CA1258343A - Alkylsilane contact lens and polymer - Google Patents
Alkylsilane contact lens and polymerInfo
- Publication number
- CA1258343A CA1258343A CA000488838A CA488838A CA1258343A CA 1258343 A CA1258343 A CA 1258343A CA 000488838 A CA000488838 A CA 000488838A CA 488838 A CA488838 A CA 488838A CA 1258343 A CA1258343 A CA 1258343A
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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 and 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 and 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 and 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
Abstract
ALKYLSILANE CONTACT LENS AND POLYMER
Abstract of the Disclosure Alkylsilane polymers and optical contact lenses fabricated therefrom are disclosed.
Abstract of the Disclosure Alkylsilane polymers and optical contact lenses fabricated therefrom are disclosed.
Description
~S J UML)--1 b~ ~' 3~3 ALKYLSILANE CON~ACT LENS AND POLYMER
Field of the Invention This invention relates to optical contact lenses and materials therefor and, in particular, to alkylsilane polymers and alkylsilane polyrner contact lenses.
Back~round 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 smal~
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 ic 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 ]iterature, in texts, treatises and technical literature which describe silicon compounds, commonly referred to as si]anes, ~583~3 particularly alkylsilanes. While the present invention departs from this chemistry in important and substantial ways, this body of chemi~try is fundamental to the present invention.
Silane chemistry i6 qulte well known and reported in the literature. ~n excellent treatment of the chemistry of silanes is given by Sommers, L.H.; Mitcht F.A;
andGoldberg, G.M., "Synthesi~ and propertie~ of Compound~
with a Fra~ework of Alternate Silicon and Carbon Atoms, J.A.C.S., 71, 2746, (1949). Surveys of this body of chemistry are found in ~IRR-OT~ER~ ~CYCLOPEDIA O~
C~E~ICAL TEC~OLOGY, 3rd Ed. at Vol. 20, pp 887-911. The chemistry of organosilicon compounds is described in OR~ANOSILICON COMPO~NDS, 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 ofpatents. Tbismassive body of literature is not considered analogous to the present invention except as to the general techniques for forming optical con~act 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 proposedtouse suchmaterials asthe 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 characteristic~ of given polymer ~2~33~3 systems, there was no reason to expec-t -that such materials would be useful as ]ens polyrners.
Summary of the Invention The present invention relates to a novel class of contact lenses comprising polymers result:i.ng from the polyrnerization or copoly-nerization alkyl silanes, having the general structure:
Ib R R -C-R R.
Ig a ~ c ll X -C Si IC-X2 Rh Rd-C-Rf Rj e wherein Ra through Rj are hydrogen or alkyl, aryl, aralkyl, or silyl moieties, which may inc].ude vinyl, allyl, acrylyl, acrylic, methacrylic, ethacrylic, or pyrrolidinonyl substituents and may also contain up to about 35 weight percent siloxyl, and wherein ei.ther X1 or X2, or both Xl and X2 are vinyl polymerizable group containing moieties. The term "vinyl polymerizable group" is used here i.n a particular sense -to mean a po].ymerizable 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 sui-table for forming the polymers and copolymers of -th:is invention are the following:
CH2=CH- ~ ~ li-CH3;
~583~
CH2=CH ~ ~$i-(CH2)n~CH3 wherein n is a positive integer from 1 to 5, S preferrably 1 to 3;
~CH~
CH2=CH- -Si- -CnH]2n~1) ~CH3, n CH CH ~i3 CH2=CH-bi-CH2=CH-31-(CH2)n~ ~
wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
CH3 $i~ ( CH2)n~~~=CH2 wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
CIH3 CH3 1l ICH3 CH3-Si-( CH 2)n~~i-(CH2)n-0-C-C=CH2, ~H3 CH3 ~'~5~33~3 wherein n i8 a positive inteyer from 1 to 5, preferrably 1 to 3;
CH3~iCH3 ~H3 CH2 ol ~H3 CH3OCH2~iCH2~i(CH2)n-O-C-C=CH3;
CH3 ~H2 CH3$iCH3 CH2 C~ CH3 CH3 l~ ~CH3 ¦ / N-(CH2)n-~i-CH2~ CH2-O-C-~=CH2, CH2~ C=O CH3 CH3 wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
Rl CH3 R2-~i-(CH2)n-O-c-c=cH2/
wherein n is a positive integer from 1 to 5, preferrably 1 to 3 and Rl, R2 and R3 are selected from the group consisting of methyl, CH3 CH3 CH=CH2 phenyl, CH3bi-, CH3~iCH2 ~ CH3$iCH2-, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl ~8343 C~13 CH3$iCH3 ~ CH3 CH -O-C-C=CH2;
CH3~iCH3 CH3~iCH3 CH3~i CH ~Si-(CH2)n-O-~-C-CH2, CH3 ¦ CH3 CH3SiCH3 wherein n is a positive integer from 1 to 5, 15preferrably 1 to 3;
&H2 ~ ~H3 O CH3 20CH3SiCH3 CH-O-C-C=CH2;
CH2- ~ H3 R~
25\Si - ~H2 CH2 C ~ i-(CH2)]n ~ C=CH2 \ /CH3 Si-----CH2 Rs wherein nis a positive integerfrom 1 to 5, preferably 1 to 3, and R4 and Rs are selected from the group consisting of methyl, ~Z~3~3 CH3 ~H3 CH=CH2 phenyl, CH3~i-, CH3SiCH2-~ CH3biCH2-t alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl R~
~H~ - Si ~ H2 / CH3 \~ 1l IH3 CH3~iCH3 CH3SitCH2)n-O-c-c=cH2 \ CH3 CH2 i i--CH2 wherein n isa positive integerfrom 1 to 5, preferably 1 to 3, and R6 and R7 are selected from the group consisting of methyl, ICH3 CIH3 1CH=CH2 phenyl, CH3Si-, CH3~SiCH2-~ CH3SIicH2-~
alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl R8 Rg CH~ CH2 S\CH3 I CH3 CH ~H-O-~-C-CH2 CH3Si ~CH2- ~CH3 Rlo ~11 wherein n isa positive integer from lto 5, preferably 1 to 3, and R8 - Rll are selected from the group consisting of methyl, CIH3 CIH3 CIH=CH2 phenyl, CH3Si-, CH3SiCH2-~ CH3S
CH3 ~H3 CH3 alkylmethoxy, phenylmethy~, and N-alkyl-pyrrol-idinonyl and ~Z~33~3 Rl2 CH3 -,~; iH----CH 2 H ~ - CH2 -~ iCH2-O-C-~=CH3 CH3-~i - CH2 wherein nisa positive integerfrom 1 to 5, preferably 1 to 3, and R12 and R13 are selected from the group consisting of methyl, CH3 ICH3 CH=CH2 phenyl, CH3bi-, CH3SiCH2-~ CH3~iCH2 alkylmethoxy, phenylmethyl, and N-alkylpyrrol-idinonyl.
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:
H3~ 14 ~1 CIH3 CH2=C C-O-CH2-(Si-CH2) n-0-C-C-CH3 ~15 wherein n is a positive integerfrom 1 to 5, preferably 1 to 3, and R14 and Rls are selected from the group consisting of methyl, CIH3 CH3 CH=CH2 phenyl, CH3Si-, CH3~iCH2-~ CH3~iCH2 ~H3 C~3 ~H3 alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl 513~3~3 H31C 1l lRl6 ~lfl 1l ¦Cll3 CH2=C-C-O-CH2-Si-(CH2)nSi-CH2-0-C-C=C~13 R17 Rlg wherein n is a posltive integer from 1 to 5, preferably 1 to 3, and R16 to R19 are selected from the group consis-ting of me-thyl, ICH3 CIH3 CH=CH2 phenyl, CH3Si-, CH3SiCH2-, CH3SiCH2-, CH3 C~13 CH3 alkylmethoxy, phenylmethyl, and N-alkylpyrrol-idinonyl.
A monomer which is predominantly silane is:
H2C=C-C-O-(CH2)n-Si -O- Si-(CH2)n-0-C-C=CH2 wherein n is a positive integer from 1 -to 5, preferably
Field of the Invention This invention relates to optical contact lenses and materials therefor and, in particular, to alkylsilane polymers and alkylsilane polyrner contact lenses.
Back~round 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 smal~
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 ic 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 ]iterature, in texts, treatises and technical literature which describe silicon compounds, commonly referred to as si]anes, ~583~3 particularly alkylsilanes. While the present invention departs from this chemistry in important and substantial ways, this body of chemi~try is fundamental to the present invention.
Silane chemistry i6 qulte well known and reported in the literature. ~n excellent treatment of the chemistry of silanes is given by Sommers, L.H.; Mitcht F.A;
andGoldberg, G.M., "Synthesi~ and propertie~ of Compound~
with a Fra~ework of Alternate Silicon and Carbon Atoms, J.A.C.S., 71, 2746, (1949). Surveys of this body of chemistry are found in ~IRR-OT~ER~ ~CYCLOPEDIA O~
C~E~ICAL TEC~OLOGY, 3rd Ed. at Vol. 20, pp 887-911. The chemistry of organosilicon compounds is described in OR~ANOSILICON COMPO~NDS, 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 ofpatents. Tbismassive body of literature is not considered analogous to the present invention except as to the general techniques for forming optical con~act 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 proposedtouse suchmaterials asthe 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 characteristic~ of given polymer ~2~33~3 systems, there was no reason to expec-t -that such materials would be useful as ]ens polyrners.
Summary of the Invention The present invention relates to a novel class of contact lenses comprising polymers result:i.ng from the polyrnerization or copoly-nerization alkyl silanes, having the general structure:
Ib R R -C-R R.
Ig a ~ c ll X -C Si IC-X2 Rh Rd-C-Rf Rj e wherein Ra through Rj are hydrogen or alkyl, aryl, aralkyl, or silyl moieties, which may inc].ude vinyl, allyl, acrylyl, acrylic, methacrylic, ethacrylic, or pyrrolidinonyl substituents and may also contain up to about 35 weight percent siloxyl, and wherein ei.ther X1 or X2, or both Xl and X2 are vinyl polymerizable group containing moieties. The term "vinyl polymerizable group" is used here i.n a particular sense -to mean a po].ymerizable 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 sui-table for forming the polymers and copolymers of -th:is invention are the following:
CH2=CH- ~ ~ li-CH3;
~583~
CH2=CH ~ ~$i-(CH2)n~CH3 wherein n is a positive integer from 1 to 5, S preferrably 1 to 3;
~CH~
CH2=CH- -Si- -CnH]2n~1) ~CH3, n CH CH ~i3 CH2=CH-bi-CH2=CH-31-(CH2)n~ ~
wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
CH3 $i~ ( CH2)n~~~=CH2 wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
CIH3 CH3 1l ICH3 CH3-Si-( CH 2)n~~i-(CH2)n-0-C-C=CH2, ~H3 CH3 ~'~5~33~3 wherein n i8 a positive inteyer from 1 to 5, preferrably 1 to 3;
CH3~iCH3 ~H3 CH2 ol ~H3 CH3OCH2~iCH2~i(CH2)n-O-C-C=CH3;
CH3 ~H2 CH3$iCH3 CH2 C~ CH3 CH3 l~ ~CH3 ¦ / N-(CH2)n-~i-CH2~ CH2-O-C-~=CH2, CH2~ C=O CH3 CH3 wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
Rl CH3 R2-~i-(CH2)n-O-c-c=cH2/
wherein n is a positive integer from 1 to 5, preferrably 1 to 3 and Rl, R2 and R3 are selected from the group consisting of methyl, CH3 CH3 CH=CH2 phenyl, CH3bi-, CH3~iCH2 ~ CH3$iCH2-, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl ~8343 C~13 CH3$iCH3 ~ CH3 CH -O-C-C=CH2;
CH3~iCH3 CH3~iCH3 CH3~i CH ~Si-(CH2)n-O-~-C-CH2, CH3 ¦ CH3 CH3SiCH3 wherein n is a positive integer from 1 to 5, 15preferrably 1 to 3;
&H2 ~ ~H3 O CH3 20CH3SiCH3 CH-O-C-C=CH2;
CH2- ~ H3 R~
25\Si - ~H2 CH2 C ~ i-(CH2)]n ~ C=CH2 \ /CH3 Si-----CH2 Rs wherein nis a positive integerfrom 1 to 5, preferably 1 to 3, and R4 and Rs are selected from the group consisting of methyl, ~Z~3~3 CH3 ~H3 CH=CH2 phenyl, CH3~i-, CH3SiCH2-~ CH3biCH2-t alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl R~
~H~ - Si ~ H2 / CH3 \~ 1l IH3 CH3~iCH3 CH3SitCH2)n-O-c-c=cH2 \ CH3 CH2 i i--CH2 wherein n isa positive integerfrom 1 to 5, preferably 1 to 3, and R6 and R7 are selected from the group consisting of methyl, ICH3 CIH3 1CH=CH2 phenyl, CH3Si-, CH3~SiCH2-~ CH3SIicH2-~
alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl R8 Rg CH~ CH2 S\CH3 I CH3 CH ~H-O-~-C-CH2 CH3Si ~CH2- ~CH3 Rlo ~11 wherein n isa positive integer from lto 5, preferably 1 to 3, and R8 - Rll are selected from the group consisting of methyl, CIH3 CIH3 CIH=CH2 phenyl, CH3Si-, CH3SiCH2-~ CH3S
CH3 ~H3 CH3 alkylmethoxy, phenylmethy~, and N-alkyl-pyrrol-idinonyl and ~Z~33~3 Rl2 CH3 -,~; iH----CH 2 H ~ - CH2 -~ iCH2-O-C-~=CH3 CH3-~i - CH2 wherein nisa positive integerfrom 1 to 5, preferably 1 to 3, and R12 and R13 are selected from the group consisting of methyl, CH3 ICH3 CH=CH2 phenyl, CH3bi-, CH3SiCH2-~ CH3~iCH2 alkylmethoxy, phenylmethyl, and N-alkylpyrrol-idinonyl.
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:
H3~ 14 ~1 CIH3 CH2=C C-O-CH2-(Si-CH2) n-0-C-C-CH3 ~15 wherein n is a positive integerfrom 1 to 5, preferably 1 to 3, and R14 and Rls are selected from the group consisting of methyl, CIH3 CH3 CH=CH2 phenyl, CH3Si-, CH3~iCH2-~ CH3~iCH2 ~H3 C~3 ~H3 alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl 513~3~3 H31C 1l lRl6 ~lfl 1l ¦Cll3 CH2=C-C-O-CH2-Si-(CH2)nSi-CH2-0-C-C=C~13 R17 Rlg wherein n is a posltive integer from 1 to 5, preferably 1 to 3, and R16 to R19 are selected from the group consis-ting of me-thyl, ICH3 CIH3 CH=CH2 phenyl, CH3Si-, CH3SiCH2-, CH3SiCH2-, CH3 C~13 CH3 alkylmethoxy, phenylmethyl, and N-alkylpyrrol-idinonyl.
A monomer which is predominantly silane is:
H2C=C-C-O-(CH2)n-Si -O- Si-(CH2)n-0-C-C=CH2 wherein n is a positive integer from 1 -to 5, preferably
2.0 1 to 3, and R20 to R23 are se]ec-ted from the group consisting of 1 3 CIH3 CH=CH2 C113Si-,CH31iCH2-, ancl C~13SiCH2-Other monomers which include two polymerizable yroups include:
2 ~ CH3 ~ -Cl-l=C~12;
CH2=CH-~ _51 - ( CH2 ) -C~l=CH2 ' :~Z5~3~
wherein n is a positive integer from 1 to 5, preferably 1 to 3,;
S CH2=CH-li- ~-Si-CH=CH2;
CH 2=CH--5 i--e3--I i -CH=CH 2;
EE H
Cl H3 ,~ Cl H3 CH2=CH~~i~(CH2)n~~ (CH2) nCH-CH2 CH3 \=/ CH3 wherein n is a positive integer from 1 to 5, preferably 1 to 3,, CH3SiCH3 H3CI ~ ~H3 CH2 R CH3 CH2=C- ~o-cH2ticH2$i(cH2)n~o-c- =CH2; and CH3~iCH3 kH2 1~24 H3~ O CH3~iCH3 IOI CIH3 CH2=C-~ ~H -- O-C- =CH2, CH3~iCH3 R2s 4~
wherein R24 and R2s are selected from the group consisting of methyl, ~H3 CH3 CH=CH2 phenyl, CH3~i-, CH3~iCH2-~ CH3~iCH2 ~H3 ~H3 CH3 alkylmethoxy, phenylmethyl, and N-alkylpyrrol-idinonyl.
In general, vinyl, allyl, acrylallyl, acrylic, methacrylic or ethacrylic derivatives of ~he 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.
lS The alkylsilane polymer lenses of this invention have been discovered to have extremely beneficial, and most unexpectedand unpredictable properties as contactlenses.
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., QX~ ~n~iQn ~n~ ~n O~yq~n~s~m~bli 5Qn~ L~ns, American Journal of Optrometry, July 1971, pp.545-555, for a discussion of Dk values) in the 20'sv the highest being about 30 to32. 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 lensesl These very surprising advantages, coupled with good optical quality could not have been 33~
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 alkylr or n-alkylpyrrolidinonemay be included to improvewettability.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 inventionl De~cri~iQn Qf ~h~ Preferred EmkLLim~n~
Nonew silanechemistry, per se, is involved in the present invention; rather, it has been discovered that alkylsilane polymer contact lenses have most ~nexpected 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 moietyt 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 chlorosilyl-alkyl methacrylate, e.g. trichlorosilyl propyl methacrylate, to give tris(trimethylsilylmethyl) silyl-propyl methacrylate.
~25~ 3 ~ample A
Trimethylsilyl Methyl ~ethacrylate Trimethylsilylmethyl methacrylate was prepared as follows: Methacrylic acid (29.6 g) was dissolved in dry ether t600 ml), sodium carbonate (18~6 g) was added slowly to form the sodium salt. Chloromethyl trimethyl silane (42.2 g) was added to the gelatenous solid formed from the preceeding salt forming reaction, followed by the addition of hydroquinone (1.00 g). 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 29.5C. 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.
E~ample B
Phenyldimethylsilyl ~ethyl ~ethacrylate Phenyldimethylsilyl Methyl Methacrylate wasprepared by reacting phenyl dimethyul chloromethyl silan~ (161 g) with methacrylic acid (132 g) and triethylamine (132 g) 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 86C. at 0.1 mm Hg. The yield, 105.2g, was51.5~ 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.
Len~ ~anufacture The following general technique was followed in the ~Z58343 preparation of lens blanks and lenses:
Monomers in the specified ratio and initiator werethoroughly mixed and dry~d 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 100C. for about 2 hours followed by a reduction to a post-cure temperature of about 80C. forapost 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.
~en~ Material No. 1 Trimethylsilyl methyl methacrylate 45~*
Methyl methacrylate 41~
N-vinyl pyrrolidinone 3%
Methacrylic acid 6%
Ethylene glycol dimethacrylate5%
Initiator** (Trace) * Percentages in all examples by weight.
** 2,2'azobis-2,4-dimethyl-4-methoxy-valeronitrile 0.001-0.5~ in all Lens examples Initial Cure Temperature 102C.
Initial Cure Time 2 hours.
Post Cure Temperature 82-85C.
Post Cure Time 16 hours.
Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Len~ ~aterial No. 2 Trimethylsil~l methyl methacrylate 30%*
~Z51~343 Methyl methacrylate 56%
N-vinyl pyrrolidinone 3~
Methacrylic acid 5%
Ethylene glycol dimethacrylate 6%
Initiator** (Trace) Initial Cure Temperature 76C.
Initial Cure Time 3/4 hours Post Cure Temperature 52-58C.
Post Cure Time 18 hours Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Lens ~aterial 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 69C.
Initial Cure Time 3/4 hours Post Cure Temperature 52-58C.
Post Cure Time 18 hours Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Len~ ~aterial No. 4 Trimethylsilyl methyl methacrylate 45 Methyl methacrylate 41~
~f~ S~ 3 ~ 3 N-vinyl pyrrolidinone 3%
Methacrylic acid 6 Ethylene glycol dimethacrylate 5 Initiator** (Trace) Initial Cure Temperature 102C.
Initial Cure Time 2 hours Post Cure Temperature 82-85C.
Post Cure Time 16 hours Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Len~ ~aterial 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 76C.
Initial Cure Time 3/4 hours Post Cure Temperature 52-58C.
Post Cure Time 18 hours Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Len~ ~aterial ~o. 6 Trimethylsilyl methyl methacrylate 60 Methyl methacrylat~ 26%
N-vinyl pyrrolidinone 3%
8~9~3 Methacryli~ acid 5%
Ethylene glycol dimethacrylate 6 Initiator** (Trace) Initial Cure Temperature69C.
Initial Cure Time 3/4 hours Post Cure Temperature 52-58C.
Post Cure Time 18 hours Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Len~ ~aterial ~o. 7 Trimethylsilyl methyl methacrylate 86 N-vinyl pyrrolidinone 3~
Methacrylic acid 5%
Ethylene glycol dimethacrylate 5%
Initiator** (Trace) Initial Cure Temperature57C.
Initial Cure Time 3/4 hours Post Cure Temperature 57C.
Post Cure Time 21 hours Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExceptional Lens ~aterial No~ 8 Trimethylsilyl methyl methacrylate 40 Methyl methacrylate 31~
N-vinyl pyrrolidinone 3%
1,3,Bis(methyacryloxy propyl~l,l';3,3'-tetrakis(trimethylsiloxy)disiloxane 20%
~'~5~33~3 Methacrylic acid 6%
Initiator** (Trace) Initial Cure Temperature 80C.
Initial Cure Time 3/4 hours.
Post Cure Temperature 55-58C.
Post Cure Time 21 hours.
Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Len~ Material No. 9 Trimethylsilyl methyl methacrylate 25%*
Methyl methacrylate 47%
N-vinyl pyrrolidinone 3%
Trimethoxysilyl propyl methacrylate 25~
Initiator** Trace Initial Cure Temperature 58C.
~ Initial Cure Time1 1/4 hours.
Post Cure Temperature 58C.
Post Cure Time 20 hours~
Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Lens ~aterial No. 10 Phenylmethylsilyl methylmethacrylate 50%*
Methyl methacrylate 36~
N-vinyl pyrrolidinone 3%
Methacrylic acid 6%
~thylene glycol dimethacrylate 5%
Initiator** Trace lg Initial Cure Temperature 58C.
Initial Cure Time 1 1/4 hours Post Cure Temperature 58C.
Post Cure Time 20 hours Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Goocl Dimensional stabilityExcellent 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 83-85C.
Post Cure Time 16 hours Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stability Excellent 30 This lens material has an exceptionally high refractive index, making it ideally suited to the manufacture of bifocal and thin lenses.
Len~ ~aterial ~o. 12 Phenylmethylsilyl methylmethacrylate 86%*
N-vinyl pyrrolidinone 3 ~2~133~3 Methacrylic acid 6%
Ethylene glycol dimethacrylate 5%
Initiator** Trace Initial Cure Temperature 104C.
Initial Cure Time 2 hours.
Post Cure Temperature 84-86C.
Post Cure Time 18 hours.
Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent This lens material has an exceptionally high refractive 15 index, making it ideally suited to the manufacture of bifocal and thin lenses.
Len~ ~aterial ~o. 13 Trimethoxylsilyl propylmethacrylate 45%*
Methyl methacrylate 41%
N-vinyl pyrrolidinone 3%
Methacrylic acid 5%
Ethylene glycol dimethacrylate 5%
Initiator** Trace Initial Cure Temperature 102C.
Initial Cure Time 2 hours.
Post Cure Temperature 82-85C.
Post Cure Time 16 hours.
Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Len~ Material ~o~ 14 Trimethylsilyl methyl methacrylate 45%*
~5~33~3 Hydroxyethyl methacrylate 10%
N-vinyl pyrrolidinone 50%
Methacrylic acid 4%
Ethylene glycol dimethacrylate1%
Initiator** Trace Initial Cure Temperature 57C.
Initial Cure Time 2 hours.
Post Cure Temperature 57C.
Post Cure Time 20 hours.
Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent 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.
Len~ Material ~o~ 15 Phenyldimethylsilyl methylmethacrylate 20%*
Hydroxyethyl methacrylate 74 Methacrylic acid 5~
Triethylene glycol dimethacrylate 5%
Initiator** Trace Initial Cure Temperature 102C.
Initial Cure Time 2 hours.
Post Cure Temperature 84-86C.
Post Cure Time 18 hours.
Lens Qualitie~:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent 35 This lens material has an exceptionally high refractive 83~3 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.
S Len~ ~aterial ~o. 16 Phenyltetramethyldisilylmethylene-methylmethacrylate 50%*
Methyl methacrylate 38.5%
Methacrylic acid 6%
Ethylene glycol dimethacrylate 5~
N-vinylpyrrolidinone 3%
Initiator** Trace Initial Cure Temperature 100C.
Initial Cure Time 2 hoursO
Post ~ure Temperature 82-83C.
Post Cure Time 17 hours.
Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent This lens material has an exceptionally high refractive index, making it ideally suited to the manufacture of bifocal and thin lenses.
Di~cu~sion and ~quivalents These lens materials had excellent optical properties and ~ome had outstanding refractive index characteristics. All were ideal for the manufacture of high quality excèptionally comfortable lenses. Some had moderate to high hydration capacity, in addition to being excellent, clear comfortable lens characteristics.
Oneof the important discoveries of this invention is that these len~ materials are far more comfortable for thewearerthanthe most nearly comparable lense~ formed of ~58~43 siloxanyl polymers, the silicone polymers of the prior art and o~ 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, thuscontributing to healthier eyetiss~e andgreater 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 com~ort is the wettability ofthelens materials of this invention. Silanes have typically been used in ~aterproofing applications and one would predict a highly hydrophobic lens material. Quite surprisingly, however, thelenses ofthis invention arequite hydrophylic and, indeed, in some formulations, hydrate to a moderate to high level.
Another surprising characteristic of lens materialsofthepresent invention isthat it ispossibleto form excellent lens materials with excellent optical, refractive, mechanical and comfort properties ~ithout 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 ~ avast numberoElensmaterials ancllenses which can be manufactured within the scope of this invention. Many analogous and homologous monomers ofthe 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 83~L~
2~
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 silaneswith a cross-linking monomer and a monomer, s~ch as n-vinylpyrrolidinone or hydroxyethyl methacrylate~ or both, which contributes to the wettability or hydration of the lensl or to both wettability and hydration of lenses.
Thishydrophylic constituent may compriser preferrably, at least 2 to 3% and may comprise up to about 75~ or more of the polymeric lens material.
Exemplary percentages of ~elected formulations are shown in the following tables:
I
Trimethylsilyl methyl methacrylate 5 to 95 weight %
Methyl methacrylate1 to 50 wieght %
N-vinyl pyrrolidinone1 to 50 wieght %
Methacrylic acid1 to 10 weight ~
Ethylene glycol dimethacrylate1 to 10 weight %
II
Trimethylsilyl methyl methacrylate 20 to 90 weight ~
Methyl methacrylate20 to 60 weight %
N-vinyl pyrrolidinone1 to 10 weight %
III
Trimethylsilyl methyl methacrylate 20 to 90 ~eight ~
N-vinyl pyrrolidinone3 to 60 weight %
Methacrylic acid1 to 10 weight %
IV
Trimethylsilyl methyl methacrylate 20 to 95 weight N-vinyl pyrrolidinone5 to 80 weight V
Trimethylsilyl mekhyl methacrylate 25 to 95 weight %
Hydroxyethyl methacrylate5 to 75 weitht VI
Trimethylsilyl methyl methacrylate 5 to 95 weight %
Methyl methacrylate5 to 90 weight %
~Z5~33~3 1,3,Bistmethyacryloxy propyl~l,l';3,3'-tetrakis(trimethylsiloxy)disiloxane 5 to 35 ~eight 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
Trimetho~ylsilyl 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 %
XI~
Phenyltetramethyldisilylmethylene-20methylmethacrylate 5 to 95weight ~
Methacrylic acid 5 to 60weight %
Typically, in the preferred embodiments, a hydrophylicmonome~would also comprise the polymerization mix.
25It has also been found advantageous to include methacrylic acidand/ormethyl methacrylate asa monomer in the formation of the polymerized lense material; however~
one ofthe surprising discoveries of this invention is that high ~uality lenses can be formed without either of these 30constituents.
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 35invention:
~5i33~3 Ib R R -C-R R.
Ig a I c X -C --S i----C - X
Rh Rd-C-Rf R
Re wherein Ra through R; are hydrogen or alkyl, aryl, aralkyl, or silyl moi.eties, which may inc].ude vinyl, allyl, acrylyl, acrylic, methacryli.c, ethacrylic, or pyrrolidinonyl substituents and may also contain up to about 35 weight percent siloxyl, and wherein either X]
or X2, or both Xl and X2 are vinyl polymeri.zable group containing moie-ties. The term "vinyl polymerizable group" is used here in a particular sense to mean a 1~; polymerizable group conta:ining the carborl-carborl doub]e bond which is polymerized in the formation of polyvinyl polymers, i.e. the following structures:
-C=C- and -C-C=C-;
exemplary o.f which vinyl polyrnerizable groups are:
vinyl, allyl, acrylyl, acrylyl, me-thacrylyl, or styryl.
Exemplary of the monomers suitable for forming the polymers and copolymers of this invention are the following:
.
CM~=CH- ~ -Si-CH3;
CH2=CH- ~ -Si-(CH2)n~CH3 wherein n is a positive integer from I to 5, preferably 1 to 3;
:~25~3~3 r CH3~
CH2=CH- -Si- -CnH]2n~1) CH3 n CH2-C~i-~i-~3 ;
CH2=CH~
CH2=CH~Si~(CH2)n~
wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
CH3 I Cl H3 CH3_~i_(CH2) n_O_C_C=CH2 wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
2 5 CIH3 CH3 ~ CIH3 CH3-li-(CH2)n-Si-(CH2)n-0-C-C=CH2, CH3 C~3 wherein n i~ a positive integer from 1 to 5, preferrably 1 to 3;
~ZS~39L~
oH3 ll H 2 CH35iCH3 CH3 CH2 1l CIH3 CH30CH2SiCH2~i(CH2)n-0-C-C=CH3;
CH3 ~H2 CH3~iCH3 CH2 - C ~ CH3 CH3 'CH3 ~ H2)n~li-cH2 -bi~cH2-o-c-c=cH
CH2 C= CH3 CH3 wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
R2-Xi-(cH2)n-o-c-c-cH2 wherein n is a positive integer from 1 to 5, preferrably 1 to 3 and Rl~ R2 and R3 are selected from the group consisting of methyl, ~H3 C,H3 ~H-CH2 phenyl, CH3Si-, CH3~iCH2-~ CH3SiCH2-~
CH3 1H3 ~H3 alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl CH3SiCH3 R C, H3 CH O-C-C-CH2;
CH3SiCH3
2 ~ CH3 ~ -Cl-l=C~12;
CH2=CH-~ _51 - ( CH2 ) -C~l=CH2 ' :~Z5~3~
wherein n is a positive integer from 1 to 5, preferably 1 to 3,;
S CH2=CH-li- ~-Si-CH=CH2;
CH 2=CH--5 i--e3--I i -CH=CH 2;
EE H
Cl H3 ,~ Cl H3 CH2=CH~~i~(CH2)n~~ (CH2) nCH-CH2 CH3 \=/ CH3 wherein n is a positive integer from 1 to 5, preferably 1 to 3,, CH3SiCH3 H3CI ~ ~H3 CH2 R CH3 CH2=C- ~o-cH2ticH2$i(cH2)n~o-c- =CH2; and CH3~iCH3 kH2 1~24 H3~ O CH3~iCH3 IOI CIH3 CH2=C-~ ~H -- O-C- =CH2, CH3~iCH3 R2s 4~
wherein R24 and R2s are selected from the group consisting of methyl, ~H3 CH3 CH=CH2 phenyl, CH3~i-, CH3~iCH2-~ CH3~iCH2 ~H3 ~H3 CH3 alkylmethoxy, phenylmethyl, and N-alkylpyrrol-idinonyl.
In general, vinyl, allyl, acrylallyl, acrylic, methacrylic or ethacrylic derivatives of ~he 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.
lS The alkylsilane polymer lenses of this invention have been discovered to have extremely beneficial, and most unexpectedand unpredictable properties as contactlenses.
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., QX~ ~n~iQn ~n~ ~n O~yq~n~s~m~bli 5Qn~ L~ns, American Journal of Optrometry, July 1971, pp.545-555, for a discussion of Dk values) in the 20'sv the highest being about 30 to32. 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 lensesl These very surprising advantages, coupled with good optical quality could not have been 33~
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 alkylr or n-alkylpyrrolidinonemay be included to improvewettability.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 inventionl De~cri~iQn Qf ~h~ Preferred EmkLLim~n~
Nonew silanechemistry, per se, is involved in the present invention; rather, it has been discovered that alkylsilane polymer contact lenses have most ~nexpected 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 moietyt 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 chlorosilyl-alkyl methacrylate, e.g. trichlorosilyl propyl methacrylate, to give tris(trimethylsilylmethyl) silyl-propyl methacrylate.
~25~ 3 ~ample A
Trimethylsilyl Methyl ~ethacrylate Trimethylsilylmethyl methacrylate was prepared as follows: Methacrylic acid (29.6 g) was dissolved in dry ether t600 ml), sodium carbonate (18~6 g) was added slowly to form the sodium salt. Chloromethyl trimethyl silane (42.2 g) was added to the gelatenous solid formed from the preceeding salt forming reaction, followed by the addition of hydroquinone (1.00 g). 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 29.5C. 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.
E~ample B
Phenyldimethylsilyl ~ethyl ~ethacrylate Phenyldimethylsilyl Methyl Methacrylate wasprepared by reacting phenyl dimethyul chloromethyl silan~ (161 g) with methacrylic acid (132 g) and triethylamine (132 g) 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 86C. at 0.1 mm Hg. The yield, 105.2g, was51.5~ 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.
Len~ ~anufacture The following general technique was followed in the ~Z58343 preparation of lens blanks and lenses:
Monomers in the specified ratio and initiator werethoroughly mixed and dry~d 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 100C. for about 2 hours followed by a reduction to a post-cure temperature of about 80C. forapost 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.
~en~ Material No. 1 Trimethylsilyl methyl methacrylate 45~*
Methyl methacrylate 41~
N-vinyl pyrrolidinone 3%
Methacrylic acid 6%
Ethylene glycol dimethacrylate5%
Initiator** (Trace) * Percentages in all examples by weight.
** 2,2'azobis-2,4-dimethyl-4-methoxy-valeronitrile 0.001-0.5~ in all Lens examples Initial Cure Temperature 102C.
Initial Cure Time 2 hours.
Post Cure Temperature 82-85C.
Post Cure Time 16 hours.
Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Len~ ~aterial No. 2 Trimethylsil~l methyl methacrylate 30%*
~Z51~343 Methyl methacrylate 56%
N-vinyl pyrrolidinone 3~
Methacrylic acid 5%
Ethylene glycol dimethacrylate 6%
Initiator** (Trace) Initial Cure Temperature 76C.
Initial Cure Time 3/4 hours Post Cure Temperature 52-58C.
Post Cure Time 18 hours Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Lens ~aterial 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 69C.
Initial Cure Time 3/4 hours Post Cure Temperature 52-58C.
Post Cure Time 18 hours Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Len~ ~aterial No. 4 Trimethylsilyl methyl methacrylate 45 Methyl methacrylate 41~
~f~ S~ 3 ~ 3 N-vinyl pyrrolidinone 3%
Methacrylic acid 6 Ethylene glycol dimethacrylate 5 Initiator** (Trace) Initial Cure Temperature 102C.
Initial Cure Time 2 hours Post Cure Temperature 82-85C.
Post Cure Time 16 hours Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Len~ ~aterial 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 76C.
Initial Cure Time 3/4 hours Post Cure Temperature 52-58C.
Post Cure Time 18 hours Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Len~ ~aterial ~o. 6 Trimethylsilyl methyl methacrylate 60 Methyl methacrylat~ 26%
N-vinyl pyrrolidinone 3%
8~9~3 Methacryli~ acid 5%
Ethylene glycol dimethacrylate 6 Initiator** (Trace) Initial Cure Temperature69C.
Initial Cure Time 3/4 hours Post Cure Temperature 52-58C.
Post Cure Time 18 hours Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Len~ ~aterial ~o. 7 Trimethylsilyl methyl methacrylate 86 N-vinyl pyrrolidinone 3~
Methacrylic acid 5%
Ethylene glycol dimethacrylate 5%
Initiator** (Trace) Initial Cure Temperature57C.
Initial Cure Time 3/4 hours Post Cure Temperature 57C.
Post Cure Time 21 hours Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExceptional Lens ~aterial No~ 8 Trimethylsilyl methyl methacrylate 40 Methyl methacrylate 31~
N-vinyl pyrrolidinone 3%
1,3,Bis(methyacryloxy propyl~l,l';3,3'-tetrakis(trimethylsiloxy)disiloxane 20%
~'~5~33~3 Methacrylic acid 6%
Initiator** (Trace) Initial Cure Temperature 80C.
Initial Cure Time 3/4 hours.
Post Cure Temperature 55-58C.
Post Cure Time 21 hours.
Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Len~ Material No. 9 Trimethylsilyl methyl methacrylate 25%*
Methyl methacrylate 47%
N-vinyl pyrrolidinone 3%
Trimethoxysilyl propyl methacrylate 25~
Initiator** Trace Initial Cure Temperature 58C.
~ Initial Cure Time1 1/4 hours.
Post Cure Temperature 58C.
Post Cure Time 20 hours~
Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Lens ~aterial No. 10 Phenylmethylsilyl methylmethacrylate 50%*
Methyl methacrylate 36~
N-vinyl pyrrolidinone 3%
Methacrylic acid 6%
~thylene glycol dimethacrylate 5%
Initiator** Trace lg Initial Cure Temperature 58C.
Initial Cure Time 1 1/4 hours Post Cure Temperature 58C.
Post Cure Time 20 hours Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Goocl Dimensional stabilityExcellent 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 83-85C.
Post Cure Time 16 hours Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stability Excellent 30 This lens material has an exceptionally high refractive index, making it ideally suited to the manufacture of bifocal and thin lenses.
Len~ ~aterial ~o. 12 Phenylmethylsilyl methylmethacrylate 86%*
N-vinyl pyrrolidinone 3 ~2~133~3 Methacrylic acid 6%
Ethylene glycol dimethacrylate 5%
Initiator** Trace Initial Cure Temperature 104C.
Initial Cure Time 2 hours.
Post Cure Temperature 84-86C.
Post Cure Time 18 hours.
Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent This lens material has an exceptionally high refractive 15 index, making it ideally suited to the manufacture of bifocal and thin lenses.
Len~ ~aterial ~o. 13 Trimethoxylsilyl propylmethacrylate 45%*
Methyl methacrylate 41%
N-vinyl pyrrolidinone 3%
Methacrylic acid 5%
Ethylene glycol dimethacrylate 5%
Initiator** Trace Initial Cure Temperature 102C.
Initial Cure Time 2 hours.
Post Cure Temperature 82-85C.
Post Cure Time 16 hours.
Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent Len~ Material ~o~ 14 Trimethylsilyl methyl methacrylate 45%*
~5~33~3 Hydroxyethyl methacrylate 10%
N-vinyl pyrrolidinone 50%
Methacrylic acid 4%
Ethylene glycol dimethacrylate1%
Initiator** Trace Initial Cure Temperature 57C.
Initial Cure Time 2 hours.
Post Cure Temperature 57C.
Post Cure Time 20 hours.
Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent 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.
Len~ Material ~o~ 15 Phenyldimethylsilyl methylmethacrylate 20%*
Hydroxyethyl methacrylate 74 Methacrylic acid 5~
Triethylene glycol dimethacrylate 5%
Initiator** Trace Initial Cure Temperature 102C.
Initial Cure Time 2 hours.
Post Cure Temperature 84-86C.
Post Cure Time 18 hours.
Lens Qualitie~:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent 35 This lens material has an exceptionally high refractive 83~3 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.
S Len~ ~aterial ~o. 16 Phenyltetramethyldisilylmethylene-methylmethacrylate 50%*
Methyl methacrylate 38.5%
Methacrylic acid 6%
Ethylene glycol dimethacrylate 5~
N-vinylpyrrolidinone 3%
Initiator** Trace Initial Cure Temperature 100C.
Initial Cure Time 2 hoursO
Post ~ure Temperature 82-83C.
Post Cure Time 17 hours.
Lens Qualities:
Clarity Excellent Hardness Good Machinability Good Wettability Good Dimensional stabilityExcellent This lens material has an exceptionally high refractive index, making it ideally suited to the manufacture of bifocal and thin lenses.
Di~cu~sion and ~quivalents These lens materials had excellent optical properties and ~ome had outstanding refractive index characteristics. All were ideal for the manufacture of high quality excèptionally comfortable lenses. Some had moderate to high hydration capacity, in addition to being excellent, clear comfortable lens characteristics.
Oneof the important discoveries of this invention is that these len~ materials are far more comfortable for thewearerthanthe most nearly comparable lense~ formed of ~58~43 siloxanyl polymers, the silicone polymers of the prior art and o~ 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, thuscontributing to healthier eyetiss~e andgreater 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 com~ort is the wettability ofthelens materials of this invention. Silanes have typically been used in ~aterproofing applications and one would predict a highly hydrophobic lens material. Quite surprisingly, however, thelenses ofthis invention arequite hydrophylic and, indeed, in some formulations, hydrate to a moderate to high level.
Another surprising characteristic of lens materialsofthepresent invention isthat it ispossibleto form excellent lens materials with excellent optical, refractive, mechanical and comfort properties ~ithout 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 ~ avast numberoElensmaterials ancllenses which can be manufactured within the scope of this invention. Many analogous and homologous monomers ofthe 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 83~L~
2~
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 silaneswith a cross-linking monomer and a monomer, s~ch as n-vinylpyrrolidinone or hydroxyethyl methacrylate~ or both, which contributes to the wettability or hydration of the lensl or to both wettability and hydration of lenses.
Thishydrophylic constituent may compriser preferrably, at least 2 to 3% and may comprise up to about 75~ or more of the polymeric lens material.
Exemplary percentages of ~elected formulations are shown in the following tables:
I
Trimethylsilyl methyl methacrylate 5 to 95 weight %
Methyl methacrylate1 to 50 wieght %
N-vinyl pyrrolidinone1 to 50 wieght %
Methacrylic acid1 to 10 weight ~
Ethylene glycol dimethacrylate1 to 10 weight %
II
Trimethylsilyl methyl methacrylate 20 to 90 weight ~
Methyl methacrylate20 to 60 weight %
N-vinyl pyrrolidinone1 to 10 weight %
III
Trimethylsilyl methyl methacrylate 20 to 90 ~eight ~
N-vinyl pyrrolidinone3 to 60 weight %
Methacrylic acid1 to 10 weight %
IV
Trimethylsilyl methyl methacrylate 20 to 95 weight N-vinyl pyrrolidinone5 to 80 weight V
Trimethylsilyl mekhyl methacrylate 25 to 95 weight %
Hydroxyethyl methacrylate5 to 75 weitht VI
Trimethylsilyl methyl methacrylate 5 to 95 weight %
Methyl methacrylate5 to 90 weight %
~Z5~33~3 1,3,Bistmethyacryloxy propyl~l,l';3,3'-tetrakis(trimethylsiloxy)disiloxane 5 to 35 ~eight 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
Trimetho~ylsilyl 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 %
XI~
Phenyltetramethyldisilylmethylene-20methylmethacrylate 5 to 95weight ~
Methacrylic acid 5 to 60weight %
Typically, in the preferred embodiments, a hydrophylicmonome~would also comprise the polymerization mix.
25It has also been found advantageous to include methacrylic acidand/ormethyl methacrylate asa monomer in the formation of the polymerized lense material; however~
one ofthe surprising discoveries of this invention is that high ~uality lenses can be formed without either of these 30constituents.
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 35invention:
~5i33~3 Ib R R -C-R R.
Ig a I c X -C --S i----C - X
Rh Rd-C-Rf R
Re wherein Ra through R; are hydrogen or alkyl, aryl, aralkyl, or silyl moi.eties, which may inc].ude vinyl, allyl, acrylyl, acrylic, methacryli.c, ethacrylic, or pyrrolidinonyl substituents and may also contain up to about 35 weight percent siloxyl, and wherein either X]
or X2, or both Xl and X2 are vinyl polymeri.zable group containing moie-ties. The term "vinyl polymerizable group" is used here in a particular sense to mean a 1~; polymerizable group conta:ining the carborl-carborl doub]e bond which is polymerized in the formation of polyvinyl polymers, i.e. the following structures:
-C=C- and -C-C=C-;
exemplary o.f which vinyl polyrnerizable groups are:
vinyl, allyl, acrylyl, acrylyl, me-thacrylyl, or styryl.
Exemplary of the monomers suitable for forming the polymers and copolymers of this invention are the following:
.
CM~=CH- ~ -Si-CH3;
CH2=CH- ~ -Si-(CH2)n~CH3 wherein n is a positive integer from I to 5, preferably 1 to 3;
:~25~3~3 r CH3~
CH2=CH- -Si- -CnH]2n~1) CH3 n CH2-C~i-~i-~3 ;
CH2=CH~
CH2=CH~Si~(CH2)n~
wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
CH3 I Cl H3 CH3_~i_(CH2) n_O_C_C=CH2 wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
2 5 CIH3 CH3 ~ CIH3 CH3-li-(CH2)n-Si-(CH2)n-0-C-C=CH2, CH3 C~3 wherein n i~ a positive integer from 1 to 5, preferrably 1 to 3;
~ZS~39L~
oH3 ll H 2 CH35iCH3 CH3 CH2 1l CIH3 CH30CH2SiCH2~i(CH2)n-0-C-C=CH3;
CH3 ~H2 CH3~iCH3 CH2 - C ~ CH3 CH3 'CH3 ~ H2)n~li-cH2 -bi~cH2-o-c-c=cH
CH2 C= CH3 CH3 wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
R2-Xi-(cH2)n-o-c-c-cH2 wherein n is a positive integer from 1 to 5, preferrably 1 to 3 and Rl~ R2 and R3 are selected from the group consisting of methyl, ~H3 C,H3 ~H-CH2 phenyl, CH3Si-, CH3~iCH2-~ CH3SiCH2-~
CH3 1H3 ~H3 alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl CH3SiCH3 R C, H3 CH O-C-C-CH2;
CH3SiCH3
3~
CH3SiCH3 CH3 ¦ CH3 1l CIH3 CH3Si -CH -Si-(CH2)n-0-C~C=CH2, 5CH3 ¦ CH3 CH3SiCH3 wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
5H~ -S~ H3 0 CH3 CH3S\iCH3 ~ H-O-C-C=CH2;
CH2 -SlCH3 R~
CH2)Jn~O~c~c=cH2 ~Si--CH2 25wherein n is a positive integerfrom l to 5, preferably 1 to 3, and R~ and Rs are ~elected from the group consisti.nc~ of methyl, CIH3 ~H3 CH-CH2 phenyl, CH3Si-, CH3SiCH2-~ CH3$iCH2 alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl 33~
~6 CH 2 ~ H 2 CH3 \ R 7H3 CH3SiCH3CH3Si(CH2)n-O-c-c=cH2 5 \ CH3 CH 2 ~ CH 2 wherein n is a positive integer frc>m 1 to 5, preferably to 3, and R6 and R7 are selected from the group consisting of methyl, CIH3 ClH3 CH=CH2 phenyl, CH37i ~ CH3SiCH2-~ CH3~!,iCH2-' alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl R~ 8 1~9 CH~,Si~~-CH2----~\CH3 j~ ~H3 ~H ,CH-O--C-C=CH2 CH~Si---CH2-~-SiCH3 ~ 10 ~11 wherein n is a positive integer from 1 to 5, preferably to 3, and R~ - Rll are selected from the group consisting of methyl, ~H3 CH3 CH=CH2 phenyl, ClH3Si-, CH31iCH2-~ CH3SiCH2 ~H3 CH3 CH3 alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl and ~ 'h~83~3 Rl2 CH3~ C,H2 / CH3 \ 1l C~H3 HC - Si CH2 - ~iCH2`o-C-C-CH3 \ CH3 CH3~ CH2 wherein n is a positive integer from l to 5, preferably l to 3, and Rl2 and Rl3 are selected from the group consisting of methyl, C~H3 ~CH3 CH=CH2 phenyl, CH3Si-, CH3SiCH2-, CH3~iCH2-~
alkylmethoxy, phenylmethyl, and N-alkylpyrrol-idinonyl 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:
H3C~ 1l lR14 g CIH3 CH2= -C-O-CH2- ( ~ i-CH2) n-0-C-C=CH3 ~ 15 wherein n is a positive integer from 1 to 5, preferably l to 3, and Rl4 and Rls are selected from the group consisting of methyl, CH3 CH3 CH=CH2 phenyl, CH3Si-, CH3SiCH2-~ CH3SiCH2-~
C~3 CH3 CH3 alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl H3~ R ~16 Rl8 1~ ~CH3 CH2=(~:-C-O-CH2-~ i- ( CH2) nli-CH2-0-C-C=CH3 R17 ~l9 ,83~3 wherein n is a positive integer :from I to 5, preferab~y 1 to 3, and R16 to Rlg are selected from the group consisting of methyl, phenyl, C CH3SiCH2-, CH3SiCH2-, alkylmethoxy, pheny]methyl, and N--alkylpyrrol-idinonyl.
A monomor which is predominantly silane is:
H3C1 11 Rl2o R122 11 C1~13 H2C=C-C-O-(CH2)n-Si -O- Si-(CH2) -0-C-C=CH2 wherein n is a positive integer from 1 to 5, preferab~y 1 to 3, and R20 to R23 are se]ected from the group consisting of:
CIH3 CIH3 CH=CH2 CH3Si-, CH3SiCH2-, and CH3SiCH2-Other monomers which include two polymerizable groups include:
CH2=CH- ~ 5~ ~ -Cl-l=CH2;
CH2=CH~ Si-(CH2)n-CH=CH2 c~,3 wherein n is a positive in-teger from 1 to 5, preferably 1 to 3;
~5~3~3 CH2=CH-,3 - ~ _5i_CH=CM2;
CH2=CH-si- ~ ff~3 CH2=CH~Si~(CH2)n~ ~ ~~i-(CH2)nCH=CH2 ~ H3 H3 wherein n is a positive integer from 1 to 5, preferably 1 to 3,;
CH3~i~H3 H3~ ~ CH3 CH2 R CH3 CH2=~-C-o-cH2sicH2$i(cH2)n-o-c-c=cH2; and CH3 ~fl2 CH3SiCH3 ~H2 ~2~
H3~, R CH3~1CH3 R CH3 30 CH2=C-C - CH -O-~-~=CH2, Cf]3,3iCH3 wherein R24 and R2s are selected from the group consisting of methyl, ~251~3~3 ~H3 IH3 ~-CH2 phenyl, CH3~i-,CH31iCH2-~ CH3~iCH2-' H3 C~3 ~H3 alkylmethoxy, phenylmethyl, and N-alkylpyrrol-idinonyl.
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 equivalen~ to the specific, exemplary monomers, and polymers and copolymers of the same may be used as contact lens materials and lenses7 Indu~trial Application This invention is useful in the optical industry lS and, particularly, in the manufacture of optical contact lenses for the correction of certain human visual defects
CH3SiCH3 CH3 ¦ CH3 1l CIH3 CH3Si -CH -Si-(CH2)n-0-C~C=CH2, 5CH3 ¦ CH3 CH3SiCH3 wherein n is a positive integer from 1 to 5, preferrably 1 to 3;
5H~ -S~ H3 0 CH3 CH3S\iCH3 ~ H-O-C-C=CH2;
CH2 -SlCH3 R~
CH2)Jn~O~c~c=cH2 ~Si--CH2 25wherein n is a positive integerfrom l to 5, preferably 1 to 3, and R~ and Rs are ~elected from the group consisti.nc~ of methyl, CIH3 ~H3 CH-CH2 phenyl, CH3Si-, CH3SiCH2-~ CH3$iCH2 alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl 33~
~6 CH 2 ~ H 2 CH3 \ R 7H3 CH3SiCH3CH3Si(CH2)n-O-c-c=cH2 5 \ CH3 CH 2 ~ CH 2 wherein n is a positive integer frc>m 1 to 5, preferably to 3, and R6 and R7 are selected from the group consisting of methyl, CIH3 ClH3 CH=CH2 phenyl, CH37i ~ CH3SiCH2-~ CH3~!,iCH2-' alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl R~ 8 1~9 CH~,Si~~-CH2----~\CH3 j~ ~H3 ~H ,CH-O--C-C=CH2 CH~Si---CH2-~-SiCH3 ~ 10 ~11 wherein n is a positive integer from 1 to 5, preferably to 3, and R~ - Rll are selected from the group consisting of methyl, ~H3 CH3 CH=CH2 phenyl, ClH3Si-, CH31iCH2-~ CH3SiCH2 ~H3 CH3 CH3 alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl and ~ 'h~83~3 Rl2 CH3~ C,H2 / CH3 \ 1l C~H3 HC - Si CH2 - ~iCH2`o-C-C-CH3 \ CH3 CH3~ CH2 wherein n is a positive integer from l to 5, preferably l to 3, and Rl2 and Rl3 are selected from the group consisting of methyl, C~H3 ~CH3 CH=CH2 phenyl, CH3Si-, CH3SiCH2-, CH3~iCH2-~
alkylmethoxy, phenylmethyl, and N-alkylpyrrol-idinonyl 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:
H3C~ 1l lR14 g CIH3 CH2= -C-O-CH2- ( ~ i-CH2) n-0-C-C=CH3 ~ 15 wherein n is a positive integer from 1 to 5, preferably l to 3, and Rl4 and Rls are selected from the group consisting of methyl, CH3 CH3 CH=CH2 phenyl, CH3Si-, CH3SiCH2-~ CH3SiCH2-~
C~3 CH3 CH3 alkylmethoxy, phenylmethyl, and N-alkyl-pyrrol-idinonyl H3~ R ~16 Rl8 1~ ~CH3 CH2=(~:-C-O-CH2-~ i- ( CH2) nli-CH2-0-C-C=CH3 R17 ~l9 ,83~3 wherein n is a positive integer :from I to 5, preferab~y 1 to 3, and R16 to Rlg are selected from the group consisting of methyl, phenyl, C CH3SiCH2-, CH3SiCH2-, alkylmethoxy, pheny]methyl, and N--alkylpyrrol-idinonyl.
A monomor which is predominantly silane is:
H3C1 11 Rl2o R122 11 C1~13 H2C=C-C-O-(CH2)n-Si -O- Si-(CH2) -0-C-C=CH2 wherein n is a positive integer from 1 to 5, preferab~y 1 to 3, and R20 to R23 are se]ected from the group consisting of:
CIH3 CIH3 CH=CH2 CH3Si-, CH3SiCH2-, and CH3SiCH2-Other monomers which include two polymerizable groups include:
CH2=CH- ~ 5~ ~ -Cl-l=CH2;
CH2=CH~ Si-(CH2)n-CH=CH2 c~,3 wherein n is a positive in-teger from 1 to 5, preferably 1 to 3;
~5~3~3 CH2=CH-,3 - ~ _5i_CH=CM2;
CH2=CH-si- ~ ff~3 CH2=CH~Si~(CH2)n~ ~ ~~i-(CH2)nCH=CH2 ~ H3 H3 wherein n is a positive integer from 1 to 5, preferably 1 to 3,;
CH3~i~H3 H3~ ~ CH3 CH2 R CH3 CH2=~-C-o-cH2sicH2$i(cH2)n-o-c-c=cH2; and CH3 ~fl2 CH3SiCH3 ~H2 ~2~
H3~, R CH3~1CH3 R CH3 30 CH2=C-C - CH -O-~-~=CH2, Cf]3,3iCH3 wherein R24 and R2s are selected from the group consisting of methyl, ~251~3~3 ~H3 IH3 ~-CH2 phenyl, CH3~i-,CH31iCH2-~ CH3~iCH2-' H3 C~3 ~H3 alkylmethoxy, phenylmethyl, and N-alkylpyrrol-idinonyl.
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 equivalen~ to the specific, exemplary monomers, and polymers and copolymers of the same may be used as contact lens materials and lenses7 Indu~trial Application This invention is useful in the optical industry lS and, particularly, in the manufacture of optical contact lenses for the correction of certain human visual defects
Claims (25)
1. Contact lenses comprising polymers resulting from the polymerization of one or more disilane monomers of the following structure:
, or wherein n is a positive integer from 1 to 3, each of Ra through Rf including Ra' through Rf' is a hydrogen, alkyl, aryl, aralkyl, or silyl moiety which silyl moiety may optionally include vinyl, allyl, acrylyl, acrylic, methacrylic, ethacrylic, or pyrrolidinonyl substituents, and optionally including up to about 35 weight percent siloxyl and wherein either or both of X1 and X2 are vinyl polymerizable group containing moieties.
, or wherein n is a positive integer from 1 to 3, each of Ra through Rf including Ra' through Rf' is a hydrogen, alkyl, aryl, aralkyl, or silyl moiety which silyl moiety may optionally include vinyl, allyl, acrylyl, acrylic, methacrylic, ethacrylic, or pyrrolidinonyl substituents, and optionally including up to about 35 weight percent siloxyl and wherein either or both of 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.
wherein n is a positive integer from 1 to 3.
3. 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 wherein n is a positive integer from 1 to 3.
wherein n is a positive integer from 1 to 3 and R1, R2 and R3 are selected from the group consisting of wherein n is a positive integer from 1 to 3.
4. Contact lenses comprising polymers and copolymers resulting from the polymerization or copolymerization of one or more of the following:
or wherein n is a positive integer from 1 to 5, and R4 and R5 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, and R4 and R5 are selected from the group consisting of methyl, phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl.
5. 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, and R6 and R7 are selected from the group consisting of methyl, phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl.
wherein R8 - R11 are selected from the group consisting of methyl, phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl;
or wherein R12 and R13 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, and R6 and R7 are selected from the group consisting of methyl, phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl.
wherein R8 - R11 are selected from the group consisting of methyl, phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl;
or wherein R12 and R13 are selected from the group consisting of methyl, phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl.
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 2 to 5, 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, and R16 through R19 are selected from the group consisting of methyl, phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl.
wherein n is a positive integer from 2 to 5, 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, and R16 through R19 are selected from the group consisting of methyl, phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl.
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 5, and R20 to R23 are selected from the group consisting of the polymer being characterized as predominantly a silane polymer.
wherein n is a positive integer from 1 to 5, and R20 to R23 are selected from the group consisting of the polymer being characterized as predominantly a silane polymer.
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, wherein R24 and R25 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, wherein R24 and R25 are selected from the group consisting of methyl, phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl.
9. 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 weight %
N-vinyl pyrrolidinone 1 to 50 weight %
Methacrylic acid 1 to 10 weight %
Ethylene glycol dimethacrylate 1 to 10 weight %.
Trimethylsilyl methyl methacrylate 5 to 95 weight %
Methyl methacrylate 1 to 50 weight %
N-vinyl pyrrolidinone 1 to 50 weight %
Methacrylic acid 1 to 10 weight %
Ethylene glycol dimethacrylate 1 to 10 weight %.
10. 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 %.
Trimethylsilyl methyl methacrylate 20 to 90 weight %
Methyl methacrylate 20 to 60 weight %
N-vinyl pyrrolidinone 1 to 10 weight %.
11. 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 l to 10 weight %.
Trimethylsilyl methyl methacrylate 20 to 90 weight %
N-vinyl pyrrolidinone 3 to 60 weight %
Methacrylic acid l to 10 weight %.
12. 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 %
Trimethylsilyl methyl methacrylate 20 to 95 weight %
N-vinyl pyrrolidinone 5 to 80 weight %
13. 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 weight %.
Trimethylsilyl methyl methacrylate 25 to 95 weight %
Hydroxyethyl methacrylate 5 to 75 weight %.
14. 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 %.
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 %.
15. 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 %.
Phenylmethylsilyl methylmethacrylate 5 to 95 weight %
Methyl methacrylate 5 to 50 weight %.
16. 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 %.
Phenylmethylsilyl methylmethacrylate 5 to 95 weight %
Methacrylic acid 5 to 50 weight %.
17. A polymeric contact lens comprising the polymer resulting from the copolymerization of the following:
Trimethoxysilyl propylmethacrylate 5 to 95 weight %
Methyl methacrylate 5 to 60 weight %.
Trimethoxysilyl propylmethacrylate 5 to 95 weight %
Methyl methacrylate 5 to 60 weight %.
18. A polymeric contact lens comprising the polymer resulting from the copolymerization of the following:
Trimethyoxysilyl propylmethacrylate 5 to 95 weight %
Hydroxyethyl methacrylate 5 to 50 weight %.
Trimethyoxysilyl propylmethacrylate 5 to 95 weight %
Hydroxyethyl methacrylate 5 to 50 weight %.
19. 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 %.
Phenyldimethylsilyl methylmethacrylate 10 to 95 weight %
Hydroxyethyl methylmethacrylate 5 to 90 weight %.
20. A polymeric contact lens comprising the polymer resulting from the copolymerization of the following:
Phenyltetramethyldisilylmethylene-methylmethacrylate 5 to 95 weight %
Methacrylic acid 5 to 60 weight %
Phenyltetramethyldisilylmethylene-methylmethacrylate 5 to 95 weight %
Methacrylic acid 5 to 60 weight %
21. The contact lenses of claim 4 wherein n is a positive integer from 1 to 3.
22. The contact lenses of claim 5 wherein n is a positive integer from 1 to 3.
23. 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 2 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 3, and R16 through R19 are selected from the group consisting of methyl, phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl.
wherein n is a positive integer from 2 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 3, and R16 through R19 are selected from the group consisting of methyl, phenyl, alkylmethoxy, phenylmethyl, and N-alkyl-pyrrolidinonyl.
24. The contact lenses of claim 7 wherein n is a positive integer from 1 to 3.
25. The contact lenses of claim 8 wherein n is a positive integer from 1 to 3.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US64159484A | 1984-08-17 | 1984-08-17 | |
| US641,594 | 1984-08-17 | ||
| US74212285A | 1985-06-05 | 1985-06-05 | |
| US742,122 | 1985-06-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1258343A true CA1258343A (en) | 1989-08-08 |
Family
ID=27093802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000488838A Expired CA1258343A (en) | 1984-08-17 | 1985-08-16 | Alkylsilane contact lens and polymer |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0194277A4 (en) |
| CA (1) | CA1258343A (en) |
| WO (1) | WO1986001219A1 (en) |
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|---|---|---|---|---|
| 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 |
| WO2001036517A2 (en) * | 1999-08-11 | 2001-05-25 | 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 |
| AU2005275241B2 (en) * | 2004-07-14 | 2011-12-01 | 3M Deutschland Gmbh | Dental compositions conataining carbosilane polymers |
| JP4755182B2 (en) * | 2004-07-14 | 2011-08-24 | スリーエム イーエスピーイー アーゲー | Dental composition containing Si-H functional carbosilane component |
| ATE447924T1 (en) * | 2004-07-14 | 2009-11-15 | 3M Innovative Properties Co | DENTAL COMPOSITIONS WITH CARBOSILANE MONOMERS |
| EP1765261B1 (en) * | 2004-07-14 | 2015-08-19 | 3M Deutschland GmbH | Dental composition containing unsaturated carbosilane containing components |
| US7557231B2 (en) * | 2006-06-30 | 2009-07-07 | Bausch & Lomb Incorporated | Carboxylic tris-like siloxanyl monomers |
| EP2688892B1 (en) * | 2011-03-21 | 2020-11-18 | Momentive Performance Materials Inc. | Siloxane monomers containing hydrolysis resistance carbosiloxane linkage and thin films containing the same for contact lens application |
| 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 |
| 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)
| 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 |
-
1985
- 1985-08-08 WO PCT/US1985/001522 patent/WO1986001219A1/en not_active Application Discontinuation
- 1985-08-08 EP EP19850904314 patent/EP0194277A4/en not_active Withdrawn
- 1985-08-16 CA CA000488838A patent/CA1258343A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0194277A4 (en) | 1987-02-03 |
| WO1986001219A1 (en) | 1986-02-27 |
| EP0194277A1 (en) | 1986-09-17 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |