CA1226696A - Silicone-containing contact lens material and contact lenses made thereof - Google Patents
Silicone-containing contact lens material and contact lenses made thereofInfo
- Publication number
- CA1226696A CA1226696A CA000436190A CA436190A CA1226696A CA 1226696 A CA1226696 A CA 1226696A CA 000436190 A CA000436190 A CA 000436190A CA 436190 A CA436190 A CA 436190A CA 1226696 A CA1226696 A CA 1226696A
- Authority
- CA
- Canada
- Prior art keywords
- resin system
- accordance
- contact lens
- mole fraction
- mole
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Eyeglasses (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Abstract of the Disclosure An unsaturated multifunctional organopolysiloxane is used as a contact lens material in its polymerized form or as a polymerizate with other selected monomers. The contact lens material of this invention is preferably prepared from an acrylate or methacrylate substituted functional polyorganosiloxane.
Description
~5jfia~
Skye SILICONE-CONTAINING CONTACT LENS MATERIAL AND
CONTACT LENSES MADE THEREOF
Background of the Invention Contact lenses which derive their oxygen permeability from organosiloxane moieties require a substantial content of organosiloxane to provide sufficient oxygen transport to the cornea.
In general organosiloxane molecules tend to be incompatible in many compositions which include other monomers. For example, dissolving organosiloxane in methyl methacrylate and polymerizing said solution often results in an opaque material unsuitable for contact lens use.
Prior art has demonstrated that short organosiloxane units chemically bonded to an unsaturated, polymerizable group provide a means ox copolymerizing such organosiloxane monomers with other monomers to achieve a compatible and therefore, transparent material.
On the other hand, organosiloxane units containing only one unsaturated, polymerizable group often times will not provide a random copolymer when copolymerized with other monomers, particularly hydrophilic monomers. This situation leads to phase ~Z~j~9G~
2P1~8/713 Skye separation and an opaque material. In certain cases the phase separation is not detectable visually but is evidenced in the physical properties of the material. This condition can provide a material that exhibits brittle behavior and a propensity to fracture.
Tune physical properties of highly cross linked polymer prepared from dimethylsiloxane diacrylate oligomers has been known in the art. In general, microphage separation is suppressed as the amount of dimethylsiloxane groups in the prepolymer increases. This phenomenon is attributed to the absence of long organic sequences. Overall, the work of Katz J. Polyp. Sat. Chum. Ed. 16(3) 597 (1978) teaches against the copolymerization of such reactive organosiloxane monomers since organic sequences form leading to phase separation.
However, in a contact lens material it has been found desirable to include one or more comonomers to provide a proper balance of physical properties.
For contact lens applications it is therefore desirable to provide a random copolymer that contains a substantial amount of compatibilized organosiloxane units. The present invention utilizes branched organopolysiloxane structures containing multiple unsaturated, polymerizable groups These materials, when copolymerized with Skye 06/15/~3 other monomers provide compositions which are transparent, highly oxgen-permeable and durable.
The random nature of the polymerization process is enhanced by the presence of multiple, unsaturated polymerizable groups. The compatibilization of the organopolysiloxane monomers disclosed is improved through the use of highly branched organopolysiloxane moieties.
Summary of the Invention -It is an object of this invention to provide novel, unsaturated, multi functional ~organopolysiloxanes useful in forming contact lenses alone or in combination with other organic materials.
Another object of this invention is to provide polymerizates of unsaturated, multi functional organopolysiloxanes in the form of contact lenses which selections can be used alone or in combination with other organic materials.
An additional object of this invention is to provide contact lens materials and contact lenses in accordance with this invention which are oxygen-permeable, dimensionally stable, hydrophilic and of good optical transparency and clarity.
Still another object of this invention is to provide contact lenses in accordance with the preceding objects wherein outstanding hard and 2Z~9~
Skye semi-hard oxygen-permeable lenses are formed having good strength with reduced brittleness as compared to prior art organosiloxane-containing contact lenses .
According to the invention a contact lens is formed of an unsaturated, multi functional organopolysiloxanes having the formula:
;
Where:
R is hydrogen or methyl I is a diva lent alkaline radical having from one to five carbon atoms R" is a monovalent hydrocarbon radical having from one to five carbon atoms, a substituted monovalent hydrocarbon radical having from one to five carbon atoms, a phenol group, a substituted phenol group or a cyclohexyl group.
"a" + "b" + "c" = 1, where "a", "b" and "c" are each greater than I.
Preferably, the unsaturated, multi functional organopolysiloxanes of this invention are of the following composition:
~L2~6~
Skye I ~-(CH2)3-Sio~ ~)25 ) Sue ¦
"a" + "b" + "c" = 1, where "a", "b" and "c" are each greater than 0 The organopolysiloxanes are branched structures composed of three distinct structural units. The first unit is preferably a reactive organofunctional trisiloxane such as ~-methacryloxypropyl selection.
The second unit is preferably a chain extender such as a dimethylsiloxane unit while the third unit acts as a cap or end group and is preferably a trimethylsiloxane unit.
Preferably the unsaturated multi functional organopolysiloxanes of this invention have a viscosity of from 7 to 70 centistokes at 25C as measured with a capillary viscometer in ASTM Test No. D-446. The preferred mole fraction range of each of the three units is such that a = from 0.10 to 0.40 moles fraction, b = 0.25 to 0.80 mole fraction and c = 0.10 to 0.40 mole fraction.
In certain preferred embodiments a contact lens -I foe Skye material has a first component of the above formula in an amount of from 30 to 60% by weight with a = 0.20 to 0.35 mole fraction b = OWE to 0.60 mole fraction c = 0.20 to 0.40 mole fraction 69 to 40% by weight of methylmethacrylate and 1 to 10% by weight of vinylpyrrolidone, acrylic acid, methacrylic acid or mixtures thereof, with a mixture of the components being polymerized by free radical lo polymerization to 95~ completion or higher.
It is a feature of this invention that contact lenses made from the materials of this invention are preferably hard or semi-rigid, are easily fabricated and finished by conventional means have excellent dimensional stability, are inherently wettable with suitable refractive index and have good light transmission properties Such lenses are durable, have good oxygen permeability, are biocompatible with the eye, substantially non-hydrating, are chemically stable and have resistance to pretenses accumulation with reasonable scratch resistance. They can be worn safely and comfortably by users for extended periods of time while providing the wearer with good vision. This minimizes handling of the lenses and greatly improves anticipated life.
Skye 382~S/44S
Description of Preferred Embodiments It should be understood that any of the novel or~anopolysiloxanes of this invention are composed of a variety of molecules, not one specific composition, and therefore are described as by an average or typical composition with perhaps more than one polymerizable group. Such structures are known and described as mixed structures or otherwise known and described as resins.
The three-unit unsaturated, multi functional organopolysiloxanes of this invention which can be described as resins or resin systems can be prepared utilizing various reaction techniques widely known to the art. Most preferred is the cohydrolysis route in which chlorosilane or alkoxysilane intermediates are used. The cohydrolysis reaction may be carried out in the presence of water miscible solvents such as methanol or ethanol as well as in the presence of water immersible solvents such as deathly ether, dibutyl ether, Tulane, naphtha or chloroform.
The use of acetoxysilane intermediates in conjunction with an ethanol/sulfuric acid catalyst system may also be employed to produce the 25 unsaturated, multi functional organopolysiloxanes of this invention.
In cohydrolysis, a mixture of reactants are I
Skye chosen with the amount of each selected to provide the mole fractions desired in the final product.
Thus the mole fractions as set forth above with regard to "a", "b" and "c" define the structural limits in each particular composition. A slurry of the reactants in water, with the possible inclusion of an organic solvent, as known in the art is carried out. Sufficient time is allowed for hydrolysis and condensation to take place.
Typically times of from 2 hours to 2 days are used to permit completion at temperatures of from -20 to 98C and more preferably at room temperature. The organic phase carries the product formed and is separated from the water since the organic phase is immiscible with the water. Low molecular weight by-product is stripped from the organic phase preferably with the use of heat and vacuum as known in the art to remove molecular weights below about 200. The crude product remaining after by-product removal is extracted with a base solution, washed and then dried and is the purified final product referred to as a resin product capable of pharaoh reaction to form final high molecular weight polymerizates which can be formed or shaped into - 25 contact lenses and which act as contact lens materials.
Such cohydrolysis procedures are well known in Skye the art. Preferably ethanol-sulfuric acid catalyst is used wren alkoxysilanes and acetoxysilanes are used as reactants. Preferably the sullenness are mixed as in the above-noted procedure with an ethanol sulfuric acid catalyst containing a small amount of water. The reaction times and temperatures preferably are as described above as well as the workup of the crude product. Such reactions are detailed in US. patent 3,808,178.
Typically, the starting materials of this invention are chosen from the following classes of reactive sullenness:
R O
I O'ER -six Sioux R"3SiX
Where:
R is hydrogen or methyl R' is a diva lent alkaline radical having from one to about five carbon atoms.
R" is a monovalent hydrocarbon radical having ~lZ2~i~9~
Skye 06/15/~3 -from one to about five carbon atoms, a substituted monovalent hydrocarbon radical having from one to about five carbon atoms, a phenol group, a substituted phenol group or a eyelohexyl group.
"x" is a readily hydrolyzable group such as sheller, methoxy, ethics, methoxyethoxy, or attics.
The mole ratios of the various reactants will, to a large extent, control the molecular weight and structures of the resultant organopolysiloxanes.
Other factors, such as temperature of reaction and the presence of a solvent will also influence the composition of the product organopolysiloxane.
It should be understood that any of the novel organopol~siloxanes of this invention are composed of a variety of molecules, not one specific composition, and therefore must be described by an average or typical composition with perhaps more than one polymerizable group. Such structures are known and described as mixed structures or sometimes known as resins.
Preferably contact lens compositions can comprise an unsaturated, multifunetional organopolysiloxane polymerized alone or compolymerized with other monomers. The eopolymers can have incorporated therein a wetting agent such as a hydrofoil monomer and a hardness modifying agent which may be a hardening agent such as methyl ~.2~tjfi~36 Skye methacrylate or softening agents such as certain other acrylates or methacryates.
Physical properties of the compositions disclosed in this invention can be varied trough structural changes in the multi functional organopolysiloxane component and/or by varying the type and percent of comonomer.
In one embodiment of this invention oxygen transporting, transparent, inherently wettable contact lenses made from the polymerized organopolysiloxane resins of this invention alone.
In another embodiment of this invention polymeric compositions comprising the organopolysiloxane resins of this invention copolymerized with one or more other monomers.
Such other comonomers are preferably hardening or softening agents or hydrophilic agents. As for example, hardness modifying agents can be an ester of a Cluck mandrake or polyhydric alkanol or phenol and an acid selected from the class consisting essentially of acrylic, methacrylic, itaconic acid and mixtures thereof. Hydrophilic monomers can be of many different materials as will be described.
- 25 When comonomers are used, the polymeric compositions of the invention are preferably prepared by means of conventional free radical I it PLY
Skye 3~28S/44S
polymerization techniques. The free radical initiator is incorporated in amounts of from 0.01 to
Skye SILICONE-CONTAINING CONTACT LENS MATERIAL AND
CONTACT LENSES MADE THEREOF
Background of the Invention Contact lenses which derive their oxygen permeability from organosiloxane moieties require a substantial content of organosiloxane to provide sufficient oxygen transport to the cornea.
In general organosiloxane molecules tend to be incompatible in many compositions which include other monomers. For example, dissolving organosiloxane in methyl methacrylate and polymerizing said solution often results in an opaque material unsuitable for contact lens use.
Prior art has demonstrated that short organosiloxane units chemically bonded to an unsaturated, polymerizable group provide a means ox copolymerizing such organosiloxane monomers with other monomers to achieve a compatible and therefore, transparent material.
On the other hand, organosiloxane units containing only one unsaturated, polymerizable group often times will not provide a random copolymer when copolymerized with other monomers, particularly hydrophilic monomers. This situation leads to phase ~Z~j~9G~
2P1~8/713 Skye separation and an opaque material. In certain cases the phase separation is not detectable visually but is evidenced in the physical properties of the material. This condition can provide a material that exhibits brittle behavior and a propensity to fracture.
Tune physical properties of highly cross linked polymer prepared from dimethylsiloxane diacrylate oligomers has been known in the art. In general, microphage separation is suppressed as the amount of dimethylsiloxane groups in the prepolymer increases. This phenomenon is attributed to the absence of long organic sequences. Overall, the work of Katz J. Polyp. Sat. Chum. Ed. 16(3) 597 (1978) teaches against the copolymerization of such reactive organosiloxane monomers since organic sequences form leading to phase separation.
However, in a contact lens material it has been found desirable to include one or more comonomers to provide a proper balance of physical properties.
For contact lens applications it is therefore desirable to provide a random copolymer that contains a substantial amount of compatibilized organosiloxane units. The present invention utilizes branched organopolysiloxane structures containing multiple unsaturated, polymerizable groups These materials, when copolymerized with Skye 06/15/~3 other monomers provide compositions which are transparent, highly oxgen-permeable and durable.
The random nature of the polymerization process is enhanced by the presence of multiple, unsaturated polymerizable groups. The compatibilization of the organopolysiloxane monomers disclosed is improved through the use of highly branched organopolysiloxane moieties.
Summary of the Invention -It is an object of this invention to provide novel, unsaturated, multi functional ~organopolysiloxanes useful in forming contact lenses alone or in combination with other organic materials.
Another object of this invention is to provide polymerizates of unsaturated, multi functional organopolysiloxanes in the form of contact lenses which selections can be used alone or in combination with other organic materials.
An additional object of this invention is to provide contact lens materials and contact lenses in accordance with this invention which are oxygen-permeable, dimensionally stable, hydrophilic and of good optical transparency and clarity.
Still another object of this invention is to provide contact lenses in accordance with the preceding objects wherein outstanding hard and 2Z~9~
Skye semi-hard oxygen-permeable lenses are formed having good strength with reduced brittleness as compared to prior art organosiloxane-containing contact lenses .
According to the invention a contact lens is formed of an unsaturated, multi functional organopolysiloxanes having the formula:
;
Where:
R is hydrogen or methyl I is a diva lent alkaline radical having from one to five carbon atoms R" is a monovalent hydrocarbon radical having from one to five carbon atoms, a substituted monovalent hydrocarbon radical having from one to five carbon atoms, a phenol group, a substituted phenol group or a cyclohexyl group.
"a" + "b" + "c" = 1, where "a", "b" and "c" are each greater than I.
Preferably, the unsaturated, multi functional organopolysiloxanes of this invention are of the following composition:
~L2~6~
Skye I ~-(CH2)3-Sio~ ~)25 ) Sue ¦
"a" + "b" + "c" = 1, where "a", "b" and "c" are each greater than 0 The organopolysiloxanes are branched structures composed of three distinct structural units. The first unit is preferably a reactive organofunctional trisiloxane such as ~-methacryloxypropyl selection.
The second unit is preferably a chain extender such as a dimethylsiloxane unit while the third unit acts as a cap or end group and is preferably a trimethylsiloxane unit.
Preferably the unsaturated multi functional organopolysiloxanes of this invention have a viscosity of from 7 to 70 centistokes at 25C as measured with a capillary viscometer in ASTM Test No. D-446. The preferred mole fraction range of each of the three units is such that a = from 0.10 to 0.40 moles fraction, b = 0.25 to 0.80 mole fraction and c = 0.10 to 0.40 mole fraction.
In certain preferred embodiments a contact lens -I foe Skye material has a first component of the above formula in an amount of from 30 to 60% by weight with a = 0.20 to 0.35 mole fraction b = OWE to 0.60 mole fraction c = 0.20 to 0.40 mole fraction 69 to 40% by weight of methylmethacrylate and 1 to 10% by weight of vinylpyrrolidone, acrylic acid, methacrylic acid or mixtures thereof, with a mixture of the components being polymerized by free radical lo polymerization to 95~ completion or higher.
It is a feature of this invention that contact lenses made from the materials of this invention are preferably hard or semi-rigid, are easily fabricated and finished by conventional means have excellent dimensional stability, are inherently wettable with suitable refractive index and have good light transmission properties Such lenses are durable, have good oxygen permeability, are biocompatible with the eye, substantially non-hydrating, are chemically stable and have resistance to pretenses accumulation with reasonable scratch resistance. They can be worn safely and comfortably by users for extended periods of time while providing the wearer with good vision. This minimizes handling of the lenses and greatly improves anticipated life.
Skye 382~S/44S
Description of Preferred Embodiments It should be understood that any of the novel or~anopolysiloxanes of this invention are composed of a variety of molecules, not one specific composition, and therefore are described as by an average or typical composition with perhaps more than one polymerizable group. Such structures are known and described as mixed structures or otherwise known and described as resins.
The three-unit unsaturated, multi functional organopolysiloxanes of this invention which can be described as resins or resin systems can be prepared utilizing various reaction techniques widely known to the art. Most preferred is the cohydrolysis route in which chlorosilane or alkoxysilane intermediates are used. The cohydrolysis reaction may be carried out in the presence of water miscible solvents such as methanol or ethanol as well as in the presence of water immersible solvents such as deathly ether, dibutyl ether, Tulane, naphtha or chloroform.
The use of acetoxysilane intermediates in conjunction with an ethanol/sulfuric acid catalyst system may also be employed to produce the 25 unsaturated, multi functional organopolysiloxanes of this invention.
In cohydrolysis, a mixture of reactants are I
Skye chosen with the amount of each selected to provide the mole fractions desired in the final product.
Thus the mole fractions as set forth above with regard to "a", "b" and "c" define the structural limits in each particular composition. A slurry of the reactants in water, with the possible inclusion of an organic solvent, as known in the art is carried out. Sufficient time is allowed for hydrolysis and condensation to take place.
Typically times of from 2 hours to 2 days are used to permit completion at temperatures of from -20 to 98C and more preferably at room temperature. The organic phase carries the product formed and is separated from the water since the organic phase is immiscible with the water. Low molecular weight by-product is stripped from the organic phase preferably with the use of heat and vacuum as known in the art to remove molecular weights below about 200. The crude product remaining after by-product removal is extracted with a base solution, washed and then dried and is the purified final product referred to as a resin product capable of pharaoh reaction to form final high molecular weight polymerizates which can be formed or shaped into - 25 contact lenses and which act as contact lens materials.
Such cohydrolysis procedures are well known in Skye the art. Preferably ethanol-sulfuric acid catalyst is used wren alkoxysilanes and acetoxysilanes are used as reactants. Preferably the sullenness are mixed as in the above-noted procedure with an ethanol sulfuric acid catalyst containing a small amount of water. The reaction times and temperatures preferably are as described above as well as the workup of the crude product. Such reactions are detailed in US. patent 3,808,178.
Typically, the starting materials of this invention are chosen from the following classes of reactive sullenness:
R O
I O'ER -six Sioux R"3SiX
Where:
R is hydrogen or methyl R' is a diva lent alkaline radical having from one to about five carbon atoms.
R" is a monovalent hydrocarbon radical having ~lZ2~i~9~
Skye 06/15/~3 -from one to about five carbon atoms, a substituted monovalent hydrocarbon radical having from one to about five carbon atoms, a phenol group, a substituted phenol group or a eyelohexyl group.
"x" is a readily hydrolyzable group such as sheller, methoxy, ethics, methoxyethoxy, or attics.
The mole ratios of the various reactants will, to a large extent, control the molecular weight and structures of the resultant organopolysiloxanes.
Other factors, such as temperature of reaction and the presence of a solvent will also influence the composition of the product organopolysiloxane.
It should be understood that any of the novel organopol~siloxanes of this invention are composed of a variety of molecules, not one specific composition, and therefore must be described by an average or typical composition with perhaps more than one polymerizable group. Such structures are known and described as mixed structures or sometimes known as resins.
Preferably contact lens compositions can comprise an unsaturated, multifunetional organopolysiloxane polymerized alone or compolymerized with other monomers. The eopolymers can have incorporated therein a wetting agent such as a hydrofoil monomer and a hardness modifying agent which may be a hardening agent such as methyl ~.2~tjfi~36 Skye methacrylate or softening agents such as certain other acrylates or methacryates.
Physical properties of the compositions disclosed in this invention can be varied trough structural changes in the multi functional organopolysiloxane component and/or by varying the type and percent of comonomer.
In one embodiment of this invention oxygen transporting, transparent, inherently wettable contact lenses made from the polymerized organopolysiloxane resins of this invention alone.
In another embodiment of this invention polymeric compositions comprising the organopolysiloxane resins of this invention copolymerized with one or more other monomers.
Such other comonomers are preferably hardening or softening agents or hydrophilic agents. As for example, hardness modifying agents can be an ester of a Cluck mandrake or polyhydric alkanol or phenol and an acid selected from the class consisting essentially of acrylic, methacrylic, itaconic acid and mixtures thereof. Hydrophilic monomers can be of many different materials as will be described.
- 25 When comonomers are used, the polymeric compositions of the invention are preferably prepared by means of conventional free radical I it PLY
Skye 3~28S/44S
polymerization techniques. The free radical initiator is incorporated in amounts of from 0.01 to
2.0% by weight of the entire composition, at reaction temperatures of from 25C to 125C, to initiate and complete the polymerization.
Conventional bulk polymerization procedures can be used to produce castings which can be machined and polished by conventional procedures to produce contact lenses. Alternatively, the polymerization may be carried out directly in a contact lens mold.
The starting resin system is preferably polymerized to over 95~ completion by free radical catalysts.
The multi functional organopolysiloxane resins can provide for high oxygen permeability while strength and biocompatibility can be provided by other portions of the copolymer when comonomers are used. The use of methacrylate or acrylate esters provide for strength and hardness or resiliency in some cases and act to soften the material in other cases. Incorporation of a hydrophilic monomer can greatly increase the nettability of the material to achieve biocompatibility.
The novel resin compositions of this invention are prepared from an organopolysiloxane containing multiple, unsaturated polymerizable groups. Optical contact lenses are fabricated from polymerize en of these resin system monomers preferably incorporating ~l.2~j69~
2P128/~13 Skye other comonomers to provide the proper balance of physical and chemical properties desired in a contact lens. Typically, the multi functional organopolysiloxane resin systems useful in this invention can be polymerized alone and formed into contact lenses or copolymerized with other organic components, and have the following formula:
L r j I
Where:
R is hydrogen or methyl R' is a diva lent alkaline radical having from one to about five carbon atoms.
R" is a monovalent hydrocarbon radical having from one to about five carbon atoms, a substituted monovalent hydrocarbon radical having from one to about five carbon atoms, a phenol group, a substituted phenol group or a cyclohexyl group.
I
Skye "a" + "b" -I "c" = 1, where "a", "b" and "c" are all greater than I
The comonomers used along with the multi functional organopolysiloxanes in lens compositions of this invention, can be any polymerizable monomer which is capable of undergoing free radical polymerization and enhances a desirable property such as machinability, durability and biocompatibility.
Illustration of comonomers which can be usefully employed in accordance with this invention are given below.
Preferably the comonomers can be hardening or softening agents such as an ester of a Cluck mandrake or polyhydric alkanol or phenol and an acid selected from the class consisting essentially of acrylic and methacrylic acid. A hydrophilic hardening agent such as an itaconate moo- or dip ester can be used in addition.
The derivatives of acrylic, methacrylic and itaconic acid such as methyl ethyl propel n-butyl - isopropyl Huxley hoopla cyclohexyl 2-ethylhexyl I
Skye 382~S/~4~
ethoxyethyl butoxyethyl 2-hydroxyethyl 2- or 3-hydroxypropyl
Conventional bulk polymerization procedures can be used to produce castings which can be machined and polished by conventional procedures to produce contact lenses. Alternatively, the polymerization may be carried out directly in a contact lens mold.
The starting resin system is preferably polymerized to over 95~ completion by free radical catalysts.
The multi functional organopolysiloxane resins can provide for high oxygen permeability while strength and biocompatibility can be provided by other portions of the copolymer when comonomers are used. The use of methacrylate or acrylate esters provide for strength and hardness or resiliency in some cases and act to soften the material in other cases. Incorporation of a hydrophilic monomer can greatly increase the nettability of the material to achieve biocompatibility.
The novel resin compositions of this invention are prepared from an organopolysiloxane containing multiple, unsaturated polymerizable groups. Optical contact lenses are fabricated from polymerize en of these resin system monomers preferably incorporating ~l.2~j69~
2P128/~13 Skye other comonomers to provide the proper balance of physical and chemical properties desired in a contact lens. Typically, the multi functional organopolysiloxane resin systems useful in this invention can be polymerized alone and formed into contact lenses or copolymerized with other organic components, and have the following formula:
L r j I
Where:
R is hydrogen or methyl R' is a diva lent alkaline radical having from one to about five carbon atoms.
R" is a monovalent hydrocarbon radical having from one to about five carbon atoms, a substituted monovalent hydrocarbon radical having from one to about five carbon atoms, a phenol group, a substituted phenol group or a cyclohexyl group.
I
Skye "a" + "b" -I "c" = 1, where "a", "b" and "c" are all greater than I
The comonomers used along with the multi functional organopolysiloxanes in lens compositions of this invention, can be any polymerizable monomer which is capable of undergoing free radical polymerization and enhances a desirable property such as machinability, durability and biocompatibility.
Illustration of comonomers which can be usefully employed in accordance with this invention are given below.
Preferably the comonomers can be hardening or softening agents such as an ester of a Cluck mandrake or polyhydric alkanol or phenol and an acid selected from the class consisting essentially of acrylic and methacrylic acid. A hydrophilic hardening agent such as an itaconate moo- or dip ester can be used in addition.
The derivatives of acrylic, methacrylic and itaconic acid such as methyl ethyl propel n-butyl - isopropyl Huxley hoopla cyclohexyl 2-ethylhexyl I
Skye 382~S/~4~
ethoxyethyl butoxyethyl 2-hydroxyethyl 2- or 3-hydroxypropyl
3-methoxy-2-hydroxypropyl tetrahydrofurfuryl aureole ally glycidoxy 10 are useful.
Other comonomers may include N-vinylcarbazole, N-vinylpyrrolidone, hydroxy naphthyl methacrylate, strolls, such as styrenes methylstyrene, methoxy styrenes and Aztecs styrenes Allylic monomers, such as Delilah diglycol bicarbonate, Delilah phthalate, Delilah carbonate and triallyl sonority are also useful comonomers.
The nettability of the compositions disclosed in this invention may be enhanced by the inclusion of hydrophilic neutral monomers, hydrophilic cat ionic monomers and hydrophilic anionic monomers and mixtures of these, all of which act as wetting agents. The classes of these compounds are hydrophilic acrylates and methacrylates, acrylamides, methacrylamides and vinyl-lactams.
Representative hydrophilic neutral monomers which impart hydrophilic properties to the surface of contact lens materials of this invention include:
N-vinylpyrrolidone acrylamide it Skye methacrylamide N,N-dimethylacrylamide or methacrylamide 2-hydroxyethyl acrylate or methacrylate 2- or 3-hydroxypropyl acrylate or methacrylate glycerol acrylate or methacrylate glycidyl acrylate or methacrylate 3-methoxy-2-hydroxypropyl acrylate or methacrylate moo esters of acrylic and methacrylic acid with polyethers of the general formula:
EGO (On Hen I) oh Wherein "n" is a number from 1 to about 4 and "x" is a number from 2 to about 10.
