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EP0194277A4 - Alkylsilane contact lens and polymer. - Google Patents

Alkylsilane contact lens and polymer.

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Publication number
EP0194277A4
EP0194277A4 EP19850904314 EP85904314A EP0194277A4 EP 0194277 A4 EP0194277 A4 EP 0194277A4 EP 19850904314 EP19850904314 EP 19850904314 EP 85904314 A EP85904314 A EP 85904314A EP 0194277 A4 EP0194277 A4 EP 0194277A4
Authority
EP
European Patent Office
Prior art keywords
weight
copolymerization
following
positive integer
polymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19850904314
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German (de)
French (fr)
Other versions
EP0194277A1 (en
Inventor
William M Foley
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MC CARRY JOHN D
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MC CARRY JOHN D
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Publication date
Application filed by MC CARRY JOHN D filed Critical MC CARRY JOHN D
Publication of EP0194277A1 publication Critical patent/EP0194277A1/en
Publication of EP0194277A4 publication Critical patent/EP0194277A4/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/04—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F30/08—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses

Definitions

  • This invention relates to optical contact lenses and materials therefor and, in particular, to alkylsilane polymers and alkylsilane polymer contact lenses.
  • silane chemistry is quite well known and reported in the literature.
  • An excellent treatment of the chemistry of silanes is given by Sommers, L.H.; Mitch, P.A; and Goldberg, G.M. , "Synthesis and properties of Compounds with a Framework of Alternate Silicon and Carbon Atoms, J.A.C.S., 71, 2746, (1949).
  • Silanes have been utilized in preparative organic chemistry and for a number of specialty applications, including waterproofing compounds for morter and fabrics and the like, as accellerators in some polymer operations, and as intermediates in the preparation of organosiloxanes.
  • the present invention relates to a novel class of contact lenses comprising polymers resulting from the polymerization or copolyrnerization alkyl silanes, having the general structure:
  • R a through R j are hydrogen or alkyl, aryl, aralkyl, or silyl moieties, which may include vinyl, allyl, acrylyl, acrylic, methacrylic, ethacrylic, or pyrrolidinonyl substituents and may also contain up to about 35 weight percent siloxyl, and wherein either X 1 or X 2 , or both X 1 and X 2 are vinyl polymerizable group containing moieties.
  • the term "vinyl polymerizable group” is used here in a particular sense to mean a polymerizable group containing the carbon-carbon double bond which is polymerized in the formation of polyvinyl polymers, i.e. the following structures:
  • Exemplary of the monomers suitable for forming the polymers and copolymers of this invention are the following:
  • n is a positive integer from 1 to 5, preferrably 1 to 3;
  • n is a positive integer from 1 to 5, preferrably 1 to 3;
  • n is a positive integer from 1 to 5, preferrably 1 to 3;
  • n is a positive integer from 1 to 5, preferrably 1 to 3;
  • n is a positive integer from 1 to 5, preferrably 1 to 3;
  • n is a positive integer from 1 to 5, preferrably 1 to 3 and R 1 , R 2 and R 3 are selected from the group consisting of methyl,
  • n is a positive integer from 1 to 5, preferrably 1 to 3;
  • n is a positive integer from 1 to 5, preferably 1 to 3, and R 4 and R 5 are selected from the group consisting of methyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl
  • n is a positive integer from 1 to 5, preferably 1 to 3, and R 6 and R 7 are selected from the group consisting of methyl,
  • n is a positive integer from 1 to 5, preferably 1 to 3, and R 8 - R 11 are selected from the group consisting of methyl,
  • n is a positive integer from 1 to 5, preferably
  • R 12 and R 13 are selected from the group consisting of methyl
  • phenyl alkylmethoxy, phenylmethyl, and N-alkylpyrrolidinonyl.
  • Silanes with two polymerizable groups and polymers thereof and lenses of such polymers are also contemplated within the scope of the invention.
  • Exemplary of such monomers are:
  • n is a positive integer from 1 to 5, preferably 1 to 3, and R 14 and R 15 are selected from the group consisting of methyl,
  • phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl wgerein is a positive integer from 1 to 5, preferably
  • R 1 6 to R 19 are selected from the group consisting of methyl
  • n is a positive integer from 1 to 5, preferably 1 to 3, and R 20 to R 23 are selected from the group consisting of
  • n is a positive integer from 1 to 5, preferably 1 to 3,;
  • n is a positive integer from 1 to 5, preferably 1 to 3,;
  • R 24 and R 25 are selected from the group consisting of methyl
  • phenyl alkylmethoxy, phenylmethyl, and N-alkylpyrrolidinonyl.
  • vinyl, allyl, acrylallyl, acrylic, methacrylic or ethacrylic derivatives of the compounds referred to which include one or more polymerizable groups such as vinyl, allyl, acrylic, methacrylic or ethacrylic may be considered equivalent to the specific, exemplary monomers, and polymers and copolymers of the same may be used as contact lens materials and lenses.
  • the alkylsilane polymer lenses of this invention have been discovered to have extremely beneficial, and most unexpected and unpredictable properties as contact lenses.
  • the most comparable lenses, of siloxyl based polymers have an oxygen permeability, Dk value (see, e.g. Fatt, I. and St.
  • the alkylsilane polymer lenses of this invention have a calculated Dk value of as high as 40 or morel
  • the exremely high Dk value as shown by wearer comfort, has been demonstrated for the contact lenses of this invention.
  • these alkylsilane polymer lenses have an even greater resistance to protein contamination than the silicone polymer lenses.
  • These alkylsilane polymer lenses are also harder and, very surprisingly, can be made wettable by inclusion of appropriate hydrophylic substituents much easier than comparable silicone polymer contact lenses! These very surprising advantages, coupled with good optical quality could not have been predicted, or even guessed at in advance.
  • These lens polymers can be formulated with a relatively high phenyl substituent content, giving lenses having a high index of refraction which can be made thinner and lighter than conventional contact lenses, and more easily fabricated into bifocal lenses than is possible with conventional and know lens polymers.
  • Surface characteristics can be modified by inclusion of specific moieties in the polymer; for example, methoxy alkyl, ethoxy alkyl, or nalkylpyrrolidinone may be included to improve wettability.
  • Monomers having two polymerizable groups may be used, thus resulting in a fully crosslinked lens polymer. It is even possible to prepare highly hydrated lenses from the polymers of this inventionI Description of the Preferred Embodiment
  • alkylsilane polymer contact lenses have most unexpected and unpredicted advantages over other lenses and, more particularly, over the most comparable lenses, those formed of silicone polymers.
  • the alkylsilanes used in forming the polymers from which the lenses of the present invention are manufactured are most conveniently prepared by the action of a polymerizable vinyl group containing moiety, e.g. methacrylic acid, on a chloroalkyl or bromoalkyl substituted silane, such as chloromethyl trimethylsilane or di-chloromethyl dimethylsilane, in the presence of a base such as pyridine or triethyl amine.
  • the higher homologues of the series are conveniently prepared by the action of the Grignard Reagent of a silane, such as trimethylsilylmethyl magnesium chloride on a chlorosilylalkyl methacrylate, e.g. trichlorosilyl propyl methacrylate, to give tris (trimethylsilylmethyl) silylpropyl methacrylate.
  • a polymerizable vinyl group containing moiety e.g. methacrylic acid
  • Trimethylsilylmethyl methacrylate was prepared as follows: Methacrylic acid (29.6 g) was dissolved in dry ether (600 ml), sodium carbonate (18.6g) was added slowly to form the sodium salt. Chloromethyl trimethyl silane
  • the product was washed with basic carbonate solution until the wash was free of color and then washed with distilled water to remove any hydroquinone which may have been carried over during distillation, and dried over magnesium sulfate and stored under refrigeration.
  • Phenyldimethylsilyl Methyl Methacrylate was prepared by reacting phenyl dimethyul chloromethyl silane (161 g) with methacrylic acid (132g) and triethylamine (132g) in benzene (300 ml), with hydroquinone (1.0 g) added to inhibit polymerization during the reaction. The mixture was refluxed for 64 hours. The resulting product was washed, dried and distilled, and the boiling point of the product was found to be 86°C. at 0.1 mm Hg. The yield, 105.2g, was 51.5% of theoretical. The product was further washed and stored as in example I. These procedures are, of course, well known reactions. Similar reactions and techniques are suitable for the preparation of the monomers of interest.
  • Monomers in the specified ratio and initiator were thoroughly mixed and dryed over magnesium sulfate and filtered.
  • the dryed, filtered monomer mixture was placed in molds under nitrogen atmosphere and cured be slowly raising the temperature to about 100°C. for about 2 hours followed by a reduction to a post-cure temperature of about 80°C. for a post cure of about 15 hours.
  • the resulting lens blank was examined and is then machined to form contact lenses according to conventional procedures for the manufacture of contact lenses.
  • This lens material has an exceptionally high refractive index, making it ideally suited to the manufacture of bifocal and thin lenses.
  • Phenyldimethylsilyl methylmethacrylate 60%* Methyl methacrylate 26% N-vinyl pyrrolidinone 3% Methacrylic acid 6% Ethylene glycol dimethacrylate 5% Initiator** Trace
  • This lens material has an exceptionally high refractive index, making it ideally suited to the manufacture of bifocal and thin lenses.
  • This lens material has an exceptionally high refractive index, making it ideally suited to the manufacture of bifocal and thin lenses.
  • this lens material On hydrating in 0.9% saline solution, this lens material reached an equilibrium hydration level of 42.7°, providing a clear, rigid hydrating lens material.
  • This lens material has an exceptionally high refractive index, making it ideally suited to the manufacture of bifocal and thin lenses, and, additionally, reached an equalibrium of 18.5% hydration in 0.9% saline, thus providing a clear, rigid hydrating lens material.
  • lens materials had excellent optical properties and some had outstanding refractive index characteristics. All were ideal for the manufacture of high quality exceptionally comfortable lenses. Some had moderate to high hydration capacity, in addition to being excellent, clear comfortable lens characteristics.
  • lens materials are far more comfortable for the wearer than the most nearly comparable lenses formed of siloxanyl polymers, the silicone polymers of the prior art and of my earlier filed copending patent applications. Wearer comfort is somewhat subjective but reflects real differences. Two objective observations are believed to explain the unexpectedly high comfort factor of the lenses of this invention. First, oxygen permeability is very high, thus contributing to healthier eye tissue and greater comfort. Second, these lens materials are exceptionally resistant to the buildup of proteins on the lens surfaces. A third, highly unexpected, factor believed to contribute to wearer comfort is the wettability of the lens materials of this invention. Silanes have typically been used in waterproofing applications and one would predict a highly hydrophobic lens material. Quite surprisingly, however, the lenses of this invention are quite hydrophylic and, indeed, in some formulations, hydrate to a moderate to high level.
  • lens materials of the present invention is that it is possible to form excellent lens materials with excellent optical, refractive, mechanical and comfort properties without the presence of methyl methacrylate, or with only very minor amounts of methyl methacrylate
  • lens material formulations are only exemplary of a vast number of lens materials and lenses which can be manufactured within the scope of this invention.
  • Many analogous and homologous monomers of the silane family may be substitued for those shown in the examples.
  • Initiators may be selected from among the many which are suitable for intiating the polymerization of vinyl group containing monomers.
  • the alkyl silanes of this invention comprise greater than 5% and preferrably greater than 20% of the polymeric lenses and lens materials and my comprise up to about 95%, preferrably up to about 90%, of such materials and lenses.
  • the lens material is formed from the polymerization of alkyl silanes with a cross-linking monomer and a monomer, such as n-vinylpyrrolidinone or hydroxyethyl methacrylate, or both, which contributes to the wettability or hydration of the lens, or to both wettability and hydration of lenses.
  • This hydrophylic constituent may comprise, preferrably, at least 2 to 3% and may comprise up to about 75% or more of the polymeric lens material.
  • Trimethylsilyl methyl methacrylate 25 to 95 weight % Hydroxyethyl methacrylate 5 to 75 weight %
  • a hydrophylic monomer would also comprise the polymerization mix. It has also been found advantageous to include methacrylic acid and/or methyl methacrylate as a monomer in the formation of the polymerized lense material; however, one of the surprising discoveries of this invention is that high quality lenses can be formed without either of these constituents.
  • R a through R j are hydrogen or alkyl, aryl, aralkyl, or silyl moieties, which may include vinyl, allyl, acrylyl, acrylic, methacrylic, ethacrylic, or pyrrolidinonyl substituents and may also contain up to about 35 weight percent siloxyl, and wherein either X 1 or X 2 , or both X 1 and X 2 are vinyl polymerizable group containing moieties.
  • the term "vinyl polymerizable group” is used here in a particular sense to mean a polymerizable group containing the carbon-carbon double bond which is polymerized in the formation of polyvinyl polymers, i.e. the following structures:
  • Exemplary of the monomers suitable for forming the polymers and copolymers of this invention are the following:
  • n is a positive integer from 1 to 5, preferably 1 to 3; wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
  • n is a positive integer from 1 to 5, preferrably 1 to 3;
  • n is a positive integer from 1 to 5, preferrably 1 to 3;
  • h is a positive integer from 1 to 5, preferrably 1 to 3;
  • n is a positive integer from 1 to 5, preferrably 1 to 3 and R 1, R 2 and R 3 are selected from the group consisting of methyl,
  • n is a positive integer from 1 to 5, preferrably 1 to 3;
  • n is a positive integer from 1 to 5, preferably
  • R 4 and R 5 are selected from the group consisting of methyl
  • n is a positive integer from 1 to 5, preferably
  • R 8 - R 11 are selected from the group consisting of methyl
  • n is a positive integer from 1 to 5, preferably
  • R 12 and R 13 are selected from the group consisting of methyl
  • phenyl alkylmethoxy, phenylmethyl, and N-alkylpyrrolidinonyl.
  • Silanes with two polymerizable groups and polymers thereof and lenses of such polymers are also contemplated within the scope of the invention.
  • Exemplary of such monomers are:
  • n is a positive integer from 1 to 5, preferably 1 to 3, and R 14 and R 15 are selected from the group consisting of methyl,
  • n is a positive integer from 1 to 5, preferably
  • R 16 to R 19 are selected from the group consisting of methyl
  • alkylmethoxy, phenylmethyl, and N-alkylpyrrol-idinonyl A monomor which is predominantly silane is:
  • n is a positive integer from 1 to 5, preferably 1 to 3, and R 20 to R 23 are selected from the group consisting of:
  • n is a positive integer from 1 to 5, preferably 1 to 3; wherein n is a positive integer from 1 to 5, preferably 1 to 3,;
  • R 24 and R 25 are selected from the group consisting of methyl, phenyl, alkylmethoxy, phenylmethyl, and N-alkylpyrrolidinonyl.
  • vinyl, allyl, acrylallyl, acrylic, methacrylic or ethacrylic derivatives of the compounds referred to which include one or more polymerizable groups such as vinyl, allyl, acrylic, methacrylic or ethacrylic may be considered equivalent to the specific, exemplary monomers, and polymers and copolymers of the same may be used as contact lens materials and lenses.
  • This invention is useful in the optical industry and, particularly, in the manufacture of optical contact lenses for the correction of certain human visual defects.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Alkylsilane polymers and optical contact lenses fabricated therefrom.

Description

ALKYLSILANE CONTACT LENS AND POLYMER Cross-Reference to Related Application
This is a continuation-in-part of my copending application Serial No. 641, 594, filed August 17, 1984, now to be abandoned.
Field of the Invention This invention relates to optical contact lenses and materials therefor and, in particular, to alkylsilane polymers and alkylsilane polymer contact lenses.
Background of the Invention Many polymeric materials have been evaluated for potential utility as contact lens material, but a very limited number of materials have been found to form contact lenses which are satisfactory. Advances in contact lens materials and techniques have come in small steps, which have been excruciatingly slow and difficult. Polymers and methods which appeared attractive have fallen by the wayside. The problems are myriad and predictability is low. It is difficult and frequently impossible to predict optical quality, strength and flexibility, resistance to protein build-up, machining and fabrication characteristics, dimensional stability, oxygen permeability, and general biological compatability. It is impossible to predict, or even to speculate as to possible optical, oxygen permeability, and biological characteristics of structural and industrial silanes such as disclosed by Campbell, U.S. Patent No. 2,958,681 for example. Reference is made to the literature, in texts, treatises and technical literature which describe silicon compounds, commonly referred to as silanes, particularly alkylsilanes. While the present invention departs from this chemistry in important and substantial ways, this body of chemistry is fundamental to the present invention. Silane chemistry is quite well known and reported in the literature. An excellent treatment of the chemistry of silanes is given by Sommers, L.H.; Mitch, P.A; and Goldberg, G.M. , "Synthesis and properties of Compounds with a Framework of Alternate Silicon and Carbon Atoms, J.A.C.S., 71, 2746, (1949). Surveys of this body of chemistry are found in KIRK-OTHMER, ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, 3rd Ed. at Vol. 20, pp 887-911. The chemistry of organosilicon compounds is described in ORGANOSILICON COMPOUNDS, Bazant, Chvalovsky and Rathovsky, Academic Press, Inc., New York, 1965.
The literature on contact lenses and contact lenses and contact lenses containing silicone compounds is massive, including hundreds of patents. This massive body of literature is not considered analogous to the present invention except as to the general techniques for forming optical contact lenses, e.g. cutting and polishing.
Silanes have been utilized in preparative organic chemistry and for a number of specialty applications, including waterproofing compounds for morter and fabrics and the like, as accellerators in some polymer operations, and as intermediates in the preparation of organosiloxanes.
While the chemistry, vis-a-vis reaction conditions, of alkyl silanes is known and reasonably well understood, it has not, to the inventor's knowledge, been proposed to use such materials as the principal constituent polymer in contact lenses. In particular, the unique characteristics of such contact lenses has not been reported, insofar as is known to the inventor. Given the uncertainty as to lens characteristics of given polymer systems, there was no reason to expect that such materials would be useful as lens polymers.
Summary of the Invention The present invention relates to a novel class of contact lenses comprising polymers resulting from the polymerization or copolyrnerization alkyl silanes, having the general structure:
wherein Ra through Rj are hydrogen or alkyl, aryl, aralkyl, or silyl moieties, which may include vinyl, allyl, acrylyl, acrylic, methacrylic, ethacrylic, or pyrrolidinonyl substituents and may also contain up to about 35 weight percent siloxyl, and wherein either X1 or X2, or both X1 and X2 are vinyl polymerizable group containing moieties. The term "vinyl polymerizable group" is used here in a particular sense to mean a polymerizable group containing the carbon-carbon double bond which is polymerized in the formation of polyvinyl polymers, i.e. the following structures:
-C=C- and -C-C=C-; exemplary of which vinyl polymerizable groups are: vinyl, allyl, acrylyl, acrylyl, methacrylyl, or styryl.
Exemplary of the monomers suitable for forming the polymers and copolymers of this invention are the following:
wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
wherein n is a positive integer from 1 to 5, preferrably 1 to 3 and R1, R2 and R3 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
wherein n is a positive integer from 1 to 5, preferably 1 to 3, and R4 and R5 are selected from the group consisting of methyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl
wherein n is a positive integer from 1 to 5, preferably 1 to 3, and R6 and R7 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl
wherein n is a positive integer from 1 to 5, preferably 1 to 3, and R8 - R11 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl and
wherein n is a positive integer from 1 to 5, preferably
1 to 3, and R12 and R13 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkylpyrrolidinonyl.
