CA2622733A1 - Silicone hydrogel contact lenses, optical medical devices and compositions thereof - Google Patents

Abstract

Highly comfortable oxygen permeable and hydrophilic contact lenses are manufactured from a copolymer of an ethylenically unsaturated monomers;
bis[tris(trimethylsiloxy)silylpropyl]methacrylamide, bis[tris(trimethylsiloxy)silylpropyl]acrylamide, 3-tris(trimethylsiloxy)silylpropylmethacrylamide, 3-tris(trimethylsiloxy)silylpropylacrylamide, 2-(N-ethylperfluoroalkylsulfonamido)ethylmethacrylate and organosilicone ester monomers of acrylic and methacrylic acid and ethylenically unsaturated ester monomers of methacrylic acid having alkyl hydroxy groups, N-vinyl 2-pyrolidinone, dimethylacrylamide, methacrylic acid, and methods for the manufacturing thereof.

Description

SILICONE HYDROGEL

CONTACT LENSES, OPTICAL MEDICAL DEVICES
AND COMPOSITIONS THEREOF
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to bis[tris(trimethylsiloxy)silylpropyl]methacrylamide, bis[tris(trimethylsiloxy)silylpropyl]acrylamide, 3-tris(trimethylsiloxy)silylpropylmethacrylamide, and 3-tris(trimethylsiloxy)silylpropylacrylamide which are used to produce polymers for the purpose of manufacturing various types of contact lenses and other optical devices, including hydrophilic contact lenses. 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 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 Nicolson describes, in U.S. Patent No. 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 No. 4,095, 877, Stoy teaches how to cross-link 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 No. 4,711,943, silicone hydrogel contact lens describes copolymers made from amidosilicone methacrylates as his invention.

In an earlier Novicky patent, U.S. Patent No. 4,748,224, he describes silicone-sulfone contact lenses as RGP lenses and semi-RGP's. In the U.S. Patent No. 7,098,282 Novicky describes a new organosulfone monomer and its use for hydrophillic silicone hydrogel contact lenses. 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.

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 may 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 further 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 monomers:
(1) bis[tris(trimethylsiloxy)silylpropyl]methacrylamide having the following general formula:
0 ~CHZ)m - Sl[O - Sl(CH3)313 CH2= C-C-N
R (CHZ)n - Si[O - Si(CH3)3]3 where m is an integer from 1 to 4 and R is an alkyl group (2) bis[tris(trimethylsiloxy)silylpropyl]acrylamide:
0 CHz),n - Si[O - Sl(CH3)3]3 CHZ= C-C-N
H (CHZ),,, - Si[O - Si(CH3)3]3 where m is an integer from 1 to 5

(3) 3-tris(trimethylsiloxy)silylpropylmethacrylamide, and 3-tris(trimethylsiloxy)silylpropylacrylamide having the following formulas:
O 0 - S1(CH3)3 CH2=C-C-N-(CH2)3-Si-0 -Si (CH3)3 I ~
CH3 H O - S1(CH3)3 and 0 O - Si (CH3)3 CH2=C-C-N-(CH2)3-Si/ O-Si (CH3)3 H H O - Si (CH3)3

(4) Another useful perfluoroalkylsulfoneamidoethyl methacrylate monomer is: 2-(N-ethylperfluorobutylsulfonamido)ethylmethacrylate:
Q O

CHz=C- iC~-O-(CHz)n-N-S-(CF2)m-CF3 R, R2 0 wherein R, and Rz which may be the same or different, are hydrogen, alkyl, cyclic or phenyl 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-ethylperfluoroalkylsulfonylamido)ethyl acrylate or mixtures thereof.
Representative of the hydroxyalkyl monomer of acrylic or methacrylic acid are those having te following general formula:

il ii CH2=C - C- O-(CH2)n - OH and CH2=C - C- O-(CH2)n - OH
I I

2,3 dihydroxypropyl methacrylate 2,3 dihydroxypropyl acrylate where n is an integer from 1 to 5, Representative of heteroatom hydrophilic monomer are those having the following general formulas:
\~~ I CH3 H CH3 O
NO and N-C-C=CH2 and N-C-C=CH2 ~ i II ~ I
CH=CH2 CH3 0 CH3 CH3 N-vinyl 2-pyrrolidinone dimethylacrylamide dimethylmethacrylamide Additionally oxygen permeability monomer is represented by organosiloxanylalkyl ester monomers of acrylic and methacrylic acid have the structural formula:

A X O R
I II I
A Si - O Si -(CH2) - O- C- C= CH2 (I-Si) A Y
jm wherein, X and Y are Ci to C6, alkyl, cyclic or phenyl groups and/or groups of the following structure:
A
A Si - O
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 O R
D Si - O (CH2)n - O- C- C= CH2 (II-Si) 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, hydroxy group or alkyl group A third useful group of oganosiloxanylalkyl ester monomers of acrylic and methacrylic acids are represented by the following structural formula:

x 0 CH3 - Si - (CH2)n - O - C - C = CH2 (III-Si) Y R
wherein, X and Y are groups of the following structure:
A
A Si-O-A
m

-5-m being an integer from 1 to 5, n is an integer from 1 to 3, where A is selected from Ci to C6, alkyl, cyclic or phenyl groups and R is a methyl group or hydrogen.
The copolymer plastic can be further modified to suppress deposits on the surface of the lens by incorporation of the fluorocarbone ester monomers of acrylic and methacrylic acids, namely:
perfluoroalkyl ester monomer having the general formula:
R
CF3(CF2)n -(CH2)m - O- C- C= CH2 O
and R
CF3(CF2 - CF2O)n - (CH2)m - O - U - C = CH2 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:
1 H,1 H, 7H-Dodecafluoroheptyl acrylate;

1 H,1 H, 7H-Dodecafluroheptyl methacrylate;
1 H,1 H-Heptafluorobutyl acrylate;

1 H,1 H-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;
1 H,1 H,2H,2H-Perfluorodecyl acrylate;
1 H,1 H,2H,2H-Perflurodecyl methacrylate;
1 H,1 H,9H-Perflurononyl acrylate;

-6-1 H,1 H,9H-Perfluorononyl methacrylate;
1 H,1 H-Perfluoro-n-octyl acrylate;
1 H,1 H,2H,2H-Perfluorooctyl acrylate;
mono-1 H,1 H-Perfluorooctyl itaconate;
1 H,1 H-Perfluoro-n-octyl methacrylate;
1 H,1 H,2H,2H-Perfluorooctyl methacrylate;
1 H,1 H,11 H-Perfluoroundecyl acrylate;
1 H,1 H,11 H-Perfluoroundecyl methacrylate;
and alkyl sulfone monomers can also be incorporated.
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,

-7-methacryloxyethyl propyl sulfone methacryloxyethyl butyl sulfone, 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 80 weight percent of ethylenically unsaturated monomers bis [tris(trimethylsiloxy)silylpropyl] acrylamide, bis[tris(trimethylsiloxy)silylpropyl]methacrylamide, 3-tris(trimethylsiloxy)silylpropylmethacrylamide, and 3-tris(trimethylsiloxy)silylpropylacrylamide 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 30 weight percent organosilicone monomer;

( d) from 2 to 40 weight percent of unsaturated wettability agent monomers, such as N-vinyl2-pyrrolidinone, dimethylacrylamide and dimethylmethacrylamide or mixtures thereof;
( e) from about 0 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,

-8-tetraethyleneglycol dimethacrylate, polysiloxanyalkyldimethacylate monomer or mixtures thereof;
( g) from about 1 to 20 weight percent of alkyl or cyclic esters monomer of methacrylic acid and acrylic acid;
(h) from about 0 to 20 weight percent of perfluoroalkyl ester monomer of acrylic and methacrylic acids or mixtures thereof and The polymerization of the oxygen permeable wettable contact lens material is disclosed in the prior art using free-radical polymerization techniques such as disclosed in Novicky U.S.
Patent No. 4,861,850.
Examples 1-3 illustrate the preparation of organosiliconeamide ester monomers of acrylic and methacrylic acid.
Another composition according to the invention is a contact lens material comprising from about 5 to 80 weight percent of the group consisting of bis [tris(trimethylsiloxy)silylpropyl]methacrylamide, bis[tris(trimethylsiloxy)silylpropyl]acrylamide, 3-tris(trimethylsiloxy)silylpropylmethacrylamide, and 3-tris(trimethylsiloxy)silylpropylacrylamide.
from about 2 to 30 weight percent of organosilicone monomer selected from the group consisting of (I-Si), (II-Si), (III-Si) of the following formulas:

A X O R
A SI - O Si -(CH2)n - O- C- C= CH2 (I-Si) A Y
m wherein X and Y are C, to C6, alkyl, cyclic or phenyl groups and/or groups of the following structures:
A
A Si - O

' A m m being an integer from 1 to 6, n being and integer from 1 to 3, A is selected from C, to C6, alkyl or phenyl groups, and R is a methyl group or hydrogen;

-9-a group of organosiloxanylalkyl ester monomers of acrylic and methacrylic acid represented by the following formula:
A X O R
D Si - O Si -(CH2)n - O- C- C= CHZ (II-Si) A m Y

wherein, X and Y are C, to C6, alkyl or phenyl groups or groups of the following structure:
A
A Si - O
A
m m being an integer from 1 to 6, n being an integer from 1 to 3, A is selected from C, to C6, alkyl or phenyl groups, R is a methyl group or hydrogen and D is hydrogen or hydroxy group.; and a group of organosiloxanylalkyl ester monomers of acrylic and methacrylic acids represented by the following structural formula:

' I I
CH3 - Si - (CH2)n - O - C - C = CH2 (III-Si) Y R
wherein X and Y are groups of the following structure:
A
A Si - 0 A m m being an integer from 1 to 5, n is an integer from 1 to 3, wherein, A is selected from C, to C61 alkyl, cyclic or phenyl groups and R is a methyl group or hydrogen and mixtures thereof;

from about 1 to 40 weight percent of 2-hydroxyethyl methacrylate or 2,3-dihydroxypropyl methacrylate, dimethylacrylamide, dimethylmethacrylamide, N-vinyl 2-pyrrolidinone or mixtures thereof from about 1 to 30 weight percent of perfluoroalkyl ester monomer of acrylic or methacrylic acid; and from about 1 to 10 weight percent of cross-linking agents selected from the group

-10-consisting of ethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, tetraethyleneglycol dimethacrylate, dimethacrylate siloxyanyl ester monomer, ehtyleneglycol diacrylate, tetraethylene-glycol diacrylate, divinyl benzene sulfone or mixtures thereof; said contact lens material additionally embodies methacrylic acid or acrylic acid each in an amount up to an amount sufficient to constitute, with other compounds, 100 weight percent of the contact lens material.

This example illustrates the preparation of the representative copolymer plastic material for hydrophilic contact lenses. To a 200 ml flask was added 40 grams of 3-tris(trimethylsiloxy)silylpropylmethacrylamide, 40 grams of dimethylacrylamide, and 15 grams of N-vinyl 2-pyrrolidinone, 4 grams of diethyleneglycoldimethacrylate, and 0.2 grams of 2,2-Azobis(2,4-dimethyl valeronitrile) as catalyst was added. The mixture was stirred together thoroughly until all catalyst was dissolved. The mixture was then poured into polypropylene caps of 12.7 mm diameter and placed in an aluminum plate in a thermostated oven at a programmable temperature starting from 25 C to 130 C. After 4 hours in the polymerization oven the temperature of the oven was turned off and slowly cooled down over a period of 3 hours to room temperature. The polymer plastic was removed from the molds (caps) and was cut to the shape of contact lens. The contact lens was hydrated in the contact lens hydrating solution for a period of 24 hours. The lens became soft and hydrophilic having about 33% water content.

This example illustrates the preparation of bis[tris(trimethylsiloxy)silylpropyl]metacrylamide To a three-necked, round bottom 221iter flask equipped with mechanical stirrer and cooling system is added 121iter of dry hexane, 650 grams of bis[tris(trimethylsiloxy)silylpropyl]amine and 202.4 grams of triethylamine. The flask is then cooled to about 15 C. When the temperature is reached, start the addition from additional funnel of 206.8 grams of metacrylylchloride with 252 ml of hexane, all additions take about one hour of time. Then the temperature is raised to 38 C and the stirring continued for four hours. After the reaction is complete the reaction mixture is cooled down to 10 C and the white precipitation, triethylamine hydrochloride, which formed during the reaction is filtered off through frit filter type C, which was previously precoated with Celite 545. Next the hexane containing product is distilled off at room temperature which

-11-removes all traces of the hexane. Distillation proceeds under vacuum first at 160 C and 2.5 mm Hg pressure and then at 175 C and about 0.5 mm Hg pressure. The product bis[tris(trimethylsiloxy)silylpropyl]metacrylamide was collected. The infrared spectrum confirmed structure of the product. The product yield 726 grams of bis [tris(trimethylsiloxy)silylpropyl]metacrylamide This illustrates the preparation of representative copolymer plastic material for hydrophilic contact lenses:

To a 200 ml flask was added 10 grams of HEMA (2-hydroxyethylmethacrylate), 15 grams of N-vinyl 2-pyrrolidinone, 40 grams of 3-tris(trimethylsiloxy)silylpropylmethacrylamide, 20 grams of bis[tris(trimethylsiloxy)silylpropyl]metacrylamide, and 10 grams of 2-(N-ethylperfluoroalkylsulfonamido)ethylmethacrylate, 4.5 grams of dimethylacrylamide, 0.5 grams of HEMA-PC (phosphoro monomer for the purpose of retaining constant wettability of the lens), and 0.5 grams of 2,2-Azobis(2,4-dimethyl valeronitrile). All components were mixed thoroughly and poured into polypropylene tubes/molds closed with stoppers and polymerized in a water bath 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 solution (such as Alcon OPTI-FREE), the plastic became an hydrophilic lens having a water content of about 29 weight percent. Oxygen permeability of the material was measured using Schema-Versatae Mode1920 instrument and the Dk value for the material was determined to be 129 (cm2/sec) (ml 02/mi sol x mm Hg).

This example illustrates the preparation of direct casting of contact lenses.
To a 200 ml flask was added 20 grams of 2-(N-ethylperfluoroalkylsulfonamido)ethylmethacrylate, 15 grams of dimethylacrylamide, 45 grams of 3-tris(trimethylsiloxy)silylpropylmethacrylamide, 5 grams of methyl methacrylate, 2 grams of methacrylic acid, 3 grams of TriEGMA and 0.5 grams of free radical catalyst VAZO 67. All components were thoroughly mixed and poured into contact lens casting molds. Polymerization was carried out in the thermostatic oven at room temperature

-12-(21 C ) by gradually increasing to 115 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 1.17 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.

This example illustrates the preparation of the representative copolymer plastic material for hydrophilic contact lenses. To a 200 ml flask was added 5 grams of distilled HEMA, 15 grams of N-vinyl 2-pyrrolidinone, 1.5 grams of diethyleneglycol dimethacrylate, 0.5 grams of methacrylic acid, 20 grams of 3-tris(trimethylsiloxy)silylpropylmethacrylamide, 20 grams of bis[tris(trimethylsiloxy)silylpropyl]metacrylamide and 10 grams of cyclohexyl 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 thermostated 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.

This example illustrates the preparation of copolymer plastic material with an additional monomer. To a 200 ml flask was added 15 grams of distilled HEMA, 10 grams of N-vinyl 2-pyrrolidinone, 20 grams of bis[tris(trimethylsiloxy)silylpropyl]metacrylamide acylate, 15 grams of 2-(N-ethylperfluorobutylsulfonylamido)ethyl methacrylate, 10 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 and

-13-polymerized in a thermostated oven starting from 30 C to 127 C, 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.

Samples of optically clear plastic hydrophilic contact lenses were prepared in accordance with EXAMPLE 4; however, component compositions were different as described in the following table:
TABLE

Example Number Components (Parts) 7 8 9 10 11 12 2-(N-ethylperfluorobutylsulfonamido)ethyl methacrylate 10 5 15 - 5 5 N-vinyl 2-pyrrolidinone 15 10 12 15 20 18 2-hydroxyethylmethacrylate 10 - - 4.5 - 5 methacrylic acid 2 2 - 3 - 2 ethyleneglycol dimethacrylate 2 2 0.5 - 2 -diethyleneglycol dimethacrylate - - - 1.5 - 2 organosilicone monomer ( I-Si) 5 - - 23 - -organosilicone monomer (II-Si) - 5 - - 10 10 3-tris(trimethylsiloxy)silylpropylmethacrylamide 20 15 20 35 45 -bis[tris(trimethylsiloxy)silylpropyl]metacrylamide 20 40 8 - - 30 methyl methacrylate 5 5 10 5 5 -1,3-bis(methacrylamidopropyl)tetramethyldisiloxane 5 - 10 5 10 -bis(trimethylsiloxy)methylpropylmethacrylamide - 10 20 - - 20 dimethylacrylamide 6 - 4.5 - 3 5 mono methacrylamide terminated PDMS; -500 MW - 6 - 8 - 3 Note: All samples of the above copolymer plastics were clear after hydration.

-14-This example illustrates direct molding of corneal contact lenses.
To a 250 ml Erlenmeyer flask was added all components as in example 5 with the exception that the catalyst in example 5 was replaced with 0.4 grams of Vazo 64 free radical catalyst. The catalyst was mixed in the monomer composition until completely dissolved. The polymerization mixture was then transferred to suitable contact lens 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 110 C in a period of 2/2-3 hours. Then the temperature was gradually increased to 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 soft lens hydrating 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 24 to 25%.

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 mbdified without departing from the scope of the claims

Claims (15)

The invention claimed is:

1. A plastic material formed of a copolymer which comprises:
from about 5 to about 80 weight percent of at least one monomer selected from the group consisting of:

(1) bis[tris(trimethylsiloxy)silylpropyl]methacrylamide having the following formula:
where m is an integer from1 to 4 and R is an alkyl group (2) bis[tris(trimethylsiloxy)silylpropyl]acrylamide:

where m is an integer from 1 to 5 (3) 3-tris(trimethylsiloxy)silylpropylmethacrylamide, and 3-tris(trimethylsiloxy)silylpropylacrylamide having the following formulas:

2. A copolymer plastic material of claim 1, wherein said material is modified by incorporating from about 2 to 30 weight percent (based on the total weight of said plastic material) of alkylsulfoneamidoethyl esters monomers of acrylic and metacrylic acid.

3. A copolymer plastic material of claim 1, wherein said polymer is further modified by the incorporation of organosulfone ester monomer of acrylic and methacrylic acid or an organosulfone monomer having a vinyl polymerizable group

4. An ophthalmic device which is manufactured from oxygen permeable and hydrophilic copolymer plastic material which comprises of at least one from the following monomers:

(1) bis[tris(trimethylsiloxy)silylpropyl]methacrylamide having the following formula:
where m is an integer from1 to 4 and R is an alkyl group (2) bis[tris(trimethylsiloxy)silylpropyl]acrylamide:
where m is an integer from 1 to 5 (3) 3-tris(trimethylsiloxy)silylpropylmethacrylamide, and 3-tris(trimethylsiloxy)silylpropylacrylamide having the following formulas:

5. The ophthalmic device of claim 4, which is manufactured from oxygen permeable and hydrophilic copolymer plastic material; said plastic embodies at least one organosilicone monomer selected from the group consisting of the following formulas:

wherein X and Y are C1 to C6, alkyl, cyclic or phenyl groups and/or groups of the following structures:

m being an integer from 1 to 6, n being an integer from 1 to 3, A is selected from C1 to C6, alkyl or phenyl groups, and R is a methyl group or hydrogen;
a group of organosiloxanylalkyl ester monomers of acrylic and methacrylic acid represented by the following formula:

wherein X and Y are C1 to C6, alkyl or phenyl groups or groups of the following structure:
m being an integer from 1 to 6, n being an integer from 1 to 3, A is selected from C1 to C6, alkyl or phenyl groups, R is a methyl group or hydrogen and D is hydrogen or hydroxy group, and a group of organosiloxanylalkyl ester monomers of acrylic and methacrylic acids represented by the following structural formula:

wherein X and Y are groups of the following structure m being an integer from 1 to 5, n is an integer from 1 to 3, wherein, A is selected from C1 to C61 alkyl, cyclic or phenyl groups and R is a methyl group or hydrogen.

6. A contact lens material comprising from about 5 to 65 weight percent of a compound selected from the group consisting of bis[tris(trimethylsiloxy)silylpropyl]methacrylamide, bis[tris(trimethylsiloxy)silylpropyl]acrylamide, 3-tris(trimethylsiloxy)silylpropylmethacrylamide, and 3-tris(trimethylsiloxy)silylpropylacrylamide; from about 2 to 30 weight percent of organosilicone monomer selected from the group consisting of (I-Si), (H-Si), (III-Si) of the following formulas:

wherein X and Y are C1 to C6, alkyl cyclic or phenyl groups and/or groups of the following structures:

m being an integer from 1 to 6, n being an integer from 1 to 3, A is selected from C1 to C6, alkyl or phenyl groups, D is hydrogen ot hydroxy group and R is a methyl group or hydrogen;
a group of organosiloxanylalkyl ester monomers of acrylic and methacrylic acid is represented by the following formula:

wherein, X and Y are C1 to C6, alkyl or phenyl groups or groups of the following structure:
m being an integer from 1 to 6, n being an integer from 1 to 3, A is selected from C1 to C6, alkyl or phenyl groups, R is a methyl group or hydrogen and D is hydrogen or hydroxy group; and a group of organosiloxanylalkyl ester monomers of acrylic and methacrylic acids represented by the following structural formula:

wherein X and Y are groups of the following structure:
m being an integer from 1 to 5, n is an integer from 1 to 3, wherein, A is selected from C1 to C6, alkyl cyclic or phenyl groups and R is a methyl group or hydrogen and mixtures thereof from about 1 to 40 weight percent of 2-hydroxyethyl methacrylate or 2, 3-dihydroxypropyl methacrylate, dimethylacrylamide, N-vinyl 2-pyrrolidinone or mixtures thereof; from about 1 to 20 weight percent of diisocynates; from about 1 to 30 weight percent of perfluoroalkyl ester monomer of acrylic or methacrylic acid; and from about 1 to 10 weight percent of cross-linking agents selected from the group consisting of ethyleneglycol dimethacrylate , diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, tetraethyleneglycol dimethacrylate, dimethacrylate siloxanyl ester monomer, ethylneglycol diacrylate, tetraethylene- glycol diacrylate, divinyl benzene sulfone or mixtures thereof; said contact lens material additionally embodies methacrylic acid or acrylic acid each in an amount up to an amount sufficient to constitute, with other components, 100 weight percent of the contact lens material.

7. A medical device which is manufactured by direct molding in which a monomer selected from the group (1), (2) and (3) (1) bis[tris(trimethylsiloxy)silylpropyl]methacrylamide having the following formula:
where m is an integer from1 to 4 and R is an alkyl group (2) bis[tris(trimethylsiloxy)silylpropyl]acrylamide:
where m is an integer from 1 to 5 (3) 3-tris(trimethylsiloxy)silylpropylmethacrylamide, and 3-tris(trimethylsiloxy)silylpropylacrylamide having the following formulas:
is mixed with N-vinyl pyrrolidinone, dimethylacrylamide and 2-N(ethylperfluorobutylsulfonamido)ethylmethacrylate or 2-N(ethylperfluorooctylsulfonamido)ethylmethacrylate and a catalyst and transferred to a mold, subjected to elevated temperature for a time sufficient to polymerize the monomer, and thereafter the polymerized material is removed from said mold and optionally hydrated.

8. A copolymer plastic material which is manufactured:
(a) from about 1 to 60 weight percent of a monomer selected from the group consisting of bis[tris(trimethylsiloxy)silylpropyl]methacrylamide, bis[tris(trimethylsiloxy)silylpropyl]acrylamide, 3-tris(trimethylsiloxy)silylpropylmethacrylamide, and 3-tris(trimethylsiloxy)silylpropylacrylamide.
(b) from about 1 to 50 weight percent of monomer selected from the group consisting of ethylenically unsaturated hydroxyalkyl monomer of acrylic or methacrylic acid and mixtures thereof;
(c) from about 5 to 30 weight percent organosilicone monomer;
(d) from 2 to 40 weight percent of unsaturated wettability monomer or mixtures thereof;
(e) 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 monomer selected from a group consisting of ethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate and tetraethyleneglycol dimethacrylate and mixtures thereof;
(g) from about 1 to 20 weight percent of alkyl or cyclic ester monomer of methacrylic acid and acrylic acid;
(h) from about 1 to 20 weight percent of perfluoroalkyl ester monomer of acrylic and methacrylic acid or mixtures thereof; and (i) from about 1 to 20 weight percent of additional cross-linking agent

9. A method of forming an ophthalmic device comprising:
(a) molding a copolymer plastic material from at least one of the following monomers:

(1) bis[tris(trimethylsiloxy)silylpropyl]methacrylamide having the following formula:
where m is an integer from1 to 4 and R is an alkyl group (2) bis[tris(trimethylsiloxy)silylpropyl]acrylamide:
where m is an integer from 1 to 5 (3) 3-tris(trimethylsiloxy)silylpropylmethacrylamide, and 3-tris(trimethylsiloxy)silylpropylacrylamide having the following formulas:
(b) curing said copolymer plastic.

10. The method of claim 9, further comprising adding to said copolymer plastic material at least one organosilicone monomer prior to said molding.

11.The method of claim 9, wherein said organosilicone monomer is at least one selected from the group consisting of:

wherein X and Y are C1 to C6, alkyl, cyclic or phenyl groups and/or groups of the following structures:

m being an integer from 1 to 6, n being an integer from 1 to 3, A is selected from C1 to C6, alkyl or phenyl groups, and R is a methyl group or hydrogen.
A group of organosiloxanylalkyl ester monomers of acrylic and methacrylic acid represented by the following formula:

wherein, X and Y are C1 to C6, alkyl or phenyl groups or groups of the following structure:
m being an integer from 1 to 6, n being an integer from1 to 3, A is selected from C1 to C6, alkyl or phenyl groups, R is a methyl group or hydrogen and D is hydrogen or hydroxy group; and A group of oganosiloxanylalkyl ester monomers of acrylic and methacrylic acids represented by the following structural formula:

wherein X and Y are groups of the following structure:
m being an integer from 1 to 5, n is an integer from 1 to 3, wherein, A is selected from C1 to C6, alkyl, cyclic or phenyl groups and R is a methyl group or hydrogen.

12. The method of claim 9, further comprising shaping a contact lens from said copolymer plastic.

13. The method of claim 9, further comprising hydrating said copolymer plastic after said curing step.

14. A contact lens made by the process of claim 9.

15. An ophthalmic device made by the process of claim 9.