The cat ionic hydrophilic monomers either can be initially in their charged form or are subsequently lo converted to their charged form after formation of the contact lens. The classes of these compounds are derived from basic or cat ionic acrylates, methacrylates, acrylamides, methacrylamides vinylpyridines, vinylimidazoles, and diallyldialkylammonium polymerizable groups. Such monomers are represented by:
N,N-dimethylaminoethyl acrylate and methacrylate 2-methacryloyloxyethyltrimethylammonium chloride and methyl sulfate 2-,4-, and 2-methyl--5-vinylpyridine 2-,4-, and 2-methyl--5-vinylpyridinium chloride and methyl sulfate N-(3-methacrylamidopropyl) -N ON -dimethylamine N-(3-methacrylamidopropyl)-N,N,N-trimethylammoniumm chloride - N-(3-methacryloyloxy-2-hydroxylpropyl)-N,N,N-trimeet hylammonium chloride Jo Z2~
Skye diallyldimethylammonium chloride and methyLsulfate The anionic hydrophilic monomers either are in their neutral form initially or are subsequently converted to their anionic form. These classes of compounds include polymerizable monomers which contain car boxy, sulfonate, and phosphate or phosphate groups. Such monomers are represented by:
acrylic acid methacrylic acid sodium assort and metnacrylate vinylsulfonic acid sodium vinylsulfonate p-styrenesulfonic acid sodium p-styrenesulfonate 2-methacryloyloxyethylsulfonic acid 3-methacryloyloxy-2-hydroxypropylsulfonic acid 2-acrylamido-2-methylpropanesulfonic acid allylsulfonic acid 2-phosphatoethyl methacrylate When comonomers are used along with the resin systems of this invention, they are used in varying amounts. The following table illustrates the percentages and formulations possible:
Formulation_ Formulation Formulation Component 1 2 3 Oxygen permeable three unit, - 30 unsaturated multi-Sue Skye functional 5 iloxane material of this 25-98~ 25-98%
invention 100% by weight by weight Hardness modifying Agent 0 75-2~ 75-1%
Hydrophilic agent 0 0 1%-10%
In certain instances it may be desirable to incorporate a cross linking agent into a composition based on the novel organopolysiloxanes disclosed herein.
Examples of cross linking agents include polyfunctional derivatives of acrylic acid, methacrylic acid, acrylamide, methacrylamide and multi-vinyl substituted benzenes, including but not limited to the following:
ethylene glycol diacrylate or dimethacrylate diethylene glycol diacrylate or dimethacrylate tetraethylene glycol diacrylate or methacrylate polyethylene glycol diacrylate or methacrylate trimethylolpropane triacrylate or trimethacrylate Bisphenol A diacrylate or dimethacrylate - ethoxylated Bisphenol A diacrylate or foe Skye 3828~/44S
dimethacrylate pentaerythritol in- and tetraacrylate or methacrylate tetramethylenediacrylate or dimethacrylate ethylene bisacrylamide or methacrylamide dim ethylene bisacrylamide or methacrylamide N,N'-dihydroxyethylene bisacrylamide or methacrylamide hexamethylene bisacrylamide or methacrylamide decamethylene bisacrylamide or methacrylamide divinely Bunsen Tune copolymers described in this invention are prepared by radical polymerization through the incorporation of a free radical initiator. The initiator is chosen from those commonly utilized to polymerize vinyl type monomers and would include the following representative initiators:
2,2'-azo-bis-isobutyronitrile
Other comonomers may include N-vinylcarbazole, N-vinylpyrrolidone, hydroxy naphthyl methacrylate, strolls, such as styrenes methylstyrene, methoxy styrenes and Aztecs styrenes Allylic monomers, such as Delilah diglycol bicarbonate, Delilah phthalate, Delilah carbonate and triallyl sonority are also useful comonomers.
The nettability of the compositions disclosed in this invention may be enhanced by the inclusion of hydrophilic neutral monomers, hydrophilic cat ionic monomers and hydrophilic anionic monomers and mixtures of these, all of which act as wetting agents. The classes of these compounds are hydrophilic acrylates and methacrylates, acrylamides, methacrylamides and vinyl-lactams.
Representative hydrophilic neutral monomers which impart hydrophilic properties to the surface of contact lens materials of this invention include:
N-vinylpyrrolidone acrylamide it Skye methacrylamide N,N-dimethylacrylamide or methacrylamide 2-hydroxyethyl acrylate or methacrylate 2- or 3-hydroxypropyl acrylate or methacrylate glycerol acrylate or methacrylate glycidyl acrylate or methacrylate 3-methoxy-2-hydroxypropyl acrylate or methacrylate moo esters of acrylic and methacrylic acid with polyethers of the general formula:
EGO (On Hen I) oh Wherein "n" is a number from 1 to about 4 and "x" is a number from 2 to about 10.
The cat ionic hydrophilic monomers either can be initially in their charged form or are subsequently lo converted to their charged form after formation of the contact lens. The classes of these compounds are derived from basic or cat ionic acrylates, methacrylates, acrylamides, methacrylamides vinylpyridines, vinylimidazoles, and diallyldialkylammonium polymerizable groups. Such monomers are represented by:
N,N-dimethylaminoethyl acrylate and methacrylate 2-methacryloyloxyethyltrimethylammonium chloride and methyl sulfate 2-,4-, and 2-methyl--5-vinylpyridine 2-,4-, and 2-methyl--5-vinylpyridinium chloride and methyl sulfate N-(3-methacrylamidopropyl) -N ON -dimethylamine N-(3-methacrylamidopropyl)-N,N,N-trimethylammoniumm chloride - N-(3-methacryloyloxy-2-hydroxylpropyl)-N,N,N-trimeet hylammonium chloride Jo Z2~
Skye diallyldimethylammonium chloride and methyLsulfate The anionic hydrophilic monomers either are in their neutral form initially or are subsequently converted to their anionic form. These classes of compounds include polymerizable monomers which contain car boxy, sulfonate, and phosphate or phosphate groups. Such monomers are represented by:
acrylic acid methacrylic acid sodium assort and metnacrylate vinylsulfonic acid sodium vinylsulfonate p-styrenesulfonic acid sodium p-styrenesulfonate 2-methacryloyloxyethylsulfonic acid 3-methacryloyloxy-2-hydroxypropylsulfonic acid 2-acrylamido-2-methylpropanesulfonic acid allylsulfonic acid 2-phosphatoethyl methacrylate When comonomers are used along with the resin systems of this invention, they are used in varying amounts. The following table illustrates the percentages and formulations possible:
Formulation_ Formulation Formulation Component 1 2 3 Oxygen permeable three unit, - 30 unsaturated multi-Sue Skye functional 5 iloxane material of this 25-98~ 25-98%
invention 100% by weight by weight Hardness modifying Agent 0 75-2~ 75-1%
Hydrophilic agent 0 0 1%-10%
In certain instances it may be desirable to incorporate a cross linking agent into a composition based on the novel organopolysiloxanes disclosed herein.
Examples of cross linking agents include polyfunctional derivatives of acrylic acid, methacrylic acid, acrylamide, methacrylamide and multi-vinyl substituted benzenes, including but not limited to the following:
ethylene glycol diacrylate or dimethacrylate diethylene glycol diacrylate or dimethacrylate tetraethylene glycol diacrylate or methacrylate polyethylene glycol diacrylate or methacrylate trimethylolpropane triacrylate or trimethacrylate Bisphenol A diacrylate or dimethacrylate - ethoxylated Bisphenol A diacrylate or foe Skye 3828~/44S
dimethacrylate pentaerythritol in- and tetraacrylate or methacrylate tetramethylenediacrylate or dimethacrylate ethylene bisacrylamide or methacrylamide dim ethylene bisacrylamide or methacrylamide N,N'-dihydroxyethylene bisacrylamide or methacrylamide hexamethylene bisacrylamide or methacrylamide decamethylene bisacrylamide or methacrylamide divinely Bunsen Tune copolymers described in this invention are prepared by radical polymerization through the incorporation of a free radical initiator. The initiator is chosen from those commonly utilized to polymerize vinyl type monomers and would include the following representative initiators:
2,2'-azo-bis-isobutyronitrile
4,4'-azo-bis-(4-cyanopentanoic acid) t-butyl peroctoate bouncily peroxide laurel peroxide methyl ethyl kitten peroxide diisopropyl peroxycarbonate The free radical initiator is normally used in ~Z~6~
2P12~/713 Skye 3828S/~4S
amounts of from 0.01 to I by weight of the entire compound. Polymerization is preferably carried out to 95% or higher of the starting material with the reaction driven to as near to 100% as possible The materials of this invention can be polymerized directly in a suitable mold to form contact lenses. The materials are all thermosetting and thus various methods of fabrication can be used. It is preferable to polymerize into sheet or rod stock from which contact lenses may be machined.
It is preferred to use the conventional approach when forming contact lenses such as used for polymethyl methacrylate (PUMA). In this approach, the formulations are polymerized directly into a sheet or rod and the contact lenses are cut as buttons, discs or other preformed shapes whiz are then machined to obtain the lens surfaces. The resulting polymeric stock of buttons possesses the optical qualities necessary to produce aberration-free oxygen-permeagble, hard contact lenses in accordance with this invention.
Tune multi functional organopolysiloxane monomers of this invention provide many advantages when utilized as the basis for contact lens materials.
- 25 The disclosed monomers are substantially organopolysiloxane but contain multiple functional groups which allows for rapid incorporation into a ~.ZZ~696 Skye ; copolymer system by free radical polymerization.
Furthermore, because of the presence of the multi functional, polymerizable groups the organopolysiloxane portion is compatibilized in the copolymer structure The oxygen demand of the human cornea has been well established and contact lenses made from the polymers and copolymers of this invention can meet and easily exceed this requirement lo because of the unique properties of the compositions, the contact lenses formed thereof have high oxygen permeability while maintaining other essential properties such as clarity, nettability and durability. Oxygen permeability is meant to include polymeric materials which have an oxygen permeability of greater than 4 x 10 11 ml 2 cm Seiko ml mm Hug.
The following Examples are given to illustrate the invention and are not meant to be limiting:
A mixture ox 150 ml (0.632 moles) ~-methacryloxypropyltrimethoxysilane, 155 ml (1.264 Mole) trimethylchlorosilane and 155 ml (1.264) mole) dimethyldichlorosilane was slowly added to 600 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40 to 50C
during the admixing.
i9ç
2~128/713 Skye After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 230 ml of product.