Silanes with two polymerizable groups and polymers thereof and lenses of such polymers are also contemplated within the scope of the invention. Exemplary of such monomers are:
wherein n is a positive integer from 1 to 5, preferably 1 to 3, and R14 and R15 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl wgerein is a positive integer from 1 to 5, preferably
1 to 3, and R1 6 to R19 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-slkylpyttol-idinonyl A monomer which is predominantly silane is:
wherein n is a positive integer from 1 to 5, preferably 1 to 3, and R20 to R23 are selected from the group consisting of
Other monomers which include two polymerizable groups include:
wherein n is a positive integer from 1 to 5, preferably 1 to 3,;
wherein n is a positive integer from 1 to 5, preferably 1 to 3,;
wherein R24 and R25 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkylpyrrolidinonyl.
In general, vinyl, allyl, acrylallyl, acrylic, methacrylic or ethacrylic derivatives of the compounds referred to which include one or more polymerizable groups such as vinyl, allyl, acrylic, methacrylic or ethacrylic may be considered equivalent to the specific, exemplary monomers, and polymers and copolymers of the same may be used as contact lens materials and lenses. The alkylsilane polymer lenses of this invention have been discovered to have extremely beneficial, and most unexpected and unpredictable properties as contact lenses. For example, the most comparable lenses, of siloxyl based polymers, have an oxygen permeability, Dk value (see, e.g. Fatt, I. and St. Helen, R., Oxygen Tension Under an Oxygen-Permeable Contact Lens, American Journal of Optrometry, July 1971, pp.545-555, for a discussion of Dk values) in the 20's, the highest being about 30 to 32. The alkylsilane polymer lenses of this invention have a calculated Dk value of as high as 40 or morel The exremely high Dk value, as shown by wearer comfort, has been demonstrated for the contact lenses of this invention. In addition, these alkylsilane polymer lenses have an even greater resistance to protein contamination than the silicone polymer lenses. These alkylsilane polymer lenses are also harder and, very surprisingly, can be made wettable by inclusion of appropriate hydrophylic substituents much easier than comparable silicone polymer contact lenses! These very surprising advantages, coupled with good optical quality could not have been predicted, or even guessed at in advance. These lens polymers can be formulated with a relatively high phenyl substituent content, giving lenses having a high index of refraction which can be made thinner and lighter than conventional contact lenses, and more easily fabricated into bifocal lenses than is possible with conventional and know lens polymers. Surface characteristics can be modified by inclusion of specific moieties in the polymer; for example, methoxy alkyl, ethoxy alkyl, or nalkylpyrrolidinone may be included to improve wettability. Monomers having two polymerizable groups may be used, thus resulting in a fully crosslinked lens polymer. It is even possible to prepare highly hydrated lenses from the polymers of this inventionI Description of the Preferred Embodiment
No new silane chemistry, per se, is involved in the present invention; rather, it has been discovered that alkylsilane polymer contact lenses have most unexpected and unpredicted advantages over other lenses and, more particularly, over the most comparable lenses, those formed of silicone polymers.
The alkylsilanes used in forming the polymers from which the lenses of the present invention are manufactured are most conveniently prepared by the action of a polymerizable vinyl group containing moiety, e.g. methacrylic acid, on a chloroalkyl or bromoalkyl substituted silane, such as chloromethyl trimethylsilane or di-chloromethyl dimethylsilane, in the presence of a base such as pyridine or triethyl amine. The higher homologues of the series are conveniently prepared by the action of the Grignard Reagent of a silane, such as trimethylsilylmethyl magnesium chloride on a chlorosilylalkyl methacrylate, e.g. trichlorosilyl propyl methacrylate, to give tris (trimethylsilylmethyl) silylpropyl methacrylate. Example A Trimethylsilyl Methyl Methacrylate
Trimethylsilylmethyl methacrylate was prepared as follows: Methacrylic acid (29.6 g) was dissolved in dry ether (600 ml), sodium carbonate (18.6g) was added slowly to form the sodium salt. Chloromethyl trimethyl silane
(42.2g) was added to the gelatenous solid formed from the preceeding salt forming reaction, followed by the addition of hydroquinone (1.00g). The mixture was refluxed for 72 hours, washed with water, dryed over magnesium sulfate, filtered and distilled giving a 21.7 g of product which boiled at 29.5°C. at 0.3 mm Hg, 37% of theoretical yield.
The product was washed with basic carbonate solution until the wash was free of color and then washed with distilled water to remove any hydroquinone which may have been carried over during distillation, and dried over magnesium sulfate and stored under refrigeration.
Example B Phenyldimethylsilyl Methyl Methacrylate Phenyldimethylsilyl Methyl Methacrylate was prepared by reacting phenyl dimethyul chloromethyl silane (161 g) with methacrylic acid (132g) and triethylamine (132g) in benzene (300 ml), with hydroquinone (1.0 g) added to inhibit polymerization during the reaction. The mixture was refluxed for 64 hours. The resulting product was washed, dried and distilled, and the boiling point of the product was found to be 86°C. at 0.1 mm Hg. The yield, 105.2g, was 51.5% of theoretical. The product was further washed and stored as in example I. These procedures are, of course, well known reactions. Similar reactions and techniques are suitable for the preparation of the monomers of interest.
Lens Manufacture The following general technique was followed in the preparation of lens blanks and lenses:
Monomers in the specified ratio and initiator were thoroughly mixed and dryed over magnesium sulfate and filtered. The dryed, filtered monomer mixture was placed in molds under nitrogen atmosphere and cured be slowly raising the temperature to about 100°C. for about 2 hours followed by a reduction to a post-cure temperature of about 80°C. for a post cure of about 15 hours. The resulting lens blank was examined and is then machined to form contact lenses according to conventional procedures for the manufacture of contact lenses.
The following examples of lenses formed by the technique described exemplify the invention.
Lens Material No. 1 Trimethylsilyl methyl methacrylate 45%*
Methyl methacrylate 41%
N-vinyl pyrrolidinone 3%
Methacrylic acid 6%
Ethylene glycol dimethacrylate 5% Initiator** (Trace)
* Percentages in all examples by weight. ** 2,2'azobis-2,4-dimethyl-4-methoxyvaleronitrile 0.001-0.5% in all Lens examples Initial Cure Temperature 102°C. Initial Cure Time 2 hours.
Post Cure Temperature 82-85°C.
Post Cure Time 16 hours.
Lens Qualities:
Clarity Excellent Hardness Good
Machinability Good
Wettability Good
Dimensional stability Excellent
Lens Material No. 2 Trimethylsilyl methyl methacrylate 30%* Methyl methacrylate 56%
N-vinyl pyrrolidinone 3%
Methacrylic acid 5%
Ethylene glycol dimethacrylate 6%
Initiator** (Trace)
Initial Cure Temperature 76°C.
Initial Cure Time 3/4 hours.
Post Cure Temperature 52-58ºC.
Post Cure Time 18 hours.
Lens Qualities:
Clarity Excellent
Hardness Good
Machinability Good
Wettability Good
Dimensional stability Excellent
Lens Material No. 3
Trimethylsilyl methyl methacrylate 60%*
Methyl methacrylate 26%
N-vinyl pyrrolidinone 3%
Methacrylic acid 5%
Ethylene glycol dimethacrylate 6%
Initiator** (Trace)
Initial Cure Temperature 69°C.
Initial Cure Time 3/4 hours.
Post Cure Temperature 52-58ºC.
Post Cure Time 18 hours.
Lens Qualities:
Clarity Excellent
Hardness Good
Machinability Good
Wettability Good
Dimensional stability Excellent
Lens Material No. 4
Trimethylsilyl methyl methacrylate 45%*
Methyl methacrylate 41% N-vinyl pyrrolidinone 3%
Methacrylic acid 6%
Ethylene glycol dimethacrylate 5%
Initiator** (Trace)
Initial Cure Temperature 102ºC.
Initial Cure Time 2 hours.
Post Cure Temperature 82-85°C.
Post Cure Time 16 hours.
Lens Qualities:
Clarity Excellent
Hardness Good
Machinability Good
Wettability Good
Dimensional stability Excellent
Lens Material No. 5
Trimethylsilyl methyl methacrylate 30%*
Methyl methacrylate 56%
N-vinyl pyrrolidinone 3%
Methacrylic acid 5%
Ethylene glycol dimethacrylate 6%
Initiator** (Trace)
Initial Cure Temperature 76°C.
Initial Cure Time 3/4 hours.
Post Cure Temperature 52-58ºC.
Post Cure Time 18 hours.
Lens Qualities:
Clarity Excellent
Hardness Good
Machinability Good
Wettability Good
Dimensional stability Excellent
Lens Material No. 6
Trimethylsilyl methyl methacrylate 60%*
Methyl methacrylate 26%
N-vinyl pyrrolidinone 3% Methacrylic acid 5% Ethylene glycol dimethacrylate 6% Initiator** (Trace)
Initial Cure Temperature 69°C. Initial Cure Time 3/4 hours. Post Cure Temperature 52-58ºC. Post Cure Time 18 hours. Lens Qualities: Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stability Excellent
Lens Material No. 7 Trimethylsilyl methyl methacrylate 86%* N-vinyl pyrrolidinone 3% Methacrylic acid 5% Ethylene glycol dimethacrylate 5% Initiator** (Trace)
Initial Cure Temperature 57°C. Initial Cure Time 3/4 hours. Post Cure Temperature 57°C. Post Cure Time 21 hours. Lens Qualities: Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stability Exceptional
Lens Material No. 8 Trimethylsilyl methyl methacrylate 40%* Methyl methacrylate 31% N-vinyl pyrrolidinone 3% 1,3,Bis(methyacryloxy propyl)1,1';3,3'tetrakis(trimethylsiloxy)disiloxane 20% Methacrylic acid 6%
Initiator** (Trace)
Initial Cure Temperature 80°C.
Initial Cure Time 3/4 hours.
Post Cure Temperature 55-58°C.
Post Cure Time 21 hours.
Lens Qualities:
Clarity Excellent
Hardness Good
Machinability Good
Wettability Good
Dimensional stability Excellent
Lens Material No. 9
Trimethylsilyl methyl methacrylate 25%*
Methyl methacrylate 47%
N-vinyl pyrrolidinone 3%
Trimethoxysilyl propyl methacrylate 25%
Initiator** Trace
Initial Cure Temperature 58ºC.
Initial Cure Time 1 1/4 hours.
Post Cure Temperature 58°C
Post Cure Time 20 hours.
Lens Qualities:
Clarity Excellent
Hardness Good
Machinability Good
Wettability Good
Dimensional stability Excellent
Lens Material No. 10
Phenylmethylsilyl methylmethacrylate 50%*
Methyl methacrylate 36%
N-vinyl pyrrolidinone 3%
Methacrylic acid 6%
Ethylene glycol dimethacrylate 5%
Initiator** Trace Initial Cure Temperature 58°C. Initial Cure Time 1 1/4 hours. Post Cure Temperature 58ºC. Post Cure Time 20 hours. Lens Qualities:
Clarity Excellent
Hardness Good
Machinability Good
Wettability Good
Dimensional stability Excellent This lens material has an exceptionally high refractive index, making it ideally suited to the manufacture of bifocal and thin lenses. Phenyldimethylsilyl methylmethacrylate 60%* Methyl methacrylate 26% N-vinyl pyrrolidinone 3% Methacrylic acid 6% Ethylene glycol dimethacrylate 5% Initiator** Trace
Initial cure temperature 104° Initial cure time 2 hours Post Cure Temperature 83-85ºC. Post Cure Time 16 hours. Lens Qualities:
Clarity Excellent
Hardness Good
Machinability Good
Wettability Good
Dimensional stability Excellent This lens material has an exceptionally high refractive index, making it ideally suited to the manufacture of bifocal and thin lenses.
Lens Material No. 12 Phenylmethylsilyl methylmethacrylate 86%* N-vinyl pyrrolidinone 3% Methacrylic acid 6%
Ethylene glycol dimethacrylate 5%
Initiator** Trace
Initial Cure Temperature 104°C.
Initial Cure Time 2 hours.
Post Cure Temperature 84-86°C.
Post Cure Time 18 hours.
Lens Qualities:
Clarity Excellent
Hardness Good
Machinability Good
Wettability Good
Dimensional stabillity Excellent
This lens material has an exceptionally high refractive index, making it ideally suited to the manufacture of bifocal and thin lenses.
Lens Material No. 13 Trimethoxylsilyl propylmethacrylate 45%* Methyl methacrylate 41% N-vinyl pyrrolidinone 3% Methacrylic acid 5% Ethylene glycol dimethacrylate 5% Initiator** Trace
Initial Cure Temperature 102ºC. Initial Cure Time 2 hours. Post Cure Temperature 82-85°C. Post Cure Time 16 hours. Lens Qualities:
Clarity Excellent
Hardness Good
Machinability Good
Wettability Good
Dimensional stability Excellent
Lens Material No. 14 Trimethylsilyl methyl methacrylate 45%* Hydroxyethyl methacrylate 10%
N-vinyl pyrrolidinone 50%
Methacrylic acid 4%
Ethylene glycol dimethacrylate 1%
Initiator** Trace
Initial Cure Temperature 57°C.
Initial Cure Time 2 hours.
Post Cure Temperature 57°C.
Post Cure Time 20 hours.
Lens Qualities:
Clarity Excellent
Hardness Good
Machinability Good
Wettability Good
Dimensional stability Excellent
On hydrating in 0.9% saline solution, this lens material reached an equilibrium hydration level of 42.7°, providing a clear, rigid hydrating lens material.
Lens Material No. 15 Phenyldimethylsilyl methylmethacrylate 20%* Hydroxyethyl methacrylate 74% Methacrylic acid 5%
Triethylene glycol dimethacrylate 5% Initiator** Trace
Initial Cure Temperature 102°C. Initial Cure Time 2 hours. Post Cure Temperature 84-86°C. Post Cure Time 18 hours. Lens Qualities:
Clarity Excellent
Hardness Good
Machinability Good
Wettability Good
Dimensional stability Excellent This lens material has an exceptionally high refractive index, making it ideally suited to the manufacture of bifocal and thin lenses, and, additionally, reached an equalibrium of 18.5% hydration in 0.9% saline, thus providing a clear, rigid hydrating lens material.
Lens Material No. 16 Phenyltetramethyldisilylmethylenemethylmethacrylate 50%* Methyl methacrylate 38.5% Methacrylic acid 6% Ethylene glycol dimethacrylate 5% N-vinylpyrrolidinone 3% Initiator** Trace
Initial Cure Temperature 100°C. Initial Cure Time 2 hours. Post Cure Temperature 82-83°C. Post Cure Time 17 hours. Lens Qualities: Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stability Excellent This lens material has an exceptionally high refractive index, making it ideally suited to the manufacture of bifocal and thin lenses.
Discussion and Equivalents These lens materials had excellent optical properties and some had outstanding refractive index characteristics. All were ideal for the manufacture of high quality exceptionally comfortable lenses. Some had moderate to high hydration capacity, in addition to being excellent, clear comfortable lens characteristics.
One of the important discoveries of this invention is that these lens materials are far more comfortable for the wearer than the most nearly comparable lenses formed of siloxanyl polymers, the silicone polymers of the prior art and of my earlier filed copending patent applications. Wearer comfort is somewhat subjective but reflects real differences. Two objective observations are believed to explain the unexpectedly high comfort factor of the lenses of this invention. First, oxygen permeability is very high, thus contributing to healthier eye tissue and greater comfort. Second, these lens materials are exceptionally resistant to the buildup of proteins on the lens surfaces. A third, highly unexpected, factor believed to contribute to wearer comfort is the wettability of the lens materials of this invention. Silanes have typically been used in waterproofing applications and one would predict a highly hydrophobic lens material. Quite surprisingly, however, the lenses of this invention are quite hydrophylic and, indeed, in some formulations, hydrate to a moderate to high level.
Another surprising characteristic of lens materials of the present invention is that it is possible to form excellent lens materials with excellent optical, refractive, mechanical and comfort properties without the presence of methyl methacrylate, or with only very minor amounts of methyl methacrylate
It will be readily understood by those skilled in the art that the foregoing lens material formulations are only exemplary of a vast number of lens materials and lenses which can be manufactured within the scope of this invention. Many analogous and homologous monomers of the silane family may be substitued for those shown in the examples. Initiators may be selected from among the many which are suitable for intiating the polymerization of vinyl group containing monomers.
In general, the alkyl silanes of this invention comprise greater than 5% and preferrably greater than 20% of the polymeric lenses and lens materials and my comprise up to about 95%, preferrably up to about 90%, of such materials and lenses. In the preferred embodiment, the lens material is formed from the polymerization of alkyl silanes with a cross-linking monomer and a monomer, such as n-vinylpyrrolidinone or hydroxyethyl methacrylate, or both, which contributes to the wettability or hydration of the lens, or to both wettability and hydration of lenses. This hydrophylic constituent may comprise, preferrably, at least 2 to 3% and may comprise up to about 75% or more of the polymeric lens material.
Exemplary percentages of selected formulations are shown in the following tables:
I Trimethylsilyl methyl methacrylate 5 to 95 weight % Methyl methacrylate 1 to 50 wieght %
N-vinyl pyrrolidinone 1 to 50 wieght %
Methacrylic acid 1 to 10 weight %
Ethylene glycol dimethacrylate 1 to 10 weight %
II Trimethylsilyl methyl methacrylate 20 to 90 weight % Methyl methacrylate 20 to 60 weight %
N-vinyl pyrrolidinone 1 to 10 weight %
III Trimethylsilyl methyl methacrylate 20 to 90 weight % N-vinyl pyrrolidinone 3 to 60 weight %
Methacrylic acid 1 to 10 weight %
IV Trimethylsilyl methyl methacrylate 20 to 95 weight % N-vinyl pyrrolidinone 5 to 80 weight % V
Trimethylsilyl methyl methacrylate 25 to 95 weight % Hydroxyethyl methacrylate 5 to 75 weitht %
VI Trimethylsilyl methyl methacrylate 5 to 95 weight % Methyl methacrylate 5 to 90 weight % 1,3,Bis(methyacryloxy propyl) 1,1';3,3'tetrakis(trimethylsiloxy)disiloxane 5 to 35 weight %
VII Phenylmethylsilyl methylmethacrylate 5 to 95 weight % Methyl methacrylate 5 to 50 weight %
VIII Phenylmethylsilyl methylmethacrylate 5 to 95 weight % Methacrylic acid 5 to 50 weight %
IX Trimethoxylsilyl propylmethacrylate 5 to 95 weight % Methyl methacrylate 5 to 60 weight %
X Trimethyoxysylyl propylmethacrylate 5 to 95 weight% Hydroxyethyl methacrylate 5 to 50 weight% XI
Phenyldimethylsilyl methylmethacrylate 10 to 95 weight % Hydroxyethyl methylmethacrylate 5 to 90 weight %
XII Phenyltetramethyldisilylmethylenemethylmethacrylate 5 to 95 weight % Methacrylic acid 5 to 60 weight %
Typically, in the preferred embodiments, a hydrophylic monomer would also comprise the polymerization mix. It has also been found advantageous to include methacrylic acid and/or methyl methacrylate as a monomer in the formation of the polymerized lense material; however, one of the surprising discoveries of this invention is that high quality lenses can be formed without either of these constituents.
Polymeric materials resulting from the polymerization or copolymerization alkyl silanes, having the following general structures and lenses formed therefrom are within the contemplation and concept of this invention wherein Ra through Rj are hydrogen or alkyl, aryl, aralkyl, or silyl moieties, which may include vinyl, allyl, acrylyl, acrylic, methacrylic, ethacrylic, or pyrrolidinonyl substituents and may also contain up to about 35 weight percent siloxyl, and wherein either X1 or X2, or both X1 and X2 are vinyl polymerizable group containing moieties. The term "vinyl polymerizable group" is used here in a particular sense to mean a polymerizable group containing the carbon-carbon double bond which is polymerized in the formation of polyvinyl polymers, i.e. the following structures:
-C=C- and -C-C=C-; exemplary of which vinyl polymerizable groups are: vinyl, allyl, acrylyl, acrylyl, methacrylyl, or styryl.
Exemplary of the monomers suitable for forming the polymers and copolymers of this invention are the following:
wherein n is a positive integer from 1 to 5, preferably 1 to 3; wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
l wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
wherein h is a positive integer from 1 to 5, preferrably 1 to 3;
wherein n is a positive integer from 1 to 5, preferrably 1 to 3 and R1, R2 and R3 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl
wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
wherein n is a positive integer from 1 to 5, preferably
1 to 3, and R4 and R5 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl wherein n is a positive integer from 1 to 5, preferably 1 to 3, and R6 and R7 are selected from the group consisting of methyl.
phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl
wherein n is a positive integer from 1 to 5, preferably
1 to 3, and R8 - R11 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl and wherein n is a positive integer from 1 to 5, preferably
1 to 3 , and R12 and R13 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkylpyrrolidinonyl.
Silanes with two polymerizable groups and polymers thereof and lenses of such polymers are also contemplated within the scope of the invention. Exemplary of such monomers are:
wherein n is a positive integer from 1 to 5, preferably 1 to 3, and R14 and R15 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl
wherein n is a positive integer from 1 to 5, preferably
1 to 3, and R16 to R19 are selected from the group consisting of methyl,
phenyl,
alkylmethoxy, phenylmethyl, and N-alkylpyrrol-idinonyl A monomor which is predominantly silane is:
wherein n is a positive integer from 1 to 5, preferably 1 to 3, and R20 to R23 are selected from the group consisting of:
Other monomers which include two polymerizable groups include:
wherein n is a positive integer from 1 to 5, preferably 1 to 3; wherein n is a positive integer from 1 to 5, preferably 1 to 3,;
wherein R24 and R25 are selected from the group consisting of methyl, phenyl, alkylmethoxy, phenylmethyl, and N-alkylpyrrolidinonyl.
In general, vinyl, allyl, acrylallyl, acrylic, methacrylic or ethacrylic derivatives of the compounds referred to which include one or more polymerizable groups such as vinyl, allyl, acrylic, methacrylic or ethacrylic may be considered equivalent to the specific, exemplary monomers, and polymers and copolymers of the same may be used as contact lens materials and lenses.
Industrial Application This invention is useful in the optical industry and, particularly, in the manufacture of optical contact lenses for the correction of certain human visual defects.

Claims

WHAT IS CLAIMED IS:
1. Contact lenses comprising polymers resulting from the polymerization or copolymerization alkyl silanes, having the general structure:
wherein Ra through Rj are hydrogen or alkyl, aryl, aralkyl, or silyl moieties, which may include vinyl, allyl, acrylyl, acrylic, methacrylic, ethacrylic, or pyrrolidinonyl substituents and may also contain up to about 35 weight percent siloxyl, and wherein either X1 or X2, or both X1 and X2 are vinyl polymerizable group containing moieties.
2. Contact lenses comprising polymers and copolymers resulting from the polymerization or copolymerization of one or more of the following:
wherein n is a positive integer from 1 to 3.
3. Contact lenses comprising polymers and copolymers resulting from the polymerization or copolymerization of:
wherein n is a positive integer from 1 to 3.
4. Contact lenses comprising polymers and copolymers resulting from the polymerization or coplymerization of one or more of:
wherein n is a positive integer from 1 to 3.
5. Contact lenses comprising polymers and copolymers resulting from the polymerization or coplymerization of one or more of:
wherein n is a positive integer from 1 to 3.
6. Contact lenses comprising polymers and copolymers resulting from the polymerization or copolymerization of one or more of the following:
wherein n is a positive integer from 1 to 3,
7. Contact lenses comprising polymers and copolymers resulting from the polymerization or copolymerization of one or more of the following:
wherein n is a positive integer from 1 to 3 and R1, R2 and R3 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl;
wherein n is a positive integer from 1 to 3.
8. Contact lenses comprising polymers and copolymers resulting from the polymerization or copolymerization of one or more of the following:
wherein n is a positive integer from 1 to 5, preferably 1 to 3, and R4 and R5 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl. e.
9. Contact lenses comprising polymers and copolymers resulting from the polymerization or copolymerization of one or more of the following:
wherein n is a positive integer from 1 to 5, preferably 1 to 3, and R6 and R7 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl;
wherein n is a positive integer from 1 to 5, preferably 1 to 3, and R8 - R11 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl; or
wherein n is a positive integer from 1 to 5, preferably
1 to 3, and R12 and R13 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkylpyrrolidinonyl.
10. Contact lenses comprising polymers and copolymers resulting from the polymerization or copolymerization of one or more of the following:
wherein n is a positive integer from 1 to 5, preferably 1 to 3, and R14 and R15 are selected from the group consisting of methyl.
phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl; or
wherein n is a positive integer from 1 to 5, preferably 1 to 3, and R16 to R19 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkylpyrrolidinonyl.
11. Contact lenses comprising polymers and copolymers resulting from the polymerization or copolymerization of one or more of the following:
wherein n is a positive integer from 1 to 5, preferably 1 to 3, and R20 to R23 are selected from the group consisting of,
the polymer being characterized as predominantly a silane polymer.
12. Contact lenses comprising polymers and copolymers resulting from the polymerization or copolymerization of one or more of the following:
wherein R24 and R25 are selected from the group consisting of methyl,
phenyl, alkylmethoxy, phenylmethyl, and N-alkylpyrrolidinonyl.
13. A polymeric contact lens comprising the polymer resulting from the copolymerization of the following:
Trimethylsilyl methyl methacrylate 5 to 95 weight % Methyl methacrylate 1 to 50 wieght %
N-vinyl pyrrolidinone 1 to 50 wieght %
Methacrylic acid 1 to 10 weight % Ethylene glycol dimethacrylate 1 to 10 weight %.
14. A polymeric contact lens comprising the polymer resulting from the copolymerization of the following:
Trimethylsilyl methyl methacrylate 20 to 90 weight % Methyl methacrylate 20 to 60 weight %
N-vinyl pyrrolidinone 1 to 10 weight %.
15. A polymeric contact lens comprising the polymer resulting from the copolymerization of the following: Trimethylsilyl methyl methacrylate 20 to 90 weight % N-vinyl pyrrolidinone 3 to 60 weight %
Methacrylic acid 1 to 10 weight %.
16. A polymeric contact lens comprising the polymer resulting from the copolymerization of the following:
Trimethylsilyl methyl methacrylate 20 to 95 weight % N-vinyl pyrrolidinone 5 to 80 weight %.
17. A polymeric contact lens comprising the polymer resulting from the copolymerization of the following:
Trimethylsilyl methyl methacrylate 25 to 95 weight % Hydroxyethyl methacrylate 5 to 75 weitht %.
18. A polymeric contact lens comprising the polymer resulting from the copolymerization of the following:
Trimethylsilyl methyl methacrylate 5 to 95 weight % Methyl methacrylate 5 to 90 weight %.
1,3,Bis(methyacryloxy propyl) 1,1';3,3'tetrakis(trimethylsiloxy) disiloxane 5 to 35 weight %.
21. A polymeric contact lens comprising the polymer resulting from the copolymerization of the following:
Phenylmethylsilyl methylmethacrylate 5 to 95 weight % Methyl methacrylate 5 to 50 weight %.
22. A polymeric contact lens comprising the polymer resulting from the copolymerization of the following:
Phenylmethylsilyl methylmethacrylate 5 to 95 weight % Methacrylic acid 5 to 50 weight %.
23. A polymeric contact lens comprising the polymer resulting from the copolymerization of the following:
Trimethoxylsilyl propylmethacrylate 5 to 95 weight % Methyl methacrylate 5 to 60 weight %.
24. A polymeric contact lens comprising the polymer resulting from the copolymerization of the following:
Trimethyoxysylyl propylmethacrylate 5 to 95 weight% Hydroxyethyl methacrylate 5 to 50 weight%.
25. A polymeric contact lens comprising the polymer resulting from the copolymerization of the following:
Phenyldimethylsilyl methylmethacrylate 10 to 95 weight % Hydroxyethyl methylmethacrylate 5 to 90 weight %.
26. A polymeric contact lens comprising the polymer resulting from the copolymerization of the following:
Phenyltetramethyldisilylmethylenemethylmethacrylate 5 to 95 weight %
Methacrylic acid 5 to 60 weight %.
EP19850904314 1984-08-17 1985-08-08 Alkylsilane contact lens and polymer. Withdrawn EP0194277A4 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US64159484A 1984-08-17 1984-08-17
US641594 1984-08-17
US74212285A 1985-06-05 1985-06-05
US742122 1985-06-05

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EP0194277A4 true EP0194277A4 (en) 1987-02-03

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EP (1) EP0194277A4 (en)
CA (1) CA1258343A (en)
WO (1) WO1986001219A1 (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63145310A (en) * 1986-12-06 1988-06-17 Agency Of Ind Science & Technol Optical plastic material
JP3599848B2 (en) * 1995-09-11 2004-12-08 株式会社メニコン Material for hydrous soft ophthalmic lens, molded article for hydrous soft ophthalmic lens comprising the same, and hydrous soft ophthalmic lens comprising the same and method for producing the same
JP3530287B2 (en) * 1995-10-24 2004-05-24 株式会社メニコン Low water content ophthalmic lens material, low water content ophthalmic lens molded article thereof, low water content ophthalmic lens made thereof, and method for producing the same
FR2766827B1 (en) * 1997-08-04 1999-09-03 Inst Francais Du Petrole WATER-SOLUBLE COPOLYMER BASED ON SILANE OR SILOXANE DERIVATIVE
AU6616100A (en) * 1999-08-11 2001-05-30 Bausch & Lomb Incorporated Method of making ocular devices
JP3965547B2 (en) * 1999-12-01 2007-08-29 信越化学工業株式会社 Polymer compound, resist material, and pattern forming method
KR100520188B1 (en) 2000-02-18 2005-10-10 주식회사 하이닉스반도체 Partially crosslinked polymer for bilayer photoresist
KR100520186B1 (en) * 2000-06-21 2005-10-10 주식회사 하이닉스반도체 Partially crosslinked polymer for bilayer photoresist
US6364934B1 (en) 2000-07-31 2002-04-02 Bausch & Lomb Incorporated Method of making ocular devices
US8084515B2 (en) * 2004-07-14 2011-12-27 3M Innovative Properties Company Dental compositions containing carbosilane polymers
CA2573716A1 (en) * 2004-07-14 2006-02-23 3M Innovative Properties Company Dental compositions containing carbosilane monomers
CN1997333A (en) * 2004-07-14 2007-07-11 3M埃斯佩股份公司 Dental composition containing Si-H functional carbosilane components
US7915324B2 (en) * 2004-07-14 2011-03-29 3M Innovative Properties Company Dental composition containing unsaturated carbosilane containing components
US7557231B2 (en) 2006-06-30 2009-07-07 Bausch & Lomb Incorporated Carboxylic tris-like siloxanyl monomers
US8772367B2 (en) 2011-03-21 2014-07-08 Momentive Performance Materials Inc. Siloxane monomers containing hydrolysis resistance carbosiloxane linkage, process for their preparation and thin films containing the same for contact lens application
JP5947875B2 (en) * 2011-03-21 2016-07-06 モメンティブ パフォーマンス マテリアルズ インコーポレイテッド Hydrolysis-resistant siloxane monomers containing carbosiloxane bonds, processes for their preparation, and thin films for contact lenses containing them
CN102584883B (en) * 2011-10-20 2014-06-04 湖北固润科技股份有限公司 Multi-silicon methacrylate and acrylate monomer and synthetic method

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US31406A (en) * 1861-02-12 Improvement in cane-harvesters
US2958681A (en) * 1956-11-30 1960-11-01 Du Pont Crystalline polyallyl-trimethylsilane
US4463149A (en) * 1982-03-29 1984-07-31 Polymer Technology Corporation Silicone-containing contact lens material and contact lenses made thereof
US4507452A (en) * 1984-03-08 1985-03-26 John D. McCarry Silicone hydride contact lens and polymer

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No relevant documents have been disclosed *
See also references of WO8601219A1 *

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EP0194277A1 (en) 1986-09-17
CA1258343A (en) 1989-08-08

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