .~ ~
r,.~~ fax .-....H.2s~,w~- .uvrsa.~z =.,a.mww .,.e",..,..._~..y."..,rv~.
ff~ '.m'srfi~rr~.wr.R..xP.F:6r,''..Y ..?.vas.. .,.~, ,t,~,.~nyMF
CA 02478151 2004-09-24
EXAMPLE 1
A sodium salt was prepared by dissolving 4000 grams of
bis(pentafluoroethylsulfonyl)-
imide in 4000 ml of pure methyl alcohol, then was added 521.0 grams of sodium
methoxide
(CH30Na) which was dissolved in 2500 rnl of absolute methanol with the
continuous stirring of a
22 liter, 3 neck flask. After 1 hour of stirring, the methanol was removed by
distillation until the
temperature in the flask reached 70-80°C. The yield of dry salt product
was 4220 grams.
To a 12 liter flask equipped with thermometer, stirrer and distilling head,
was charged
4200 grams of the aforesaid dry sodium salt and then 780 grams of ethylene
chlorohydrin
(CICHzCH20H) was added. The mixture was heated until Iiquidified. The stirring
and heating
continued until the temperature of 115°C was reached; heating and
stirring was maintained at
115°C for 7 hours thereafter. 50.0 grams of sodium methoxide an 250 ml
of methanol was added
to the mixture. After'h hour the methanol was distilled off and the
temperature of the flask was
increased to 120°C;155 grams of chlorohydrin was added to the mixture
and the temperature was
held at 115°-120°C for 6 hours.
The reaction mixture was then cooled down to 35°C and 7 liters of
diethyl ether was
added. The mixture was heated and stirred at reflux for 45 minutes, cooled
down to room
temperature and filtered with suction on a Buchner funnel precoated with
Celite-545.
The filtrate was then transferred to a 5 liter separatory funnel and washed
with 2500 ml
of H20, then with 4% NaOH solution and again with water twice.
The washed ether solution was charged to a 12 liter flask equipped with a
distilling head
and mechanical mixer and the ether was distilled offl At the end of the
distillation, reduced
pressure was applied yielding 3530 grams of product that was identified by IR
as
-13-
CA 02478151 2004-09-24
bis(pentafluoroethylsulfonyl)amidoethanol.
EXAMPLE 2
To a 3 liter, 3 neck flask, equipped with mechanical stirrer, thermometer and
water cooled
reflux condenser, was charged 320.0 grams of bis(methylsulfonyl)imide, 90.0
grams of
paraformaldehyde (94% purity) and b00 ml of dry pure methanol. Sodium
methoxide was added
to the solution until pH 10 was obtained. Heating was applied on the flask and
refluxed for a 42
hour period. The reaction mixture was cooled down to room temperature and
methanol was
slowly stripped off until the temperature reached 105°C. Again, the
flask was cooled down and
1000 ml of diethyl ether was added to the flask and stirred for '/~: hour. The
content of the 3 liter
flask was transferred to a separatory funnel and washed with water and again
with 3% HCl
solution; the final washing was completed with distilled water. Diethyl ether
extract of
bis(methylsulfonyl)amidomethanol was dryed over MgS04 anhydrous; IVIgS04 was
then removed
by filtration. The crude product in diethyl ether was purified by
distillation. The yield was 73% of
bis(methylsulfonyl)amidomethanol and the identity of the compound was
confirmed by an IR
analysis.
EXAMPLE 3
To a 5 liter, 3 neck round bottom flask equipped with mechanical stirrer,
thermometer and
reflux condenser was charged: 2500 ml of dry toluene and 300 grams of
bis(perfluoroethyl-
sulfonyl)amidoethanol which was stirred until all sulfoneamide was dissolved.
The flask was
charged with 80 grams of triethylamine. At room temperature 170.0 grams of
methacryloyl
chloride was slowly added from an additional funnel over 1'h hour period;
white ppt was formed
in the flask of (CHsCH2)3.N.HC1. When all of the methacryloyl chloride
addition was completed
-14-
_.. .rv~ . .~ w_.~. . .. a . ~~ ...,~..k~... ..~~ ~-~ ~.~ ~:~~. _ ~,..:
~...~w~-~~..~ ~~ .;~.~.~F~ ~ . .~n . ~_._~,~m.. r ~~~.. ~~. .~__
~Y~.__.~..~.~~ ~,
CA 02478151 2004-09-24
the flask was warmed up to 65-70°C for 1 hour. The flask was cooled
down to ~15°C using an
ice water mixture. White ppt was filtered off on a Buchner funnel which was
pre-coated with a
Celite-545 filter aid using suction methods.
When all filtration was completed, the triethylamine.HCl was washed with cold,
dry
toluene to extract all product. Toluene and the corresponding ester of
methacrylic acid was
combined and washed with water one time and the toluene was removed by
distillation until the
temperature reached 105°C and full vacuum ~ 0.5 rnm Hg. The product was
distilled at 105° to
120°C and full vacuum. GC analysis and amount of the product
established the yield to be 91%.
IR analysis indentified the desirable product to be
bis(perfluoroethylsulfonyl)amidoethyl
methacrylate.
EXAMPLE 4
This illustrates the preparation of representative copolymer plastic material
for hydrophilic
contact lenses:
To a 200 ml flask was added 20 grams of HEMA {2-hydroxyethylmethacrylate), 15
grams
of N-vinyl 2-pyrrolidinone, 25 grams of Bis(perfluoroalkylsulfonyl)amidoethyl
methacrylate, 30
grams of organosilicone monomer {I-Si), 10 grams of methyl methacrylate and 5
grams of
methacrylic acid and 0.5 grams of t-butylperoxyoctoate. All components were
mixed thoroughly
and poured into polypropylene tubes/molds closed with stoppers and polymerized
in a water bath
or thermostated oven set at 65°C for a period of about 20 hours. The
rods or blanks were then
put into a thermostated oven preheated at 105°C for a period of 24
hours. The copolymer plastic
was hard and suitable for the manufacturing of contact lenses. When immersed
in a saline
-15-
CA 02478151 2004-09-24
solution (such as Alcon OPTI-FREE), the plastic became an hydrophilic lens
having a water
content of about 24.2 weight percent. Oxygen permeability of the material was
measured using
Schema-Versatae Model 920 instrument and the Dk value for the material was
determined to be
87.3 (cm2/sec) (ml Oz/ml sol x mm Hg).
EXAMPLE 5
This example illustrates the preparation of direct casting of contact lenses.
To a 200 ml
flask was added 20 grams of (N-perfluoroalkylsulfonyl-N'-
methylsulfonyl)amidoethyl
methacrylate, 20 grams of 2-hydroxyethyl methacrylate, 15 grams of N-vinyl
pyrrolidinone, 30
grams of organosilicone monomer (II-Si), 15 grams of methyl methacrylate, 8
grams of
methacrylic acid, 3 grams of TEGMA and 0.5 grams of free radical catalyst VAZO
67. All
components were thoroughly mixed and poured into contact lens casting molds
(such as described
in Travnicek U. S. Patent #4,165,158). Polymerization was carried out at room
temperature
(21°C ) by gradually increasing to115°C over a period of 3
hours; this temperature was
maintained for an additional 2 hours to finish the polymerization. The oven
was turned off and
the temperature was gradually brought back down to room temperature. The
casting molds were
removed from the oven and separated. The contact lenses were removed from the
concave
portion of the mold and hydrated in Alcon OPTI-FREE multi-purpose solution.
The expansion
factor was 1.15 and the water content of the lenses was 23 weight percent. The
power of the
lenses on hydration changed 0.75 diopters. The hydrated lenses were very
clear, slippery,
wettable and suitable for hydrophilic contact lenses.
-16_
CA 02478151 2004-09-24
EXAMPLE 6
This example illustrates the preparation of the representative copolymer
plastic material
for hydrophilic contact lenses. To a 200 ml flask was added 30 grams of
distilled HEMA, 15
grams of N-vinyl 2-pyrrolidinone, 1.5 grams of diethyleneglycol
dimethacrylate, 4.5 grams of
methacrylic acid, 20 grams of Bis(methylsulfonyl)amidoalkyl methacrylate, 20
grams of
organosilicone monomer (I-Si) and 10 grams of methyl methacrylate. The mixture
was stirred
together thoroughly and 0.5 grams of IABN catalyst was added, then stirred
again until all
catalyst was dissolved. The mixture was poured into contact lens mold
cavities. The molds were
closed with the convex part of the mold, then polymerized in a tlhermostated
oven at a
programmable temperature starting from 30°C to 118°C over a 2
hour period. The molds were
slowly cooled down in the oven until room temperature was reached. The molds
were removed
from the oven and the lenses were removed from the casting molds. The lenses
were then
hydrated for a period of 2-3 days in Alcon OPTI-FREE solution.
EXAMPLE 7
This example illustrates the preparation of copolymer plastic material with an
additional
polysulfone monomer. To a 200 ml flask was added 15 grams of distilled HEMA, 5
grams of
vinylmethyl sulfone, 10 grams of N-vinyl 2-pyrrolidinone, 20 grams of
Bis(methylsulfonyl)-
amidoethyl methacrylate, 15 grams of 2-(N-
ethylperfluorobutylsulfonylamido)ethyl methacrylate
25 grams of organosilicone monomer (III-Si) and 10 grams of methyl
methacrylate. The mixture
was stirred thoroughly and 0.5 grams of IABN catalyst was added; the mixture
was stirred again
until all the catalyst was dissolved. The mixture was poured into suitable
polypropylene molds
-17-
CA 02478151 2004-09-24
and polymerized in a thermostated oven starting from 30°G to
127°G, programmable over a 3
hour period of time. The lenses were processed in the same way as in Example
3, using the Alcon
OPTI-FREE solution for the hydration of the lenses.
EXAMPLES 8-13
Samples of optically clear plastic hydrophilic contact lenses were prepared in
accordance with EXAMPLE 3; however, component compositions were different as
described in
the following table:
TABLE
ExampYe Number
Components (Parts 8 9 10 11 12 13
2-(N-ethylperfluorobutylsulfonamido)ethyl- 5 - - 5 -
methacrylate
N-vinyl2-pyrrolidinone 15 10 12 15 20 18
2-hydroayethylmethacrylate 20 25 30 14.5 20 18
methacrylic acid S 7 6 S - S
ethyleneglycol dimethacrylate 2 - 0,5 - - -
diethyleneglycol dimethacrylate - 3 - 1.S - -
organosilicone monomer ( I-Si) 30 2S 20 23 20 25
organosilicone monomer (II-Si) - - - 1 - -
I
methylvinyl sulfone _ S - _ _ _
phenyl styrene sulfone _ - g _ _ _
methyl methacrylate 5 5 10 10 10 10
methacryloxyethylmethyl sulfone - _ - 5 _ _
Bis(pertluoroalkylsulfonyl)amidoethyl20 - 3.5 15 - 19
methacrylate
N-pertluoroalkylsulfonyl-N'-methylsulfonylamidoethyl- 15 - - 25 -
methacrylate
Bis(methylsulfonyl)amidoalkyl 3 - 10 - - 5
methacrylate
-18-
a a , ~~ ~..,~..~~~,.~-~r;M .;~ ~~-~~~,~.a~~ ~~~... ~.v~,~-~,~-
..~...,~.~,.~.~,~ ~_.,~".x.~,.._wv_m~~._,~0.~,~~,~
,
CA 02478151 2004-09-24
Note: All samples of the above copolymer plastics were clear after hydration.
EXAMPLE 14
This example illustrates the preparation of prepolymers for direct molding
process of
contact lenses.
To a 2 liter, round bottom 3 neck flask equipped with double jacket, for the
capability to
heat and cool reaction mixtures by using hot and/or cold water on the jacket,
a mechanical stirrer,
reflux condenser and thermometer was added: 15 parts of methyl methacrylate,
20 parts of
2-hydroxyethyl methacrylate, 28 parts of dimethyl acrylamide, 25 parts of
bis(methylsulfonyl)-
amidoethyl methacrylate, 10 parts of organosilicone ester monomer of
rnethacrylic acid (II-Si),
1.5 parts of ethylene glycol dimethacrylate and 0.08 parts of t-butyl
peroxyoctoate.
The mixture was stirred thoroughly and slow heat was applied in the flask
using warm
water. The mixture was continuously stirred and heat was applied until the
temperature reached
70°C. After 1'/z hour the mixture became more viscose. Once the
reaction mixture had the
desirable viscosity, the hot water on jacket was turned aff and the cold water
was applied to the
flask. The reaction mixture was then cooled down to 16°C. The
prepolymer was removed from
the reaction flask, drained into a dark brown bottle and stored in the
refrigerator at 0-S°C for
future use in the direct casting or molding of contact lenses.
EXAMPLE 15
This example illustrates direct molding of corneal contact lenses.
To a 250 ml Erlenmeyer flask was added 100 grams of prepolymer prepared in
Example 14 and 0.4 grams of ~lazo 64 free radical catalyst. The catalyst was
mixed in the
prepolymer until completely dissolved. The prepolymer mixture was then
transferred to suitable
-19-
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CA 02478151 2004-09-24
contact lens molds (such as CooperVision or UItraVision molds); thereafter,
all molds were filled
and the closing caps were applied and sealed. The molds were placed in a
thermostated oven
capable of increased temperatures from 30°C to 35°C in a period
of 2'h-3 hours. Once the
temperature reached 132°C, the oven temperature was held in the range
of 132-135°C for an
additional 2 hours. The heating was turned off and the temperature was
gradually dropped down
to room temperature in about 4-5 hours.
The molds containing the contact lenses were removed from the oven and
processed by
known techniques. The contact lenses were transferred to hydration vials where
Alcon Opti-Free
soaking solution was added to hydrate the lenses. After 2 days the lenses were
inspected and it
was determined that the water content of the lens was 26.5%.
EXAMPLE 16
Preparation of Prepolymer A.
To 250 ml round bottom, 3 neck flask equipped with double jacket (far the
capability to
heat and cool reaction mixtures by using hot and/or cold water in the jacket)
a mechanical stirrer,
reflux condenser and thermometer was added: 30 parts of methyl methacrylate,
40 parts of
2-hydroxyethyl methacrylate, 5 parts of triethyleneglycol dimethacrylate,10
parts of m-toluylene
diisocyanate and 0.1 part of Vazo 64 catalyst. The monomers were mixed
thoroughly and were
continuously stirred while heat was applied the same way as in Example 15.
When viscosity of
the Prepolymer A reached the desired point, the viscous syrupy mixture was
transferred to a dark
brown bottle and stored in the refrigerator.
-20-
CA 02478151 2004-09-24
Preparation of Prepolymer B.
To a 250 ml round bottom, 3 neck flask equipped with double jacket (for the
capability to
heat and cool reaction mixtures by using hot and/or cold water in the jacket)
a mechanical stirrer,
reflux condenser and thermometer was added: 40 grams of dimethylacrylamide, 10
grams of N-
Vinyl 2-pyrrolidinone, 40 grams of organosilicone monomer (I-Si), 10 grams of
bis(N-perfluoro-
ethylsulfonyl)amidoethyl methacrylate and 0.2 grams of Vazo 64 catalyst. The
prepolymer was
prepared in the same technique as described in Example 14 and stored in the
refrigerator for use
in direct molding of contact lenses with Prepolymer A.
EXAMPLE 17
This example demonstrates direct molding of silicone hydrogel contact lenses.
To a 250 ml Erlenmeyer flask was added 50 grams of Prepolymer A and 50 grams
of
Prepolymer B which was prepared in Example 16. Also added was 0.3 S grams of
t-butylperoxyoctoate and the viscous prepoplymers were mixed thoroughly
together. The
prepolymer mixture was dispensed to contact lens molds and sealed using
molding caps. The
molds were placed in a thermostated oven in the same way as in Example 15; the
polymerization
process was identical to the above cited Example. The contact lenses were then
removed from
the molds and hydrated in Alcon Opti-Free multi purpose solution. The contact
lenses were
oxygen permeable and hydrophilic.
EXAMPLE 18
This example illustrates preparation of new hydrophilic organosilicone
monomer:
-21-
CA 02478151 2004-09-24
To a 12 liter clean and dry flask was added 6 liters of dry toluene and then
while stirring was
added 959 grams of 2,3 dihydroxypropyl methacrylate. Also to the flask was
added 500 grams of
dry pyridine. The solution was stirred and cooled down to about 5 C in the ice
water mixture.
Whe temperature reached 5 C from additional funnel was slowly added 1090 grams
of
pentamethyldisiloxanylchlorosilane over the period of about 1. S hours. During
the addition
reaction mixture was stirred and white precipitation was formed of pyridinium
hydrochloride in
the toluene. The reaction mixture was stirred over night for at least 10
hours. Then white
precipitation was filtered offthrough precoated frite filter type C. Then
toluene was stripped off,
then vacuum was applied at about 90 C and front ends were distilled off until
temperature reached
107 C. Product started distilling off at 108 C and full vacuum (0.5 mm Hg
using Sargent-Welch
M# 1402 vacuum pump) When temperature reached 113 C and full vacuum and about
95% of the
product was distilled. Product was labeled: Hydrophilic Silicone Monomer and
stored in
refrigerator for future use.
EXAMPLE 19
The examples 19 and 20 illustrates preparation of silicone-hydrogel contact
lens material
comprising at least one hydroxyorganosiloxanylalkoxy ester monomer:
To 200 ml flask it equipped with stirrer was added:
5.0 grams of HEMA, 0.5 grams of HEMA-PC (Phosphoro chilate) and dissolved:
4.0 grams of cyclohexyl methacrylate, 1.2 grams of Tri EGDMA, 8.6 grams of
NVP,4.0 grams of
bis(trifluoromethylsulfonyl)amidoethyl tnethacrylate 12.6 grams of
dimethylacrylamide, 0.60
grams of Vazo-65 catalyst, 50.0 grams of
tris(trimethylsiloxy)methacryloxypropylsillane and 14. S
grams of 2-hydroxy 3-pentamethyldisiloxanylpropyl methacrylate. A11 monomers
were stirred
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CA 02478151 2004-09-24
very well and polymerized in lens molds in thermostated oven at the
temperature of 70 C. The
resulting lenses were optically clear, having oxygen permeability of about Dk
value 125, and
water content on hydration of 11.3%.
EXAMPLE 20
200m1 flask was added
5.0 grams of HEMA, 4.0 grams of cyclohexyl methacrylate, 1.0 grams of Tri
EGDMA, 0.01
grams of D&C #6 color, 8.0 grams of NVP, 4.0 grams of
bis(pentafluoroethylsulfonyl)amidoethyl methacrylate, 2.0 gram s of 2-(N-
ethylperfluorobutyl-
sulfonamido)ethyl methacrylate, 10.5 grams of dimethylacrylamide, 0.6 grams of
Vazo-65
catalyst, 35 grams of Tris{pentamethyldisiloxanyl)methacryloxypropylsilane and
30 grams of 3-
hydroxy 2-pentamethyldisiloxanylpropyl methacrylate.
Although I have described my invention in connection with specific examples
and
preferred embodiments thereof, it is readily apparent to those skilled in the
art that the invention
may be modified without departing from the scope of the claims