This material, having a viscosity of 13.2 centistokes at 25C, was designated Sly. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in the indicated mole ratio:
GROUPS CALCULATED FOUND
clue SHEA = C-c-0cH2CH2CH2Sio3/2 0.20 0.32 (CH3)2SiO 0.40 0.42 (CH3~3siOl/2 0,40 0.26 A mixture of 150 ml (0.632 mole) ~-methacryloxypropyltrimethoxysilane, 155 ml (1.264 mole) trimethylchlorosilane and 155 ml (1.264 mole) : . 25 dimethyldichlorosilane was slowly ceded to slurry of 300 ml of diethylether and 300 ml of Skye .
water. The temperature of the hydrolysis was maintained at about 40C by allowing the ether to reflex.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium lo sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 230 ml of product.
This material, having a viscosity of 14.8 centistokes at 25C, was designated PS-2. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in the indicated mole ratio:
GROUPS CALCULATED FOUND
SUE l Z 2 2 2 3/2 0.20 0.29 (CH3)2SiO 0.40 0.44 (CH3)3SiOl/2 0.40 0.27 A mixture of 150 ml (0.632 moles) ~-methacryloxypropyltrimethoxysilane, 155 ml Jo Skye (1.264 mole) trimethylchlorosilane and 155 ml (1.264 mole) dimethyldichlorosilane was slowly added to a solution of 30Q ml methanol and 300 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40 to 50C during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 200 ml of product.
This material, having a viscosity of 24.4 centistokes at 25C, was designated PS-3. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in the indicated mole ratio:
GROUPS CALCULATED FOUND
C~31 SHEA = C-C-0CH2CH2CH2SiO3/2 0.20 0.24 (CH3~2SiO 0.40 0.46 (CH3~3siOl/2 0-40 0.30 Skye A mixture of 150 ml (0.632 moles) methacryloxypropyltrimethoxysilane, 78 ml (0.632 mole) trimethylchlorosilane and 233 ml (1.896 mole) dimethyldichlorosilane was slowly added to 600 ml of water with stirring. The temperature of the hydrolysis was maintained a approximately 40 to 50C during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 220 ml of product.
This material, having a viscosity of 30.2 centistokes at 25C, was designated PS-4. Nuclear magnetic resonance ( 5 silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
SHEA
SHEA = CH2cH2cH2si3/2 0.20 0.16 (C~3)2SiO 0.60 0.59 (CH3)3siOl/2 0.20 0.25 Sue ~P12~/713 Skye ~6/15/83 A mixture of 150 ml (0.632 mole) y-methacryloxypropyltrimethoxysilane, 78 ml (0.632 mole) trimethylchlorosilane and 233 ml (1.896 mole) dimethyldichlorosilane was slowly added to slurry of 300 ml of diethylether and 300 ml of water. The temperature ox the hydrolysis was maintained at about 40C by allowing the ether to reflex.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 225 ml of product.
This material, having a viscosity of 28.0 centistokes at 25C, was designated PS-5. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
Cff31l 2 2 2 2 3/2 0.20 0.17 (CH3)2SiO 0.60 0.57 (CH3)3siOl/2 0.20 0.26 I
Skye 382~S/44S
A mixture of 150 ml (0.632 mole) y-methacryloxypropyltrimethoxysilane, 78 ml (0.632 mole) trimethylchlorosilane and 233 ml (1~896 mole) dimethyldichlorosilane was slowly added to a solution of 300 ml methanol and 300 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40C-50C
during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 105 ml of product.
This material, having a viscosity of 63.7 centistokes at 25C, was designated PS-6. nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
-Skye GROUPS CALCULATED FOUND
Clue SHEA = C-C 0CH2CH2CH2SiO3/2 0.20 0.10 (CH3)2SiO 0.60 0.65 (CH3)3siOl/2 0~20 0.25 A mixture of 150 ml (0.632 mole) ~-methacryloxypropyltrimethoxysilane, 116 ml (0.948 mole) trimethylchlorosilane and 194 ml (1.580 mole) dimethyldichlorosilane was slowly added to 600 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40C to 50C during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 205 ml of product.
This material, having a viscosity of 21.6 centistokes at 25C, was designated PS-7. Nuclear I
Skye magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
SHEA = 0CH2CH2CH2Sio3/2 0.20 0.27 (CH3)2SiO 0.50 0.49 (CH3)3siOl/2 0.30 0.24 lo mixture of 150 ml (0.632 mole) ~-methacryloxypropyltrimethoxysilane, 116 ml (0.948 mole) trimethylchlorosilane and 194 ml (1.580 mole) dimethyldichlorosilane was slowly added to 300 ml methanol and 300 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40C to 50C during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 225 ml of i9~i Skye 06/15/~3 product This material, having a viscosity of 13.3 centistokes at SUE was designated PS-8. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
SHEA = C-C OC~2CH2CH2SiO3/2 0.20 0.27 ~CH3)2SiO 0 50 0.51 (cH3)3siol/2 0.30 0.24 A mixture of 150 ml (0.632 mole) ~-methacryloxypropyltrimethoxysilane, 232 ml (1.896 mole) trimethylchlorosilane and 232 ml (1.896 mole dimethyldichlorosilane was slowly added to 600 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40C to 50C during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium lo 2P12~/713 Skye sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 245 ml of product.
This material, having a viscosity of 10.7 centistokes at 25C, was designated PS-9. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
cry C~2 = C-C-0CH2C~2C~2SiO3/2 0.14 0.37 (CH3)2SiO 0.43 0.43 (CH3)3siOl/2 0.43 0.20 A mixture of 150 ml (0~632 mole) ~-methacryloxypropyltrimethoxysilane, 232 ml (1.896 mole) trimethylchlorosilane and 232 ml (1.896 mole) dimethyldichlorosilane was slowly added to a solution of 300 ml methanol and 300 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40C to 50C during the admixing.
After stirring overnight tune aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped prom the organic phase using high vacuum at ~26~
Skye a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 273 ml of product.
This material, having a viscosity of 8.1 centistokes at 25C, was designated PS-10. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
Clue SHEA C C 0CH2CH2CH2s 3/2 0.14 0.36 (CH3)2SiO 0.43 0.44 (CH3)3siOl/2 0.43 0.20 A mixture of 75 ml (0.316 mole) ~-methacryloxypropyltrimethoxysilane, 78 ml (0.632 mole) trimethylchlorosilane and 267 ml (2.212 mole) dimethyldichlorosilane was slowly added to 600 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40C to 50C during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an Skye equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 112 ml of product.
This material, having a viscosity of 13.1 lo centistokes at 25C, was designated Sly. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
Cl3ll 2 2 2 2 3/2 0.10 0.21 (CH3)2SiO 0.70 0.63 (CH3)3siOl/2 0.20 0.16 A mixture of 75 ml (0.316 mole ~-methacryloxypropyltrimethoxysilane, 78 ml (0.632 mole trimethylchlorosilane and 267 ml (2.212 mole) dimethyldichlorosilane was slowly added to 300 ml methanol and 300 ml of water with stirring The temperature of the hydrolysis was maintained at approximately 40C to 50C during the admixing.
Skye 3~28S/44S
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 147 ml of product.
This material having a viscosity of 9.4 centistokes at 25C, was designated PS-12. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio GROUPS CALCULATED FOUND
CHIT 3 1i OH = C-c-ocH2cH2cH2sio3/2 0~10 0022 (SHEA) Shea 0. 70 0. 60 (cH3)3siol/2 0.20 0.18 A mixture of 75 ml (0.316 mole) ~-methacryloxypropyltrimethoxysilane, 39 ml (0.316 mole) trimethylchlorosilane and 300 ml ~2.528 mole) dimethyldichlorosilane was slowly added to 600 ml of water with stirring. The temperature of the 6~i~36 Skye hydrolysis was maintained at approximately 40C to 50C during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C~ The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 125 ml of product.
Tins material, having a viscosity of 16.8 centistokes at 25C, was designated PS-13. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
CHAR
C~2 C C 0CH2CH2CH2s 3/2 0.10 0.12 (CH3)2Sio 0.80 0.74 (CH3)3siOl/2 0.10 0.14 A mixture of 75 ml (0.316 mole) US ~-methacryloxypropyltrimethoxysilane, 39 ml ~0.316 mole) trimethylchlorosilane and 300 ml (2.528 mole) ~.Z2~ 36 Skye dimethyldichlorosilane was slowly added to 300 ml methanol and 300 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40C to 50C during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 144 ml of product.
This material, having a viscosity of 13.6 centistokes at 25C, was designated PS-14. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
-SHEA
SHEA = C-C-OCH2CH2CH2SiO3~2 0.10 0.10 (CH3)2SiO 0.80 0.76 (CH3)3SiOl/2 0.10 0.14 -Sue Skye Hard oxygen-permeable lens materials are made from selected comonomer mixtures of methyl methacrylate (MA), Sly, PS-2, PS-3 and methacrylic acid (MA) using the free radical initiator 2,2'-azobisisobutyronitrile (AIBN). The formulation components (shown in Table I in parts by weight) are thoroughly mixed, transferred to test tubes which are purged with nitrogen then sealed with serum lo caps. The test tubes are then placed in a water bath at 40C and allowed to polymerize for three days. The tubes are then placed in a 65C oven for an additional time period of 2 days, after which the polymerized rods are removed from the tubes. The hard, transparent rods are then subjected to conditioning for approximately twenty-four (24) hours at 100C under vacuum to complete polymerization process and relieve any mechanical stresses present. The conditioned rods are then machined to contact lens blanks (a disc 1/2 inch in diameter by 3/16 inch thick).
Oxygen permeability values of the contact lenses produced from the materials described here were generated by a procedure as described in ASTM
D1434 except that piano contact lenses are used instead of large flat discs of material. The permeability apparatus was constructed in such a ~.22S~ 36 Skye manner as to accept actual contact lenses and calibrated with other polymeric oxygen permeability data reported in Table I, polymethyl methacrylate, polycarbonate, and polystyrene have oxygen permeability of 1,22, and 35 cm3mm/cm2 sea cm Hug x 10 10, respectively.
TABLE I
OXYGEN* HARDNESS
COMPOSITION parts by wt.) PERMEABILITY ROCKWELL R
MA Sly PS-2 PS-3 MA AIBN
60 35 -- -- 5 0.2 57 120 50 45 -- -- 5 0.2147 113 60 -- 35 -- 5 0~2 55 120 50 -- 45 -- 5 0.2140 118 60 -- -- 35 5 0.2 70 119 50 -- -- 45 5 0.2170 117 * Value in cm3mm/cm2 sea cm Hug x 101 Utilizing the Experimental Procedures of Example 15 this Example illustrates the preparation and properties of materials suitable for producing hard contact lenses.
-Sue Skye 3828S/4~S
COMPOSITION parts by wt.) HARDNESS
50 45 - - 5 0.2 114 50 - 45 - 5 0.2 114 50 - - 45 5 0.2 111 Utilizing the Experimental Procedures of Example 15 this Example illustrates the preparation 10 , and properties of materials suitable for producing hard contact lenses.
COMPOSITION (parts by wt.) HARDNESS
50 45 - 5 0.2 116 50 - 45 5 0.2 115 Utilizing the Experimental Procedures of Example 15 this Example illustrates the preparation and properties of materials suitable for producing hard contact lenses.
Skye 3828S/~4S
~40-COMPOSITION (parts by wt.) HARDNESS
_ PS-9 PS-10 MA AIBN ROCKWELL R
50 - 45 5 0~2 103 Utilizing tune Experimental Procedures of Example 15 this Example illustrates the preparation and properties of materials suitable for producing hard contact lenses.
COMPOSITION (parts by wt.) MA Sly PS-12 MA AIBN PROPERTIES
55 45 - - 0.2 T
50 45 - 5 0.2 NT
55 - 45 0.2 T
50 - 45 5 0.2 NT
T = Transparent NT = Hazy Utilizing the Experimental Procedures of Example 15 this Example illustrates the preparation and properties of materials suitable for producing hard contact lenses.
~2~6~3~
Skye COMPOSITION ( parts by wt.) - - 0.2 T
2P12~/713 Skye 3828S/~4S
amounts of from 0.01 to I by weight of the entire compound. Polymerization is preferably carried out to 95% or higher of the starting material with the reaction driven to as near to 100% as possible The materials of this invention can be polymerized directly in a suitable mold to form contact lenses. The materials are all thermosetting and thus various methods of fabrication can be used. It is preferable to polymerize into sheet or rod stock from which contact lenses may be machined.
It is preferred to use the conventional approach when forming contact lenses such as used for polymethyl methacrylate (PUMA). In this approach, the formulations are polymerized directly into a sheet or rod and the contact lenses are cut as buttons, discs or other preformed shapes whiz are then machined to obtain the lens surfaces. The resulting polymeric stock of buttons possesses the optical qualities necessary to produce aberration-free oxygen-permeagble, hard contact lenses in accordance with this invention.
Tune multi functional organopolysiloxane monomers of this invention provide many advantages when utilized as the basis for contact lens materials.
- 25 The disclosed monomers are substantially organopolysiloxane but contain multiple functional groups which allows for rapid incorporation into a ~.ZZ~696 Skye ; copolymer system by free radical polymerization.
Furthermore, because of the presence of the multi functional, polymerizable groups the organopolysiloxane portion is compatibilized in the copolymer structure The oxygen demand of the human cornea has been well established and contact lenses made from the polymers and copolymers of this invention can meet and easily exceed this requirement lo because of the unique properties of the compositions, the contact lenses formed thereof have high oxygen permeability while maintaining other essential properties such as clarity, nettability and durability. Oxygen permeability is meant to include polymeric materials which have an oxygen permeability of greater than 4 x 10 11 ml 2 cm Seiko ml mm Hug.
The following Examples are given to illustrate the invention and are not meant to be limiting:
A mixture ox 150 ml (0.632 moles) ~-methacryloxypropyltrimethoxysilane, 155 ml (1.264 Mole) trimethylchlorosilane and 155 ml (1.264) mole) dimethyldichlorosilane was slowly added to 600 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40 to 50C
during the admixing.
i9ç
2~128/713 Skye After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 230 ml of product.
This material, having a viscosity of 13.2 centistokes at 25C, was designated Sly. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in the indicated mole ratio:
GROUPS CALCULATED FOUND
clue SHEA = C-c-0cH2CH2CH2Sio3/2 0.20 0.32 (CH3)2SiO 0.40 0.42 (CH3~3siOl/2 0,40 0.26 A mixture of 150 ml (0.632 mole) ~-methacryloxypropyltrimethoxysilane, 155 ml (1.264 mole) trimethylchlorosilane and 155 ml (1.264 mole) : . 25 dimethyldichlorosilane was slowly ceded to slurry of 300 ml of diethylether and 300 ml of Skye .
water. The temperature of the hydrolysis was maintained at about 40C by allowing the ether to reflex.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium lo sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 230 ml of product.
This material, having a viscosity of 14.8 centistokes at 25C, was designated PS-2. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in the indicated mole ratio:
GROUPS CALCULATED FOUND
SUE l Z 2 2 2 3/2 0.20 0.29 (CH3)2SiO 0.40 0.44 (CH3)3SiOl/2 0.40 0.27 A mixture of 150 ml (0.632 moles) ~-methacryloxypropyltrimethoxysilane, 155 ml Jo Skye (1.264 mole) trimethylchlorosilane and 155 ml (1.264 mole) dimethyldichlorosilane was slowly added to a solution of 30Q ml methanol and 300 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40 to 50C during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 200 ml of product.
This material, having a viscosity of 24.4 centistokes at 25C, was designated PS-3. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in the indicated mole ratio:
GROUPS CALCULATED FOUND
C~31 SHEA = C-C-0CH2CH2CH2SiO3/2 0.20 0.24 (CH3~2SiO 0.40 0.46 (CH3~3siOl/2 0-40 0.30 Skye A mixture of 150 ml (0.632 moles) methacryloxypropyltrimethoxysilane, 78 ml (0.632 mole) trimethylchlorosilane and 233 ml (1.896 mole) dimethyldichlorosilane was slowly added to 600 ml of water with stirring. The temperature of the hydrolysis was maintained a approximately 40 to 50C during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 220 ml of product.
This material, having a viscosity of 30.2 centistokes at 25C, was designated PS-4. Nuclear magnetic resonance ( 5 silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
SHEA
SHEA = CH2cH2cH2si3/2 0.20 0.16 (C~3)2SiO 0.60 0.59 (CH3)3siOl/2 0.20 0.25 Sue ~P12~/713 Skye ~6/15/83 A mixture of 150 ml (0.632 mole) y-methacryloxypropyltrimethoxysilane, 78 ml (0.632 mole) trimethylchlorosilane and 233 ml (1.896 mole) dimethyldichlorosilane was slowly added to slurry of 300 ml of diethylether and 300 ml of water. The temperature ox the hydrolysis was maintained at about 40C by allowing the ether to reflex.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 225 ml of product.
This material, having a viscosity of 28.0 centistokes at 25C, was designated PS-5. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
Cff31l 2 2 2 2 3/2 0.20 0.17 (CH3)2SiO 0.60 0.57 (CH3)3siOl/2 0.20 0.26 I
Skye 382~S/44S
A mixture of 150 ml (0.632 mole) y-methacryloxypropyltrimethoxysilane, 78 ml (0.632 mole) trimethylchlorosilane and 233 ml (1~896 mole) dimethyldichlorosilane was slowly added to a solution of 300 ml methanol and 300 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40C-50C
during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 105 ml of product.
This material, having a viscosity of 63.7 centistokes at 25C, was designated PS-6. nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
-Skye GROUPS CALCULATED FOUND
Clue SHEA = C-C 0CH2CH2CH2SiO3/2 0.20 0.10 (CH3)2SiO 0.60 0.65 (CH3)3siOl/2 0~20 0.25 A mixture of 150 ml (0.632 mole) ~-methacryloxypropyltrimethoxysilane, 116 ml (0.948 mole) trimethylchlorosilane and 194 ml (1.580 mole) dimethyldichlorosilane was slowly added to 600 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40C to 50C during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 205 ml of product.
This material, having a viscosity of 21.6 centistokes at 25C, was designated PS-7. Nuclear I
Skye magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
SHEA = 0CH2CH2CH2Sio3/2 0.20 0.27 (CH3)2SiO 0.50 0.49 (CH3)3siOl/2 0.30 0.24 lo mixture of 150 ml (0.632 mole) ~-methacryloxypropyltrimethoxysilane, 116 ml (0.948 mole) trimethylchlorosilane and 194 ml (1.580 mole) dimethyldichlorosilane was slowly added to 300 ml methanol and 300 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40C to 50C during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 225 ml of i9~i Skye 06/15/~3 product This material, having a viscosity of 13.3 centistokes at SUE was designated PS-8. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
SHEA = C-C OC~2CH2CH2SiO3/2 0.20 0.27 ~CH3)2SiO 0 50 0.51 (cH3)3siol/2 0.30 0.24 A mixture of 150 ml (0.632 mole) ~-methacryloxypropyltrimethoxysilane, 232 ml (1.896 mole) trimethylchlorosilane and 232 ml (1.896 mole dimethyldichlorosilane was slowly added to 600 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40C to 50C during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium lo 2P12~/713 Skye sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 245 ml of product.
This material, having a viscosity of 10.7 centistokes at 25C, was designated PS-9. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
cry C~2 = C-C-0CH2C~2C~2SiO3/2 0.14 0.37 (CH3)2SiO 0.43 0.43 (CH3)3siOl/2 0.43 0.20 A mixture of 150 ml (0~632 mole) ~-methacryloxypropyltrimethoxysilane, 232 ml (1.896 mole) trimethylchlorosilane and 232 ml (1.896 mole) dimethyldichlorosilane was slowly added to a solution of 300 ml methanol and 300 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40C to 50C during the admixing.
After stirring overnight tune aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped prom the organic phase using high vacuum at ~26~
Skye a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 273 ml of product.
This material, having a viscosity of 8.1 centistokes at 25C, was designated PS-10. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
Clue SHEA C C 0CH2CH2CH2s 3/2 0.14 0.36 (CH3)2SiO 0.43 0.44 (CH3)3siOl/2 0.43 0.20 A mixture of 75 ml (0.316 mole) ~-methacryloxypropyltrimethoxysilane, 78 ml (0.632 mole) trimethylchlorosilane and 267 ml (2.212 mole) dimethyldichlorosilane was slowly added to 600 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40C to 50C during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an Skye equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 112 ml of product.
This material, having a viscosity of 13.1 lo centistokes at 25C, was designated Sly. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
Cl3ll 2 2 2 2 3/2 0.10 0.21 (CH3)2SiO 0.70 0.63 (CH3)3siOl/2 0.20 0.16 A mixture of 75 ml (0.316 mole ~-methacryloxypropyltrimethoxysilane, 78 ml (0.632 mole trimethylchlorosilane and 267 ml (2.212 mole) dimethyldichlorosilane was slowly added to 300 ml methanol and 300 ml of water with stirring The temperature of the hydrolysis was maintained at approximately 40C to 50C during the admixing.
Skye 3~28S/44S
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 147 ml of product.
This material having a viscosity of 9.4 centistokes at 25C, was designated PS-12. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio GROUPS CALCULATED FOUND
CHIT 3 1i OH = C-c-ocH2cH2cH2sio3/2 0~10 0022 (SHEA) Shea 0. 70 0. 60 (cH3)3siol/2 0.20 0.18 A mixture of 75 ml (0.316 mole) ~-methacryloxypropyltrimethoxysilane, 39 ml (0.316 mole) trimethylchlorosilane and 300 ml ~2.528 mole) dimethyldichlorosilane was slowly added to 600 ml of water with stirring. The temperature of the 6~i~36 Skye hydrolysis was maintained at approximately 40C to 50C during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at a temperature of about 70-75C~ The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 125 ml of product.
Tins material, having a viscosity of 16.8 centistokes at 25C, was designated PS-13. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
CHAR
C~2 C C 0CH2CH2CH2s 3/2 0.10 0.12 (CH3)2Sio 0.80 0.74 (CH3)3siOl/2 0.10 0.14 A mixture of 75 ml (0.316 mole) US ~-methacryloxypropyltrimethoxysilane, 39 ml ~0.316 mole) trimethylchlorosilane and 300 ml (2.528 mole) ~.Z2~ 36 Skye dimethyldichlorosilane was slowly added to 300 ml methanol and 300 ml of water with stirring. The temperature of the hydrolysis was maintained at approximately 40C to 50C during the admixing.
After stirring overnight the aqueous phase was separated and the organic phase was washed with an equal volume of water. The volatile were then stripped from the organic phase using high vacuum at temperature of about 70-75C. The crude product was then extracted with a sodium hydroxide/sodium sulfate solution followed by a washing with a sodium sulfate solution. The organopolysiloxane was then dried with magnesium sulfate yielding 144 ml of product.
This material, having a viscosity of 13.6 centistokes at 25C, was designated PS-14. Nuclear magnetic resonance (silicon 29) analysis showed the following groups to be present in he indicated mole ratio:
GROUPS CALCULATED FOUND
-SHEA
SHEA = C-C-OCH2CH2CH2SiO3~2 0.10 0.10 (CH3)2SiO 0.80 0.76 (CH3)3SiOl/2 0.10 0.14 -Sue Skye Hard oxygen-permeable lens materials are made from selected comonomer mixtures of methyl methacrylate (MA), Sly, PS-2, PS-3 and methacrylic acid (MA) using the free radical initiator 2,2'-azobisisobutyronitrile (AIBN). The formulation components (shown in Table I in parts by weight) are thoroughly mixed, transferred to test tubes which are purged with nitrogen then sealed with serum lo caps. The test tubes are then placed in a water bath at 40C and allowed to polymerize for three days. The tubes are then placed in a 65C oven for an additional time period of 2 days, after which the polymerized rods are removed from the tubes. The hard, transparent rods are then subjected to conditioning for approximately twenty-four (24) hours at 100C under vacuum to complete polymerization process and relieve any mechanical stresses present. The conditioned rods are then machined to contact lens blanks (a disc 1/2 inch in diameter by 3/16 inch thick).
Oxygen permeability values of the contact lenses produced from the materials described here were generated by a procedure as described in ASTM
D1434 except that piano contact lenses are used instead of large flat discs of material. The permeability apparatus was constructed in such a ~.22S~ 36 Skye manner as to accept actual contact lenses and calibrated with other polymeric oxygen permeability data reported in Table I, polymethyl methacrylate, polycarbonate, and polystyrene have oxygen permeability of 1,22, and 35 cm3mm/cm2 sea cm Hug x 10 10, respectively.
TABLE I
OXYGEN* HARDNESS
COMPOSITION parts by wt.) PERMEABILITY ROCKWELL R
MA Sly PS-2 PS-3 MA AIBN
60 35 -- -- 5 0.2 57 120 50 45 -- -- 5 0.2147 113 60 -- 35 -- 5 0~2 55 120 50 -- 45 -- 5 0.2140 118 60 -- -- 35 5 0.2 70 119 50 -- -- 45 5 0.2170 117 * Value in cm3mm/cm2 sea cm Hug x 101 Utilizing the Experimental Procedures of Example 15 this Example illustrates the preparation and properties of materials suitable for producing hard contact lenses.
-Sue Skye 3828S/4~S
COMPOSITION parts by wt.) HARDNESS
50 45 - - 5 0.2 114 50 - 45 - 5 0.2 114 50 - - 45 5 0.2 111 Utilizing the Experimental Procedures of Example 15 this Example illustrates the preparation 10 , and properties of materials suitable for producing hard contact lenses.
COMPOSITION (parts by wt.) HARDNESS
50 45 - 5 0.2 116 50 - 45 5 0.2 115 Utilizing the Experimental Procedures of Example 15 this Example illustrates the preparation and properties of materials suitable for producing hard contact lenses.
Skye 3828S/~4S
~40-COMPOSITION (parts by wt.) HARDNESS
_ PS-9 PS-10 MA AIBN ROCKWELL R
50 - 45 5 0~2 103 Utilizing tune Experimental Procedures of Example 15 this Example illustrates the preparation and properties of materials suitable for producing hard contact lenses.
COMPOSITION (parts by wt.) MA Sly PS-12 MA AIBN PROPERTIES
55 45 - - 0.2 T
50 45 - 5 0.2 NT
55 - 45 0.2 T
50 - 45 5 0.2 NT
T = Transparent NT = Hazy Utilizing the Experimental Procedures of Example 15 this Example illustrates the preparation and properties of materials suitable for producing hard contact lenses.
~2~6~3~
Skye COMPOSITION ( parts by wt.) - - 0.2 T
- 5 0.2 NT
- 45 - 0.2 - 35 5 0.2 NT
T = Transparent NT = Hazy The above Examples illustrate the preparation of the resin systems of this invention and admixture and copolymerization with methyl methacrylate and methacrylic acid As previously described, other comonomers can be used with the resin systems to form polymerized products. In some cases, the resin systems can be polymerized themselves to form hard contact lens materials When the resins of this invention are homopolymerized and used for contact lenses, it is preferred to surface treat such lenses as by conventional oxidation or grafting to make the surfaces wettable.
- 45 - 0.2 - 35 5 0.2 NT
T = Transparent NT = Hazy The above Examples illustrate the preparation of the resin systems of this invention and admixture and copolymerization with methyl methacrylate and methacrylic acid As previously described, other comonomers can be used with the resin systems to form polymerized products. In some cases, the resin systems can be polymerized themselves to form hard contact lens materials When the resins of this invention are homopolymerized and used for contact lenses, it is preferred to surface treat such lenses as by conventional oxidation or grafting to make the surfaces wettable.
Claims (22)
- Claim 1 continued:
phenyl group or a cyclohexyl group.
"a" + "b" + "c" = 1, where "a", "b" and "c" are each greater than 0 wherein "a" has a mole fraction value of from 0.10 to 0.40, "b" has a mole fraction value of from 0.25 to 0.80, and "c" has a mole fraction value of from 0.10 to 0.40. - 2. A resin system in accordance with claim 1 having a viscosity of from 7 to 70 centistokes at 25°C.
- 3. A resin system in accordance with claim 2 wherein said first-noted unit is a reactive organofunctional trisiloxane, said second-noted unit is a chain extender and said third-noted unit is an end group.
- 4. A resin system in accordance with claim 3 wherein said trisiloxane is ?-methacryloxypropylsiloxane, said chain extender is a dimethyl siloxane and said end group is a trimethyl siloxane.
- 5. A resin system for use in polymerizates of contact lens material, said resin system having the following formula:
a b c wherein "a" + "b" + "c" = 1, and "a", "b" and "c" are each greater than 0. - 6. A resin system in accordance with claim 5 wherein "a" has a mole fraction value of from 0.10 to 0.40, "b" has a mole fraction value of from 0.25 to 0.80 and "c" has a mole fraction value of from 0.10 to 0.40.
- 7. A resin system in accordance with claim 6 which has a viscosity of from 7 to 70 centistokes at 25°C
- 8. A multifunctional organopolysiloxane resin system whose starting materials comprise a reactive vinyl type silane, a disubstituted silane and a trisubstituted silane hydrolyzed together to form a resin system having a viscosity of from 7 to 70 centistokes at 25°C.
- 9. A resin system in accordance with claim 8 wherein said reactive vinyl type siloxane is a gamma methacryloxypropylsiloxane unit, said disubstituted siloxane is a dimethylsiloxane unit and said trisubstituted siloxane is a trimethylsiloxane unit each in respective mole ratios of from 0.10 to 0.40 0.25 to 0.80 and 0.10 to 0.40 mole fractions.
- 10. A multifunctional organopolysiloxane resin system formed from mono, di and tri-substituted reactive silanes, said resin comprised of mono, di and tri-substituted organosiloxane units wherein at least one vinyl type moiety per molecule is present.
- 11. A polymerizate of the resin system of claim 1 and a hardness modifying agent.
- 12. The polymerizate of claim 11 and further including a hydrophilic agent.
- 13. A polymerizate as claimed in claim 11 wherein said resin system comprises from 25 to 98%
by weight. - 14. A polymerizate in accordance with claim 13 wherein said hardness modifying agent is selected from the class consisting of esters of a C1-C20 monohydric or polyhydric alkanol or phenol and an acid selected from he class consisting essentially of acrylic, methacrylic, itaconic acid and mixtures thereof.
- 15. A polymerizate in accordance with claim 14 wheren said hardness modifying agent is methyl methacrylate.
- 16. A contact lens including a polymerizate of the resin system of claim 1.
- 17. A contact lens including a polymerizate of the resin system of claim 5.
- 18. A contact lens polymerized material formed from A) 25 to 98% by weight of the resin system having the following formula:
a b c a = 0.10 to 0.40 mole fraction b = 0.25 to 0.80 mole fraction c = 0.10 to 0.40 mole fraction, B) 75 to 2% by weight of an ester of a C1-C20 monohydric or polyhydric alkanol or phenol and an acid selected from the class consisting essentially of acrylic, methacrylic, itaconic acid and mixtures thereof, and C) 1 to 10% of a hydrophilic agent, which material is polymerized to a degree above 95% completion by free radical polymerization. - 19. A contact lens material in accordance with claim 18 wherein A) is in the range of from 30 to 60% by weight, a = 0.20 to 0.35 mole fraction b = 0.40 to 0.60 mole fraction c = 0.20 to 0.40 mole fraction B) is 69 to 40% by weight and is methylmethacrylate C) is 1 to 10% by weight.
- 20. A contact lens material in accordance with claim 19 wherein C is vinylpyrrolidone.
- 21. A contact lens material in accordance with claim 19 wherein C is acrylic acid.
- 22. A contact lens material in accordance with claim 19 wherein C is methacrylic acid.
1. A multifunctional organopolysiloxane resin system which can be polymerized into a transparent, optically clear, polymeric material having good oxygen permeability and suitable for use in contact lens fabrication, said resin system having the following formula:
Where:
R is hydrogen or methyl R' is a divalent alkylene radical having from one to five carbon atoms R" is a monovalent hydrocarbon radical having from one to five carbon atoms, a substituted monovalent hydrocarbon radical having from one to five carbon atoms, a phenyl group, a substituted
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US43048982A | 1982-09-30 | 1982-09-30 | |
| US430,489 | 1982-09-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1226696A true CA1226696A (en) | 1987-09-08 |
Family
ID=23707771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000436190A Expired CA1226696A (en) | 1982-09-30 | 1983-09-07 | Silicone-containing contact lens material and contact lenses made thereof |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5961816A (en) |
| AU (1) | AU564035B2 (en) |
| CA (1) | CA1226696A (en) |
| DE (1) | DE3329722A1 (en) |
| FR (1) | FR2533933B1 (en) |
| GB (1) | GB2129005B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0627911B2 (en) * | 1987-06-06 | 1994-04-13 | 株式会社メニコン | Contact lens material |
| ATE141305T1 (en) * | 1988-04-04 | 1996-08-15 | Loctite Corp | MTQ POLYSILOXANE RESIN, METHOD OF PRODUCTION AND COATING OR EMBEDDING COMPOSITION |
| MX169040B (en) * | 1988-07-07 | 1993-06-17 | Rohm & Haas | STABLE COOLERS OF AQUEOUS EMULSION WITH SILOXANE FUNCTIONALITY |
| DE19630100A1 (en) * | 1996-07-25 | 1998-01-29 | Inst Neue Mat Gemein Gmbh | Process for producing a shaped body suitable for optical purposes |
| JP4883683B2 (en) * | 2006-03-31 | 2012-02-22 | 旭化成ケミカルズ株式会社 | Organopolysiloxane for gas separation membrane |
| CN110072919A (en) | 2016-12-13 | 2019-07-30 | 三菱化学株式会社 | Polysiloxane, constituent polyorganosiloxane composition and its solidfied material and the electrolyte for electrolytic capacitor containing polysiloxane and the electrolytic capacitor using it |
| JP7091683B2 (en) * | 2017-02-06 | 2022-06-28 | 三菱ケミカル株式会社 | Organopolysiloxane |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1018625B (en) * | 1954-05-20 | 1957-10-31 | Dow Corning | Process for the preparation of new organopolysiloxanes |
| US4035355A (en) * | 1975-12-10 | 1977-07-12 | Dow Corning Corporation | Anaerobically curing silicone compositions |
| US4120570A (en) * | 1976-06-22 | 1978-10-17 | Syntex (U.S.A.) Inc. | Method for correcting visual defects, compositions and articles of manufacture useful therein |
| US4216303A (en) * | 1979-01-26 | 1980-08-05 | George F. Tsuetaki | Oxygen-permeable contact lens compositions, methods and articles of manufacture |
| US4259467A (en) * | 1979-12-10 | 1981-03-31 | Bausch & Lomb Incorporated | Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains |
| US4424328A (en) * | 1981-12-04 | 1984-01-03 | Polymer Technology Corporation | Silicone-containing contact lens material and contact lenses made thereof |
| EP0094153A2 (en) * | 1982-05-10 | 1983-11-16 | Dow Corning Corporation | Inherently wettable silicone resin optical devices |
-
1983
- 1983-07-29 AU AU17435/83A patent/AU564035B2/en not_active Ceased
- 1983-08-16 JP JP14889583A patent/JPS5961816A/en active Granted
- 1983-08-17 DE DE19833329722 patent/DE3329722A1/en not_active Withdrawn
- 1983-08-23 FR FR8313627A patent/FR2533933B1/en not_active Expired
- 1983-09-07 CA CA000436190A patent/CA1226696A/en not_active Expired
- 1983-09-07 GB GB08323955A patent/GB2129005B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS637367B2 (en) | 1988-02-16 |
| AU1743583A (en) | 1984-04-05 |
| JPS5961816A (en) | 1984-04-09 |
| GB2129005A (en) | 1984-05-10 |
| GB2129005B (en) | 1986-06-11 |
| AU564035B2 (en) | 1987-07-30 |
| GB8323955D0 (en) | 1983-10-12 |
| FR2533933B1 (en) | 1987-02-06 |
| FR2533933A1 (en) | 1984-04-06 |
| DE3329722A1 (en) | 1984-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4625007A (en) | Silicone-containing contact lens material and contact lenses made thereof | |
| US4826936A (en) | Silicone-containing contact lens material and contact lenses made thereof | |
| US4424328A (en) | Silicone-containing contact lens material and contact lenses made thereof | |
| US4604479A (en) | Silicone-containing contact lens material and contact lenses made thereof | |
| EP0219312B1 (en) | Improved fluorine containing polymeric compositions useful in contact lenses | |
| US4996275A (en) | Fluorine containing polymeric compositions useful in contact lenses | |
| EP1355963B1 (en) | Polymeric biomaterials containing silsesquioxane monomers | |
| US4463149A (en) | Silicone-containing contact lens material and contact lenses made thereof | |
| EP0424099B1 (en) | Method of Preparing Polymeric Compositions for Oxygen Permeable Contact Lenses | |
| US5177168A (en) | Polymeric compositions useful in oxygen permeable contact lenses | |
| CA1298928C (en) | Continuous-wear lenses having improved physical properties | |
| EP1196499B1 (en) | Contact lens material | |
| EP0059528B1 (en) | Polysiloxane with polycyclic modifier composition and biomedical devices | |
| JPH029612B2 (en) | ||
| EP0796723B1 (en) | Process for producing optic lens and optic lens obtained thereby | |
| JP3753328B2 (en) | Novel silicone-containing polymer and oxygen permeable hydrophilic contact lens from said polymer | |
| CA1226696A (en) | Silicone-containing contact lens material and contact lenses made thereof | |
| US4410674A (en) | Silicone-vinyl acetate composition for contact lenses | |
| JP3050586B2 (en) | contact lens | |
| WO1984000969A1 (en) | Prostheses contact lenses and polymers therefor | |
| JPH11171929A (en) | Molded plastic article | |
| JPH0349410B2 (en) | ||
| CA2337173A1 (en) | Contact lens material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |