EP0194277A1 - Verre de contact et polymer d'alcoylesilane - Google Patents

Verre de contact et polymer d'alcoylesilane

Info

Publication number
EP0194277A1
EP0194277A1 EP85904314A EP85904314A EP0194277A1 EP 0194277 A1 EP0194277 A1 EP 0194277A1 EP 85904314 A EP85904314 A EP 85904314A EP 85904314 A EP85904314 A EP 85904314A EP 0194277 A1 EP0194277 A1 EP 0194277A1
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Withdrawn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
EP85904314A
Other languages
German (de)
English (en)
Other versions
EP0194277A4 (fr
Inventor
William M. Foley
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MC CARRY John D
Original Assignee
MC CARRY John D
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by MC CARRY John D filed Critical MC CARRY John D
Publication of EP0194277A1 publication Critical patent/EP0194277A1/fr
Publication of EP0194277A4 publication Critical patent/EP0194277A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

On décrit des polymères d'alcoylesilanes et des verres de contact optiques fabriqués à partir de ces polymères.
EP19850904314 1984-08-17 1985-08-08 Verre de contact et polymer d'alcoylesilane. Withdrawn EP0194277A4 (fr)

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

Publications (2)

Publication Number Publication Date
EP0194277A1 true EP0194277A1 (fr) 1986-09-17
EP0194277A4 EP0194277A4 (fr) 1987-02-03

Family

ID=27093802

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19850904314 Withdrawn EP0194277A4 (fr) 1984-08-17 1985-08-08 Verre de contact et polymer d'alcoylesilane.

Country Status (3)

Country Link
EP (1) EP0194277A4 (fr)
CA (1) CA1258343A (fr)
WO (1) WO1986001219A1 (fr)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63145310A (ja) * 1986-12-06 1988-06-17 Agency Of Ind Science & Technol 光学用プラスチツク材料
JP3599848B2 (ja) * 1995-09-11 2004-12-08 株式会社メニコン 含水性軟質眼用レンズ用材料、それからなる含水性軟質眼用レンズ用成形体、ならびにそれからなる含水性軟質眼用レンズおよびその製法
JP3530287B2 (ja) * 1995-10-24 2004-05-24 株式会社メニコン 低含水性眼用レンズ用材料、それからなる低含水性眼用レンズ用成形体、ならびにそれからなる低含水性眼用レンズおよびその製法
FR2766827B1 (fr) * 1997-08-04 1999-09-03 Inst Francais Du Petrole Copolymere hydrosoluble a base de derive de silane ou de siloxane
AU6616100A (en) * 1999-08-11 2001-05-30 Bausch & Lomb Incorporated Method of making ocular devices
JP3965547B2 (ja) * 1999-12-01 2007-08-29 信越化学工業株式会社 高分子化合物、レジスト材料及びパターン形成方法
KR100520188B1 (ko) * 2000-02-18 2005-10-10 주식회사 하이닉스반도체 부분적으로 가교화된 2층 포토레지스트용 중합체
KR100520186B1 (ko) * 2000-06-21 2005-10-10 주식회사 하이닉스반도체 부분적으로 가교화된 2층 포토레지스트용 중합체
US6364934B1 (en) 2000-07-31 2002-04-02 Bausch & Lomb Incorporated Method of making ocular devices
CN1988875B (zh) * 2004-07-14 2012-05-02 3M埃斯佩股份公司 含有含不饱和碳硅烷的组分的牙科组合物
AU2005275246B2 (en) * 2004-07-14 2011-10-06 3M Deutschland Gmbh Dental compositions containing carbosilane monomers
EP1781724B1 (fr) * 2004-07-14 2009-07-08 3M Innovative Properties Company Compositions pour chirurgie dentaire contenant des polymères de type carbosilane
AU2004321432A1 (en) * 2004-07-14 2006-01-19 3M Espe Ag Dental composition containing Si-H functional carbosilane 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
WO2012128752A1 (fr) * 2011-03-21 2012-09-27 Momentive Performance Materials Inc. Monomères siloxanes contenant une liaison de carbosiloxane de résistance à l'hydrolyse, procédé pour leur préparation et films minces les contenant pour une application aux lentilles de contact
CN102584883B (zh) * 2011-10-20 2014-06-04 湖北固润科技股份有限公司 含多硅的甲基丙烯酸酯和丙烯酸酯类单体及合成方法

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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 *

Also Published As

Publication number Publication date
EP0194277A4 (fr) 1987-02-03
CA1258343A (fr) 1989-08-08
WO1986001219A1 (fr) 1986-02-27

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