CA1118938A - Hydrophilic, soft and oxygen permeable copolymer compositions - Google Patents
Hydrophilic, soft and oxygen permeable copolymer compositionsInfo
- Publication number
- CA1118938A CA1118938A CA000331869A CA331869A CA1118938A CA 1118938 A CA1118938 A CA 1118938A CA 000331869 A CA000331869 A CA 000331869A CA 331869 A CA331869 A CA 331869A CA 1118938 A CA1118938 A CA 1118938A
- Authority
- CA
- Canada
- Prior art keywords
- group
- composition
- weight
- alkyl
- pyrrolidone
- 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
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Classifications
-
- 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
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- 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
Abstract
THE ABSTRACT OF INVENTION
A new composition of matter specially adapted for the production of contact lenses, artificial eyes or other prosthetic devices. The composition has the characteristics of increased hydrophilicity, softness after hydration and oxygen permeability. The composition is a solid copolymer of comonomers consisting essentially of about 15 to about 65%
by weight of one or more of the hydrophilic amide group containing monomers and about 10 to about 75% by weight of one or more of the copolymeric organosiloxane. Optionally, about 0.1 to about 65% by weight of at least one property modifier, a vinyl group containing monomer such as methyl methacrylate, can be employed into the copolymers. The inven-tive material is optionally transparent, translucent or opaque depending on the type, composition and relative content of the comonomers used. In general, the transparent composi-tion is suitable for use in making contact lenses.
A new composition of matter specially adapted for the production of contact lenses, artificial eyes or other prosthetic devices. The composition has the characteristics of increased hydrophilicity, softness after hydration and oxygen permeability. The composition is a solid copolymer of comonomers consisting essentially of about 15 to about 65%
by weight of one or more of the hydrophilic amide group containing monomers and about 10 to about 75% by weight of one or more of the copolymeric organosiloxane. Optionally, about 0.1 to about 65% by weight of at least one property modifier, a vinyl group containing monomer such as methyl methacrylate, can be employed into the copolymers. The inven-tive material is optionally transparent, translucent or opaque depending on the type, composition and relative content of the comonomers used. In general, the transparent composi-tion is suitable for use in making contact lenses.
Description
THE DESCRIPTION OF INVENTION
______ HYDROPHILIC, SOFT AND OXYGEN PERMEABLE COPOLYMER COMPOSITIONS
FIELD OF INVENTION
This invention relates to novel copolymer compositions, and more particularly to hydrophilic, soft after hydra~ion and oxygen-permeable copolymers.
THE PRIOR ART AND BACKGROUND OF THE INVENTION
The basic requirements for polymeric materials in some areas of medical application are that they be hydrophilic, soft and oxygen-permeable. The prior art teaches the use of many different polymeric materials in these areas such as in contact lenses, intraocular lens and other prosthetic devices.
Although these polymers possess certain desirable properties for their specific medical application, they suffer from other undesirable characteristics which reduce their utility.
In contact lens area, the hard lens material, polymethyl methacrylate (PMMA), is durable but relatively impermeable to oxygen and further suffers from being rigid and hydro-phobic. The hydrogel contact lens based on hydrophilic polymers such as polyhydroxyethyl methacrylate ~Poly HEMA) are soft but with poor durability and dimensional stability.
It also does not have enough oxygen permeability.
Another polymeric material is silicone rub~er, one kind of polysiloxane, which can also be used in contact lens and other prosthetic devices. Although it is soft, resilient and is highly gas permeable, it is hydrophobic.
Accordingly, it would be highly useful and desirable in medical applications to provide a polymeric material having increased hydrophilicity, softness after hydration, and oxygen permeability~ As compared to the hard lens material, PMMA, the copolymers taught in the patent to Gaylord, U.S. Patent No. 3,808,178, for contact lens fabrication have relatively high oxygen permeability, but suf~er from being rigid and relatively hydrophobic. Although in Examples 3 to 9 of the patent, .. . :
`,:
Gaylord teaches the use of 5 to 9 percent by weight of HEI~
(hydroxyethylmethacrylate) to increase the wettability o~ the copolymer. The copolymerS prepared there~rom can only absorb water up to about 1% of its welght. It i8 8till relatively rigid and hydrophobic. If a larger amount of this hydrophilic monomer is used in the compositions as claimed in the Gaylord patent, dif~erent defects would occur, such as, the comonomer mixture would become incompatlble1 the copolymer prepared there-from could become heterogeneous, brittle, lacking of streng-th or opaquel or the hardness of the copolymer i8 essentially unchanged even a~ter hydration because the material is relatively hydrophobic, Similar difficulties would result with the use of other hydrophilic monomers as taught in column 4, lines 53 to 62 of the Gaylord patent. Therefore by following Gaylord's teaching to use about 0.1 to about 10~ of hydrophilic monomers to improve the wettability of the copolymera a~ ~escribed~ we still could not make the material of the pre~ent invention which has increaæd hydrophilicity, 80~'tneSS aftar hydration and oxygen permeability for the fabrication of contact lenses or other prosthetic devices In ~earch of such a material, I unexpectedly discovered a novel copolymer material which possesses these highly use~ul properties.
The novel copolymers which I have discovered are pre-pared by essentially copolymerizing the copolymeric organosilo-xane with the hydrophilic amide group containing monomer (here-after, HAGM). One o~ the novel propertios of these copolymersi8 illustrated in Fig. 1 whlch ~how8 the effects of different amounts of hydrophilic monomers in the comonomeric compositions upon ~he hydro~hillc Properties of the copolymers prepared there-from. Tha latter is expressed in the percent by weight o~ water absorption ag de~ined in Example~ 10-16 of this specification.
Fig. l al~o shows the comparison of hydrophilic properties of the copolymers prepared in the present invention and in the Gaylord patent, Curvc A of F~g. 1 is the general trend of the hydrophilic proper~ics of the materials prepar~d in this inven-tion, curve B is the gencral hydrophilic ~rend of Gaylord'scopolymers in which about 0.1 to about 10~ of hydrophilic mono-meric material can be used and curve C is a prior art pro~ec-tion when HEMA~related monomerc are used as the hydrophilic . monomer in the comonomeric mixture. It appear~ that the hydro 4 philic properties of the copolymers of ~he present invention, '.
:, : , . . . .
.
3 gl ~ 3~
~ .~
curve A, are substantially higher than those of the Gaylord materials, curve B, and also substantially higher than those of prior art projection, curve C, In addition, as described previously these copolymers of curve C would have other short comings.
In order to support the unobviousness of the present invention, a comparison of optical characteristics between those of the instant invention and those of the closest prior art, the Gaylord patent and its projection is summarized in Table I, which shows that according to the prior ar-t proiec~
tion, if the amount of HEMA used in the composition is about or larger than 15~ by volume of the composition, the copolymer obtained is opaque-a character~tic being not desirable for contact lens application. However, when a corresponding amount of VP (vinyl pyrrolidone) to HEMA i5 used in the composition, the copolymer obtained in the instant Application is transparent - a characteristic being desirable for contact lens application.
TABLE I. ~~parision of The Unobvious O~tical Charac-ris~ of The Compositions of The Instant Invention to Tho~e o~ the Prior Art Com~osi-tion~ The Ga~lord Patent and Its Pro;ect~on.
.
Examplea Comment and
______ HYDROPHILIC, SOFT AND OXYGEN PERMEABLE COPOLYMER COMPOSITIONS
FIELD OF INVENTION
This invention relates to novel copolymer compositions, and more particularly to hydrophilic, soft after hydra~ion and oxygen-permeable copolymers.
THE PRIOR ART AND BACKGROUND OF THE INVENTION
The basic requirements for polymeric materials in some areas of medical application are that they be hydrophilic, soft and oxygen-permeable. The prior art teaches the use of many different polymeric materials in these areas such as in contact lenses, intraocular lens and other prosthetic devices.
Although these polymers possess certain desirable properties for their specific medical application, they suffer from other undesirable characteristics which reduce their utility.
In contact lens area, the hard lens material, polymethyl methacrylate (PMMA), is durable but relatively impermeable to oxygen and further suffers from being rigid and hydro-phobic. The hydrogel contact lens based on hydrophilic polymers such as polyhydroxyethyl methacrylate ~Poly HEMA) are soft but with poor durability and dimensional stability.
It also does not have enough oxygen permeability.
Another polymeric material is silicone rub~er, one kind of polysiloxane, which can also be used in contact lens and other prosthetic devices. Although it is soft, resilient and is highly gas permeable, it is hydrophobic.
Accordingly, it would be highly useful and desirable in medical applications to provide a polymeric material having increased hydrophilicity, softness after hydration, and oxygen permeability~ As compared to the hard lens material, PMMA, the copolymers taught in the patent to Gaylord, U.S. Patent No. 3,808,178, for contact lens fabrication have relatively high oxygen permeability, but suf~er from being rigid and relatively hydrophobic. Although in Examples 3 to 9 of the patent, .. . :
`,:
Gaylord teaches the use of 5 to 9 percent by weight of HEI~
(hydroxyethylmethacrylate) to increase the wettability o~ the copolymer. The copolymerS prepared there~rom can only absorb water up to about 1% of its welght. It i8 8till relatively rigid and hydrophobic. If a larger amount of this hydrophilic monomer is used in the compositions as claimed in the Gaylord patent, dif~erent defects would occur, such as, the comonomer mixture would become incompatlble1 the copolymer prepared there-from could become heterogeneous, brittle, lacking of streng-th or opaquel or the hardness of the copolymer i8 essentially unchanged even a~ter hydration because the material is relatively hydrophobic, Similar difficulties would result with the use of other hydrophilic monomers as taught in column 4, lines 53 to 62 of the Gaylord patent. Therefore by following Gaylord's teaching to use about 0.1 to about 10~ of hydrophilic monomers to improve the wettability of the copolymera a~ ~escribed~ we still could not make the material of the pre~ent invention which has increaæd hydrophilicity, 80~'tneSS aftar hydration and oxygen permeability for the fabrication of contact lenses or other prosthetic devices In ~earch of such a material, I unexpectedly discovered a novel copolymer material which possesses these highly use~ul properties.
The novel copolymers which I have discovered are pre-pared by essentially copolymerizing the copolymeric organosilo-xane with the hydrophilic amide group containing monomer (here-after, HAGM). One o~ the novel propertios of these copolymersi8 illustrated in Fig. 1 whlch ~how8 the effects of different amounts of hydrophilic monomers in the comonomeric compositions upon ~he hydro~hillc Properties of the copolymers prepared there-from. Tha latter is expressed in the percent by weight o~ water absorption ag de~ined in Example~ 10-16 of this specification.
Fig. l al~o shows the comparison of hydrophilic properties of the copolymers prepared in the present invention and in the Gaylord patent, Curvc A of F~g. 1 is the general trend of the hydrophilic proper~ics of the materials prepar~d in this inven-tion, curve B is the gencral hydrophilic ~rend of Gaylord'scopolymers in which about 0.1 to about 10~ of hydrophilic mono-meric material can be used and curve C is a prior art pro~ec-tion when HEMA~related monomerc are used as the hydrophilic . monomer in the comonomeric mixture. It appear~ that the hydro 4 philic properties of the copolymers of ~he present invention, '.
:, : , . . . .
.
3 gl ~ 3~
~ .~
curve A, are substantially higher than those of the Gaylord materials, curve B, and also substantially higher than those of prior art projection, curve C, In addition, as described previously these copolymers of curve C would have other short comings.
In order to support the unobviousness of the present invention, a comparison of optical characteristics between those of the instant invention and those of the closest prior art, the Gaylord patent and its projection is summarized in Table I, which shows that according to the prior ar-t proiec~
tion, if the amount of HEMA used in the composition is about or larger than 15~ by volume of the composition, the copolymer obtained is opaque-a character~tic being not desirable for contact lens application. However, when a corresponding amount of VP (vinyl pyrrolidone) to HEMA i5 used in the composition, the copolymer obtained in the instant Application is transparent - a characteristic being desirable for contact lens application.
TABLE I. ~~parision of The Unobvious O~tical Charac-ris~ of The Compositions of The Instant Invention to Tho~e o~ the Prior Art Com~osi-tion~ The Ga~lord Patent and Its Pro;ect~on.
.
Examplea Comment and
2 - ~i2 VPc HEMAd MMAe optical ProPertieSf 1 _ 50 _ 9 41 T, The prior art
3 50 17 33 0 The prior art
4 50 20 30 0 prolection, opaque ~ 5 _ 1~O
8 5 17 33 T The instant appli-9 50- 20 30 T cation, transparent _ _ .. .... . _ . . ... _ _ aThe composition ~volume%~ were prepared by ~ollowing the general procedure as deso~lbed in the Example 2-9 of the instant Applica~ion.
~.,.
, ,, ~ :
; .,, . :~.
",- .,~
4. ~ 3~
. .
bSi2 was prepared in Example 1 of -the specification.
CVP _ N-vinyl pyrrolidone dHEMA = 2-hydroxyethyl methacrylate MMA = methyl methacrylate fBased on the visual observation to the composition rods about 11 mm in diameter. 0 = opaque~ T = transparent.
As a matter o~ fact, Gaylord limited the use of hydrophilic monomers to improve the wettability of his copolymer to a narrow range of from about o.l to about 10% by weight only as shown ~n curve B of Fig. 1.
In addition9 I have also discovered that not every percentage range of HAGM can be used in the composition of this invention, the ussful range of HAGM as indicated in the curve A of Fig, 1 is only limited within the general range-from about 15 to about 65 and most pre~erably from about 25 to about 45 percent by weight. Another novel and useful propertyof my inven-ted material i~ that it becom~ increasingly soft after hydr~--~ tion while the hardness of Gaylord' 8 material is essentially unchanged after hydration, An example of this iB illustrated in Example 17 in the speci~ication of this invention, I also discovered that my claimed composition ha~
the characteris~ic o~ increased oxygen permeability. The oxygen permeability of my invention as illustrated in Example 18 of this specif1cation is about 1,600 c.c.-mil/100 in2/24 hr/
atm whereas those a~ illustrated in the examples of the Gaylord patent are between 300 and 500 units only.
With these novel properties as described above, the composition of this invention i8 highly useful in a number of medical applications, For contact lenses, this material 3 provides a combination o~ properties that are clo9e to an ideal combination of properties o~ the best ~eatures of the hard lens material, PMMA, so~t lens material, Poly HEMA~ sillcone rubber and the Gaylord oopolymer lenses, For other pro~the-tic devices, features such as increased hydrophilicity, so~tness ~f-ter hydra-tion and gas permeability are al80 vsry useful and desirable, . .
.
, ,
8 5 17 33 T The instant appli-9 50- 20 30 T cation, transparent _ _ .. .... . _ . . ... _ _ aThe composition ~volume%~ were prepared by ~ollowing the general procedure as deso~lbed in the Example 2-9 of the instant Applica~ion.
~.,.
, ,, ~ :
; .,, . :~.
",- .,~
4. ~ 3~
. .
bSi2 was prepared in Example 1 of -the specification.
CVP _ N-vinyl pyrrolidone dHEMA = 2-hydroxyethyl methacrylate MMA = methyl methacrylate fBased on the visual observation to the composition rods about 11 mm in diameter. 0 = opaque~ T = transparent.
As a matter o~ fact, Gaylord limited the use of hydrophilic monomers to improve the wettability of his copolymer to a narrow range of from about o.l to about 10% by weight only as shown ~n curve B of Fig. 1.
In addition9 I have also discovered that not every percentage range of HAGM can be used in the composition of this invention, the ussful range of HAGM as indicated in the curve A of Fig, 1 is only limited within the general range-from about 15 to about 65 and most pre~erably from about 25 to about 45 percent by weight. Another novel and useful propertyof my inven-ted material i~ that it becom~ increasingly soft after hydr~--~ tion while the hardness of Gaylord' 8 material is essentially unchanged after hydration, An example of this iB illustrated in Example 17 in the speci~ication of this invention, I also discovered that my claimed composition ha~
the characteris~ic o~ increased oxygen permeability. The oxygen permeability of my invention as illustrated in Example 18 of this specif1cation is about 1,600 c.c.-mil/100 in2/24 hr/
atm whereas those a~ illustrated in the examples of the Gaylord patent are between 300 and 500 units only.
With these novel properties as described above, the composition of this invention i8 highly useful in a number of medical applications, For contact lenses, this material 3 provides a combination o~ properties that are clo9e to an ideal combination of properties o~ the best ~eatures of the hard lens material, PMMA, so~t lens material, Poly HEMA~ sillcone rubber and the Gaylord oopolymer lenses, For other pro~the-tic devices, features such as increased hydrophilicity, so~tness ~f-ter hydra-tion and gas permeability are al80 vsry useful and desirable, . .
.
, ,
5. ~ 31~
DISCLOSURE OF THE INVENTION
. . . _.
The invention relates to a new composition of matter specially adapted for the making of contact lenses, artificial eyes or other prosthetic devices.
An object of the invention is to provide a new and useful composition for medical prosthetic devices. Another object of the invention is to provide increased hydrophilicity, softness after hydration and oxygen permeability for hard contact lens composition.
Still another object of the invention is also to provide for increasing the oxygen permeability of soft lens compositions.
Yet another object of the invention is to provide increased hydrophilic, soft after hydration and oxygen-permeable compositions.
The novel copolymers which are disclosed are prepared by essentially copolymerizing the amide group containing monomers with copolymeric organosiloxane. Particularly effec-tive for this invention is a copolymer composition consisting essentially of:
(A) about 15 to about 65, preferably about 20 to ~ about 55 and most preferably about 25 to about 45 weight per-cent of at least one of the hydrophilic amide group containing monomers;
(B) about 10 to about 75, preferably 20 to 55 and most preferably 25 to 45 weight percent of at least one copolymeric organosiloxane; and (C) optionally, about 0.1 to about 65~ by weight of at least one ester of a Cl-C20 alkanol and an acid selected from a group consisting of acrylic and methacrylic acids.
The typical amide group containing monomers that are suitable for the practice of this invention must be hydrophilic and must contain a carbonyl functionality adjacent to the nitrogen, which can be either in the heterocyclic ring or in the noncyclic structure. In addition, such monomers must contain a polymerizable olefin containing group (hereafter, G), such as vinyl, acryloxy and methacryloxy groups (CH2=CRlCOO-), : ~ `'' , :,,~
,: ,; -: ~ : ; :,., ., -: . . , , :,. : ., , ,............ ;
: ~ ., : :. . : . . : , : , .
acrylatoalkyl and methacrylatoalkyl groups (CH2-CR1COO(CH2)m-), acrylamido and methacrylamidoalkyl groups (CH2~CRlCONH(CH2)m~), wherein Rl i~ either hydrogen or methyl group, m is an i~teger of from-one to 4. Preferably G is bonded to the nitrogen atom of the amide group. The suitable heterocyclic amide containing group of the monomer is preferably selected from a group consisting ess,entially of pyrrolidone, piperidone, imidazoli-done and succinimide. It is understood that these amide con-taining group may be substituted in th~ heterocyclic ring by one or more of low alkyl groups such as methyl, ethyl and the like. The ,uitable noncyclic amide group containing monomer is preferably selected from a group consisting essentially of N-alkyl or N,N-dial~yl acrylamide and methacryl-amide, wh,~rein each alkyl group is individually an unsubstitu-ted mono- valent hydrocarbon radical having one to 6 carbon atoms or a substituted monovalent hydrocarbon radical having from one to 6 carbon atoms where~n the substituent may be selected from a group con~isting o~ amino 9 alkoxy, carbonyl and hydroxy groups. It i8 understood o~ course that mixtures of such heterocyclic and noncyclio monomors can be em,ployëd in preparing the copolymers of the pre~ent invention.
The preferred heterocyclic monomers employed are N-vinyl lactame o~ which N-vinyl-2-pyrrolidone is the most preferred, and the preferred noncyclic monomer,~ employed are N,N-dialkyl methacrylamide of which N,N-dimethyl methacrylamide is the most preferred.
The copolym,eric organosiloxanes that are ,~uitable for the Practice of this lnvention fall within the ,general acrylated or methacryl~ted organosilicon compounds. The essential constituent uni~s of each molecular compound have the formulas~
M~ CH2-cRcoo(cH2)nR~asio ~ a~
N, R''bsiO4-b wherein the molar ratios of M ~o N are in the range of ~rom about 1 to 99 to about 99 to 1, more particularly from about 1 to 50 to ~out ~0 tc 1 and mo~t part~,ularly from about 1 to 20 to abeu~ 20 to 1,~ e~c~ed from a group consi~ting of hydrogen and methyl ,~O)J~ ,Rt a~d R~' ? which may be the same ;.
``, , , ~ ~ , , i ,.
' . .
`'` :
or different, are monovalent hydrocarbon groups ~elected from a ~roup consi~ting of Cl-C4 alkyl group~, cyclohexyl groups and phenyl groups~ n i8 an integer of from one to four inclu-sive~ a i8 an integer o~ from O to 2 inclusive and b i9 an integer o~ from zero to three inclusive.
~ he term of "molar ratio" is not used herein as based upon the actual molecular weight of the copolymer per se, but rather as based upon the molecular weight of the unit or average molecular weight o~ the units which are prssent in such copolymer, as i~ the common practice in the polymer chemistry, The defined copolymeric siloxane can contain either one or two of such monovalent hydrocarbon radicals attached to any given silicon atom, The ~' and R" groups attached to the individual silicon atoms can be the same or diffarent radicals, The copolymeric organosiloxanes prepared can themselves con-tain the SiO2, R"SiOl 5, R"2SiO, or R"3SiOo 5 siloxane units and with any desired var~ation of R" radicals attached to silicon atoms, as long as they are liquid ~o that intimate contact can be mad~ with the amide group containing monomer~
~ 20 and other monomers, The general procedures to synthesize the abo~e defined copolymeric organosiloxane which i8 suitable for the practice of this invention are well known in the art o~
cone chemistry, One of the pre~erred method~ i~ to reaot the corresponding chlorome~hyl substituted organo~ilic~n compounds with a triethylamîne salt.of ~lther ~crylic or methacrylic acid a~ illustrated in Example 1 of this specification. As is well known in the art, the chloromethyl aubstituted organo-silicon compounds employed as intermediates in the above pre-parations may them~elves be prepared by halogenating a methyltrihalo~lane and sub.~ecting the product to reaction with a Grignard reagent to replace some or all of the ~ilicon bonded halogen atoms,,followed if de~ired by the hydrolysis o~ the unreacted silicon bonded halogen atoms to produce the corres- .
ponding silo~ane.
Alternatively~ the defined copolymeric organosilo-xanes can be prepared by means of the well known acid catalyz-ed siloxane oonden~ation mothod~. One of the pref~rred methods is to react ~-me~hacryloxypropyltrime~hoxysilane with trimethyl I
.
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, ,.. . . .
, ~ ,:,, ~, :, ~ . : . : ::
8. ~ 3~
acetoxysilane or other corresponding acetoxysiloxanes as illustrated in Example 1 herein, and the other method is to mix the acrylated or methacrylated organosiloxane as specified previously with the organosiloxane as defined in formula N in S the desired ratio and the mixture ~eated in the presence of an acid catalyst such as concentrated sulfuric acid. The acid catalyst is preferably present in an amount of from 0.5 to 3 percent by weight based upon the weight of the combined reactants. This type of reaction proceeds at room temperature, but is preferably speeded up by heating the mixture at a higher temperature. Obviously, in order to prepare a mono-or multi-acrylated or methacrylated copolymeric organosiloxane which is suitable for the practice of this invention, the above mentioned methods can be properly combined to use, such 15 as those described in the U. S. Patent No. 2,956,044.
Optionally, the physical properties`of the copoly-mers in this invention can be modified by copolymerizing the composition mixture with one or more of vinyl group contain-ing monomers. For example, if desired, in order to increase the strength, hardness, or in some cases to improve the optical properties or to act as additive of the copolymers, about 0.1 to about 65, preferably 5 to 50 and most preferably 15 to 35~ by weight of one or more of the vinyl group containing monomers or an ester of a Cl-C20 alkanol and an acid selected from a class consisting of acrylic and metha-acrylic acids, such as methyl methacrylate, ethyl acrylate and methacrylate, butyl acrylate and methacrylate, amyl acrylate and methacrylate, hexyl acrylate and methacrylate, octyl acrylate and methacrylate, 2-ethylhexyl acrylate and methacrylate, decyl acrylate and methacrylate, lauryl acryl-ate and methacrylate, octadecyl acrylate and methacrylate and the like, can be incorporated into the materials by the technique of copolymeri2ation.
The rigidity of the copolymer in this invention can also be improved, if desired, by incorporating into the material with about 0.1 to about 20, preferably about 0Ol to about 5% by weight of one or more of the vinyl group containing crosslinking monomers. Representative of cross-linking monomers which are suitable for the practice of this .
.
- : . i :.. . . .. . .
: .. ,: , , .~
,: ' '' ''; ' ' ' ` ;
~_ ` 9~ 3~3 inven~ion are polyol dimethacrylate or diacrylate or a polyol acrylic or methacrylic e~ter of higher functionality, for example, mono-, di-, tri-, or tetraethylene glycol dimethacrY-late, butylen~ glycol dimethacrylate, neopentyl dlacrylate and pentaerythritol triacrylate or t~tracrylate and the like.
The copolymers o~ the in~ent~on ar~ prepared by contacting the mixture of comonomers with a free radical generating polymerization ini~iator o~ the type commonly usad in polymerizing ethylen~cally un~aturated compound~. Repre~
sentative fre~ radical polymerization initiators are organic peroxides, such as acetyl peroxide, lauroyl peroxlde, decano-yl peroxide, stearoyl peroxide, benzoyl peroxideO tertiary-butyl peroxypivalat~, acetyl peroxy isobutyl carbonate and the like. Other catalyst~, ~uch a~ ~d-azobi~i6obutyroni trile, can also be used. Alternatively, in certain case~
the mixture of the comonomer~ can al~o be polymerized by radiation initiated polymerization, Conventional polymeriza-tion technique~ can be employed to produce the novel copoly-mers. The comonomer mixtur~ con~aining the free radical 20` initiator~ generally from about 0.01 to about 5 and prefer-ably between 0.05 to 2 percent by weight, i8 heated to a temperaturs o~ ~rom about 45~C to 100C or even higher but preferably between 45C to 70C., to ini~ia~a and complete the polym~rization~
The polymerization can be carri~d out dLr~ctly in a mold with th~ de~ired oon~ig~ration euoh ~ for con~a¢t l~n8e8. Alternativ~ly,~ the polym~ri~ation mixture can ba heated in a suitable mold or conta~n~r ~o form disc~, rods, sheets or other ~orm~ which can then be fabr~cated into the de~ired ~hape using conventional squipment and technologywell known in the art. Instead o~ ~mploy~ng the bulk poly~
merizati~on technigues de~cribcd abo~e, one can e~ploy 801u-tion, emulsion or su~pGnsion polymerization to prepsre the novel copolymer~,~using tcchniques conventio~lly u~ed in the preparation o~ p~lymers ~rom ~thyl~nically un~aturated mono~
mers. The copolymer thus produced may b~ extruded, pre~ed or molded into rod~, sheets o~: o~her convenient ~hape~ which are then machin~d to produ~ a contact lens or other prosthe-tic de~rices. ~h~ ~.nventlYe oopolyn~ar~ can al~o be tintcd a~
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-; :. ,. '. . ~ ..
, . . ~ ,-.. ;...... ~ .
, ~ ~ . . . .
,........... . ~
~` ,6 10. ~ 3l~
~ ..
known in the art, The inventive copolymer i~ optionally transparent, translucen~ or opaque depending on the type, composition and relative content of the comonomers used. Generally speaking.
5 the transparent product is suitable for contact lens fabrica-tion~ -The novel copolymers have vastly increa~ed hydrophi-licity in comparison to the corresponding copolymer~ taught in U, S. Patent No. 3,808,178, the conventional hard lens matëri-10 al, polymethyl methacrylate (PMMA).or silicone rubber used inmedical application~, For example, a copolymer comprising 45~ by volume of N-vinyl pyrrolidone, 25% by volume of copo-lymeric organosiloxane, Sil prepared in xample 1 of this specification and 30~ by volume of methyl methacrylate (MMA) 15 as taught in thi~ in~ention can absorb water or hydrate up to about 26% of ~ts weight, wherea~ the hard len~ material, PI~MA, and the copolymer with the composition of 25~ of Sil and 75 of MMA as taught in the above mentioned patent can only be hydrated, up to about 0,5% of the weight. I~ the wettability 20 of the copolymar i8 improved by the addition of up to about ` 10% o~ hydrophilic HEMA in the comonomeric mixture a~ de3cr~b-ed in Examples 3-9 of the Gaylord patent~ the h~aration of the material prepared tharefrom i~ also only abou~ 1~, The cone rubber is e~sentially hydrophobic.
In additio~, the novel copolymer~ taught in this invention have va~tly increaæed ~o~tness after hydration.
For example, in the above mentioned exampl~ before hydration the hardness of the material taught in this invention i~ at about ~5 as measured by Portable Hardness Te~ter, Mod~l GYZJ
30 936, Barber-Colman Co., Ill., but after fully hydrated, it becomè~ about 15~ wherea~ the others ~till keep at about original value, PMMA at about 93 and the other~ at about 80.
Generally the degree o~ aoftness o~ the copolymer after hydra-tion in thia invention depends on the degreo of it~ hydrophi-~5 licity, The higher tho content o~ the hydrophilic comonomer inthe copolymer? the higher the degree of its hydrophilici~y and - the ~ofter the lens ~8 a~ter hydration, Xn the practice of thi~ ~nvention i~ ~ pre~cr~e~ to ~elec~ the copolymer wl~h . ..
. : ~, .: ' - .:
' , ., ~ 11~
~ .
percent of hydration between abo~ 8 -to about 35%
Furthermore, the novel copolymers have also vastly increased ga~ permeability in comparison to conventional contact lens materials, PM~,rand soft lens material, poly HE~, For example, a copolymer comprising 30 parts by volume of N-vinyl pyrrolidone, 50 parts o~ Sil and 20 parts of MMA
has an oxygen permeabili~y of ab~u~ 1~600 c.c,-mil/100 in2/
24 hrs/atm compared to an oxygen permeability o~ about 30 for P~ and ab~ 15 ~or Poly HEMA a~ described in t~ Gaylord patent, The oxygen permeability values o~ the Gaylord copo-lymers illustrated in the examples of the Caylord patent are between 300 and 5OO units only. These oxygen permeability values were determined in accordance with ASTM D1434. The substantially increased oxygen permeabllity o~ the composi-tions of thi~ invention could be due to the synergi~ticeffect of the component~ u~ed~
In the practice of this invention in contact lens area, the r~ractive index i8 an important but noncritical charac~eristic, ThUs, the refracti~e index o~ polyme~hyl ;. 20 methacrylate, the polymer most widely used in the fæbrication ` of hard contact lenses 9 i~ 1,49, The refractive ind~ces of the copolymers use~ul in the practice o~ th~s invention in the fabrication of contact lenses are pre~erably selec~ed between about 1,~ and about 1,5 which maybe ~aried by chang-ing the ratio and nature of the comonomers uæed.
BRIEF DESCRIPTION OF TXE DRAWING
ThR difference between the hydrophilic properties o~ the copolymers of this in~ention and those o~ ~he closest pr~or art, the Gaylord copolymer~9 will become ev~n further apparent upon ~he considera~1on of the ~ollowing disclosure o~ this invention, particularly when taken in con~unction with the accompanying drawin~7 Fig. I~ wherein th~ variation of hydrophilic properties of the copolymer~ are illustrated with respect to th~ percenta~e change by ~olume o~ the hydrophilic monomers used in the comonomeric mixture, Cur~e A i~ the present inventions B is the prior art~ and C i~ the prior art pro~ection, when HEMA related monomer~ are u~Qd.
.
- . : . , :
,, 12. ~ 9~
The following examples are presented to illustrate the practice of the invention and not as an indication of the limits of the scope thereof.
EXAMPLE I
This example illustrates some general procedures to synthesize the copolymeric organosiloxaneqi that are suit-able for the practice of this invention by the methods wellknown in the art.
Organosilicon.Compounds .1 and 2 (Sil) and (i~i2) The synthesis procedures of these compounds are essentially the same as that described in Example 15, U.S.
patent No. 3,808,178, except ~Methacrylatopropyltrimethoxysi-lane" should read "~-Methacryl~ypropyltrimethoxysilane", the upper oily layer is washed with water until neutral and the produce is distilled under high vacuum to remove methyl acetate, or other impurities.
,, ` ~ :' ', ~: , :` : ;' ', ' :
13.
The procedure described above can also be used to synthesize other corresponding organosilicon compounds, if trimethyl acetoxysilane used in the reaction is replaced by the other desired acetoxy siloxane, such as pentamethyl ace-toxydisiloxane, heptamethyl acetoxy trisiloxane and the like.
Apparently, the higher the numberof silicon in the acetoxy-siloxane used, the higher the vacuum and the higher the temperature of water bath, such as 80 or 90~C under high vacuum should be used in order to distill out the impurities.
When pentamethyl acetoxydisiloxane is used in the reaction, the copolymeric organosilicon compound thus prepared is called Si2.
Org'anosil'icon Compound 3 (Si3) The synthesis procedure of methacryloxymethylpenta-methyldisiloxane (Si3~ is fully described in Example 1 of U.S. Patent No. 2,956,044 and Example 1 of U. S. Patent No.
3,808,178.
Some Other Organo's'i'licon'COmpounds~ Si4, Si5 t Si5 etc-The detailed procedures to synthesize these compounds are fully described in Examples 2, 3, 4 and 5 of U. S. Patent No. 2,956,044.
'EXAMPLES''2'-9 The examples illustrate the preparations and proper-ties of the copolymers containing varying proportions of heterocyclic amide group containing monomer, e.g., N-vinyl-2-pyrrolidone (VP), the first type of organosilicon compounds, with or without MMA and crosslinking monomers, e.g., tetraethylene glycol dimethacrylate (TEGDM~. Furthermore, they also illustrate that a prosthetic device can directly be made from copolymerizing the composition mixture in a mold with a desired configuration.
The mixture of VP, Sil or Si2 with or without MMA, crosslinking agent, TEGDM, and with t-butyl peroxypivalate (t-BPP) (about 0.004 ml per ml of monomer mixture), after flushing nitrogen through the reaction mixture for 30 minutes, ,~
, . I ,' I ! ' , lL~, " ~ 38 was polymerized in a glass tube at 50~C for about 48 hour~, followed by placing at 100C oil bath for another 24 hrs.
After the tube was broken, they were all in the forms of rods.
The composi~ion and properties of the copolymers are collected in thefollowing table As indicated, all the rods are either transparent or opaque~ hard and rigid before hydration which can be cut, machined, polished and finished to contact len~es or other prosthetic devices by the techniques well known in the art. The material should have increased softness after hydration and increased oxygen permeability.
Com~osition, Vol Percent Example YP Sil Si2 ~ TEGDM Properties ~ ........ ~ .
2 33 67 0 0 H, T, R
3 50 50 0 0 H, Op., R
4 45 25 30 0 H, T, R
40 50 10 0 H, T, R
DISCLOSURE OF THE INVENTION
. . . _.
The invention relates to a new composition of matter specially adapted for the making of contact lenses, artificial eyes or other prosthetic devices.
An object of the invention is to provide a new and useful composition for medical prosthetic devices. Another object of the invention is to provide increased hydrophilicity, softness after hydration and oxygen permeability for hard contact lens composition.
Still another object of the invention is also to provide for increasing the oxygen permeability of soft lens compositions.
Yet another object of the invention is to provide increased hydrophilic, soft after hydration and oxygen-permeable compositions.
The novel copolymers which are disclosed are prepared by essentially copolymerizing the amide group containing monomers with copolymeric organosiloxane. Particularly effec-tive for this invention is a copolymer composition consisting essentially of:
(A) about 15 to about 65, preferably about 20 to ~ about 55 and most preferably about 25 to about 45 weight per-cent of at least one of the hydrophilic amide group containing monomers;
(B) about 10 to about 75, preferably 20 to 55 and most preferably 25 to 45 weight percent of at least one copolymeric organosiloxane; and (C) optionally, about 0.1 to about 65~ by weight of at least one ester of a Cl-C20 alkanol and an acid selected from a group consisting of acrylic and methacrylic acids.
The typical amide group containing monomers that are suitable for the practice of this invention must be hydrophilic and must contain a carbonyl functionality adjacent to the nitrogen, which can be either in the heterocyclic ring or in the noncyclic structure. In addition, such monomers must contain a polymerizable olefin containing group (hereafter, G), such as vinyl, acryloxy and methacryloxy groups (CH2=CRlCOO-), : ~ `'' , :,,~
,: ,; -: ~ : ; :,., ., -: . . , , :,. : ., , ,............ ;
: ~ ., : :. . : . . : , : , .
acrylatoalkyl and methacrylatoalkyl groups (CH2-CR1COO(CH2)m-), acrylamido and methacrylamidoalkyl groups (CH2~CRlCONH(CH2)m~), wherein Rl i~ either hydrogen or methyl group, m is an i~teger of from-one to 4. Preferably G is bonded to the nitrogen atom of the amide group. The suitable heterocyclic amide containing group of the monomer is preferably selected from a group consisting ess,entially of pyrrolidone, piperidone, imidazoli-done and succinimide. It is understood that these amide con-taining group may be substituted in th~ heterocyclic ring by one or more of low alkyl groups such as methyl, ethyl and the like. The ,uitable noncyclic amide group containing monomer is preferably selected from a group consisting essentially of N-alkyl or N,N-dial~yl acrylamide and methacryl-amide, wh,~rein each alkyl group is individually an unsubstitu-ted mono- valent hydrocarbon radical having one to 6 carbon atoms or a substituted monovalent hydrocarbon radical having from one to 6 carbon atoms where~n the substituent may be selected from a group con~isting o~ amino 9 alkoxy, carbonyl and hydroxy groups. It i8 understood o~ course that mixtures of such heterocyclic and noncyclio monomors can be em,ployëd in preparing the copolymers of the pre~ent invention.
The preferred heterocyclic monomers employed are N-vinyl lactame o~ which N-vinyl-2-pyrrolidone is the most preferred, and the preferred noncyclic monomer,~ employed are N,N-dialkyl methacrylamide of which N,N-dimethyl methacrylamide is the most preferred.
The copolym,eric organosiloxanes that are ,~uitable for the Practice of this lnvention fall within the ,general acrylated or methacryl~ted organosilicon compounds. The essential constituent uni~s of each molecular compound have the formulas~
M~ CH2-cRcoo(cH2)nR~asio ~ a~
N, R''bsiO4-b wherein the molar ratios of M ~o N are in the range of ~rom about 1 to 99 to about 99 to 1, more particularly from about 1 to 50 to ~out ~0 tc 1 and mo~t part~,ularly from about 1 to 20 to abeu~ 20 to 1,~ e~c~ed from a group consi~ting of hydrogen and methyl ,~O)J~ ,Rt a~d R~' ? which may be the same ;.
``, , , ~ ~ , , i ,.
' . .
`'` :
or different, are monovalent hydrocarbon groups ~elected from a ~roup consi~ting of Cl-C4 alkyl group~, cyclohexyl groups and phenyl groups~ n i8 an integer of from one to four inclu-sive~ a i8 an integer o~ from O to 2 inclusive and b i9 an integer o~ from zero to three inclusive.
~ he term of "molar ratio" is not used herein as based upon the actual molecular weight of the copolymer per se, but rather as based upon the molecular weight of the unit or average molecular weight o~ the units which are prssent in such copolymer, as i~ the common practice in the polymer chemistry, The defined copolymeric siloxane can contain either one or two of such monovalent hydrocarbon radicals attached to any given silicon atom, The ~' and R" groups attached to the individual silicon atoms can be the same or diffarent radicals, The copolymeric organosiloxanes prepared can themselves con-tain the SiO2, R"SiOl 5, R"2SiO, or R"3SiOo 5 siloxane units and with any desired var~ation of R" radicals attached to silicon atoms, as long as they are liquid ~o that intimate contact can be mad~ with the amide group containing monomer~
~ 20 and other monomers, The general procedures to synthesize the abo~e defined copolymeric organosiloxane which i8 suitable for the practice of this invention are well known in the art o~
cone chemistry, One of the pre~erred method~ i~ to reaot the corresponding chlorome~hyl substituted organo~ilic~n compounds with a triethylamîne salt.of ~lther ~crylic or methacrylic acid a~ illustrated in Example 1 of this specification. As is well known in the art, the chloromethyl aubstituted organo-silicon compounds employed as intermediates in the above pre-parations may them~elves be prepared by halogenating a methyltrihalo~lane and sub.~ecting the product to reaction with a Grignard reagent to replace some or all of the ~ilicon bonded halogen atoms,,followed if de~ired by the hydrolysis o~ the unreacted silicon bonded halogen atoms to produce the corres- .
ponding silo~ane.
Alternatively~ the defined copolymeric organosilo-xanes can be prepared by means of the well known acid catalyz-ed siloxane oonden~ation mothod~. One of the pref~rred methods is to react ~-me~hacryloxypropyltrime~hoxysilane with trimethyl I
.
".~ , :
- , , .. :.
, ,.. . . .
, ~ ,:,, ~, :, ~ . : . : ::
8. ~ 3~
acetoxysilane or other corresponding acetoxysiloxanes as illustrated in Example 1 herein, and the other method is to mix the acrylated or methacrylated organosiloxane as specified previously with the organosiloxane as defined in formula N in S the desired ratio and the mixture ~eated in the presence of an acid catalyst such as concentrated sulfuric acid. The acid catalyst is preferably present in an amount of from 0.5 to 3 percent by weight based upon the weight of the combined reactants. This type of reaction proceeds at room temperature, but is preferably speeded up by heating the mixture at a higher temperature. Obviously, in order to prepare a mono-or multi-acrylated or methacrylated copolymeric organosiloxane which is suitable for the practice of this invention, the above mentioned methods can be properly combined to use, such 15 as those described in the U. S. Patent No. 2,956,044.
Optionally, the physical properties`of the copoly-mers in this invention can be modified by copolymerizing the composition mixture with one or more of vinyl group contain-ing monomers. For example, if desired, in order to increase the strength, hardness, or in some cases to improve the optical properties or to act as additive of the copolymers, about 0.1 to about 65, preferably 5 to 50 and most preferably 15 to 35~ by weight of one or more of the vinyl group containing monomers or an ester of a Cl-C20 alkanol and an acid selected from a class consisting of acrylic and metha-acrylic acids, such as methyl methacrylate, ethyl acrylate and methacrylate, butyl acrylate and methacrylate, amyl acrylate and methacrylate, hexyl acrylate and methacrylate, octyl acrylate and methacrylate, 2-ethylhexyl acrylate and methacrylate, decyl acrylate and methacrylate, lauryl acryl-ate and methacrylate, octadecyl acrylate and methacrylate and the like, can be incorporated into the materials by the technique of copolymeri2ation.
The rigidity of the copolymer in this invention can also be improved, if desired, by incorporating into the material with about 0.1 to about 20, preferably about 0Ol to about 5% by weight of one or more of the vinyl group containing crosslinking monomers. Representative of cross-linking monomers which are suitable for the practice of this .
.
- : . i :.. . . .. . .
: .. ,: , , .~
,: ' '' ''; ' ' ' ` ;
~_ ` 9~ 3~3 inven~ion are polyol dimethacrylate or diacrylate or a polyol acrylic or methacrylic e~ter of higher functionality, for example, mono-, di-, tri-, or tetraethylene glycol dimethacrY-late, butylen~ glycol dimethacrylate, neopentyl dlacrylate and pentaerythritol triacrylate or t~tracrylate and the like.
The copolymers o~ the in~ent~on ar~ prepared by contacting the mixture of comonomers with a free radical generating polymerization ini~iator o~ the type commonly usad in polymerizing ethylen~cally un~aturated compound~. Repre~
sentative fre~ radical polymerization initiators are organic peroxides, such as acetyl peroxide, lauroyl peroxlde, decano-yl peroxide, stearoyl peroxide, benzoyl peroxideO tertiary-butyl peroxypivalat~, acetyl peroxy isobutyl carbonate and the like. Other catalyst~, ~uch a~ ~d-azobi~i6obutyroni trile, can also be used. Alternatively, in certain case~
the mixture of the comonomer~ can al~o be polymerized by radiation initiated polymerization, Conventional polymeriza-tion technique~ can be employed to produce the novel copoly-mers. The comonomer mixtur~ con~aining the free radical 20` initiator~ generally from about 0.01 to about 5 and prefer-ably between 0.05 to 2 percent by weight, i8 heated to a temperaturs o~ ~rom about 45~C to 100C or even higher but preferably between 45C to 70C., to ini~ia~a and complete the polym~rization~
The polymerization can be carri~d out dLr~ctly in a mold with th~ de~ired oon~ig~ration euoh ~ for con~a¢t l~n8e8. Alternativ~ly,~ the polym~ri~ation mixture can ba heated in a suitable mold or conta~n~r ~o form disc~, rods, sheets or other ~orm~ which can then be fabr~cated into the de~ired ~hape using conventional squipment and technologywell known in the art. Instead o~ ~mploy~ng the bulk poly~
merizati~on technigues de~cribcd abo~e, one can e~ploy 801u-tion, emulsion or su~pGnsion polymerization to prepsre the novel copolymer~,~using tcchniques conventio~lly u~ed in the preparation o~ p~lymers ~rom ~thyl~nically un~aturated mono~
mers. The copolymer thus produced may b~ extruded, pre~ed or molded into rod~, sheets o~: o~her convenient ~hape~ which are then machin~d to produ~ a contact lens or other prosthe-tic de~rices. ~h~ ~.nventlYe oopolyn~ar~ can al~o be tintcd a~
! `
.. ~ ,. . ... ...
. .
. . . ~ . .
-; :. ,. '. . ~ ..
, . . ~ ,-.. ;...... ~ .
, ~ ~ . . . .
,........... . ~
~` ,6 10. ~ 3l~
~ ..
known in the art, The inventive copolymer i~ optionally transparent, translucen~ or opaque depending on the type, composition and relative content of the comonomers used. Generally speaking.
5 the transparent product is suitable for contact lens fabrica-tion~ -The novel copolymers have vastly increa~ed hydrophi-licity in comparison to the corresponding copolymer~ taught in U, S. Patent No. 3,808,178, the conventional hard lens matëri-10 al, polymethyl methacrylate (PMMA).or silicone rubber used inmedical application~, For example, a copolymer comprising 45~ by volume of N-vinyl pyrrolidone, 25% by volume of copo-lymeric organosiloxane, Sil prepared in xample 1 of this specification and 30~ by volume of methyl methacrylate (MMA) 15 as taught in thi~ in~ention can absorb water or hydrate up to about 26% of ~ts weight, wherea~ the hard len~ material, PI~MA, and the copolymer with the composition of 25~ of Sil and 75 of MMA as taught in the above mentioned patent can only be hydrated, up to about 0,5% of the weight. I~ the wettability 20 of the copolymar i8 improved by the addition of up to about ` 10% o~ hydrophilic HEMA in the comonomeric mixture a~ de3cr~b-ed in Examples 3-9 of the Gaylord patent~ the h~aration of the material prepared tharefrom i~ also only abou~ 1~, The cone rubber is e~sentially hydrophobic.
In additio~, the novel copolymer~ taught in this invention have va~tly increaæed ~o~tness after hydration.
For example, in the above mentioned exampl~ before hydration the hardness of the material taught in this invention i~ at about ~5 as measured by Portable Hardness Te~ter, Mod~l GYZJ
30 936, Barber-Colman Co., Ill., but after fully hydrated, it becomè~ about 15~ wherea~ the others ~till keep at about original value, PMMA at about 93 and the other~ at about 80.
Generally the degree o~ aoftness o~ the copolymer after hydra-tion in thia invention depends on the degreo of it~ hydrophi-~5 licity, The higher tho content o~ the hydrophilic comonomer inthe copolymer? the higher the degree of its hydrophilici~y and - the ~ofter the lens ~8 a~ter hydration, Xn the practice of thi~ ~nvention i~ ~ pre~cr~e~ to ~elec~ the copolymer wl~h . ..
. : ~, .: ' - .:
' , ., ~ 11~
~ .
percent of hydration between abo~ 8 -to about 35%
Furthermore, the novel copolymers have also vastly increased ga~ permeability in comparison to conventional contact lens materials, PM~,rand soft lens material, poly HE~, For example, a copolymer comprising 30 parts by volume of N-vinyl pyrrolidone, 50 parts o~ Sil and 20 parts of MMA
has an oxygen permeabili~y of ab~u~ 1~600 c.c,-mil/100 in2/
24 hrs/atm compared to an oxygen permeability o~ about 30 for P~ and ab~ 15 ~or Poly HEMA a~ described in t~ Gaylord patent, The oxygen permeability values o~ the Gaylord copo-lymers illustrated in the examples of the Caylord patent are between 300 and 5OO units only. These oxygen permeability values were determined in accordance with ASTM D1434. The substantially increased oxygen permeabllity o~ the composi-tions of thi~ invention could be due to the synergi~ticeffect of the component~ u~ed~
In the practice of this invention in contact lens area, the r~ractive index i8 an important but noncritical charac~eristic, ThUs, the refracti~e index o~ polyme~hyl ;. 20 methacrylate, the polymer most widely used in the fæbrication ` of hard contact lenses 9 i~ 1,49, The refractive ind~ces of the copolymers use~ul in the practice o~ th~s invention in the fabrication of contact lenses are pre~erably selec~ed between about 1,~ and about 1,5 which maybe ~aried by chang-ing the ratio and nature of the comonomers uæed.
BRIEF DESCRIPTION OF TXE DRAWING
ThR difference between the hydrophilic properties o~ the copolymers of this in~ention and those o~ ~he closest pr~or art, the Gaylord copolymer~9 will become ev~n further apparent upon ~he considera~1on of the ~ollowing disclosure o~ this invention, particularly when taken in con~unction with the accompanying drawin~7 Fig. I~ wherein th~ variation of hydrophilic properties of the copolymer~ are illustrated with respect to th~ percenta~e change by ~olume o~ the hydrophilic monomers used in the comonomeric mixture, Cur~e A i~ the present inventions B is the prior art~ and C i~ the prior art pro~ection, when HEMA related monomer~ are u~Qd.
.
- . : . , :
,, 12. ~ 9~
The following examples are presented to illustrate the practice of the invention and not as an indication of the limits of the scope thereof.
EXAMPLE I
This example illustrates some general procedures to synthesize the copolymeric organosiloxaneqi that are suit-able for the practice of this invention by the methods wellknown in the art.
Organosilicon.Compounds .1 and 2 (Sil) and (i~i2) The synthesis procedures of these compounds are essentially the same as that described in Example 15, U.S.
patent No. 3,808,178, except ~Methacrylatopropyltrimethoxysi-lane" should read "~-Methacryl~ypropyltrimethoxysilane", the upper oily layer is washed with water until neutral and the produce is distilled under high vacuum to remove methyl acetate, or other impurities.
,, ` ~ :' ', ~: , :` : ;' ', ' :
13.
The procedure described above can also be used to synthesize other corresponding organosilicon compounds, if trimethyl acetoxysilane used in the reaction is replaced by the other desired acetoxy siloxane, such as pentamethyl ace-toxydisiloxane, heptamethyl acetoxy trisiloxane and the like.
Apparently, the higher the numberof silicon in the acetoxy-siloxane used, the higher the vacuum and the higher the temperature of water bath, such as 80 or 90~C under high vacuum should be used in order to distill out the impurities.
When pentamethyl acetoxydisiloxane is used in the reaction, the copolymeric organosilicon compound thus prepared is called Si2.
Org'anosil'icon Compound 3 (Si3) The synthesis procedure of methacryloxymethylpenta-methyldisiloxane (Si3~ is fully described in Example 1 of U.S. Patent No. 2,956,044 and Example 1 of U. S. Patent No.
3,808,178.
Some Other Organo's'i'licon'COmpounds~ Si4, Si5 t Si5 etc-The detailed procedures to synthesize these compounds are fully described in Examples 2, 3, 4 and 5 of U. S. Patent No. 2,956,044.
'EXAMPLES''2'-9 The examples illustrate the preparations and proper-ties of the copolymers containing varying proportions of heterocyclic amide group containing monomer, e.g., N-vinyl-2-pyrrolidone (VP), the first type of organosilicon compounds, with or without MMA and crosslinking monomers, e.g., tetraethylene glycol dimethacrylate (TEGDM~. Furthermore, they also illustrate that a prosthetic device can directly be made from copolymerizing the composition mixture in a mold with a desired configuration.
The mixture of VP, Sil or Si2 with or without MMA, crosslinking agent, TEGDM, and with t-butyl peroxypivalate (t-BPP) (about 0.004 ml per ml of monomer mixture), after flushing nitrogen through the reaction mixture for 30 minutes, ,~
, . I ,' I ! ' , lL~, " ~ 38 was polymerized in a glass tube at 50~C for about 48 hour~, followed by placing at 100C oil bath for another 24 hrs.
After the tube was broken, they were all in the forms of rods.
The composi~ion and properties of the copolymers are collected in thefollowing table As indicated, all the rods are either transparent or opaque~ hard and rigid before hydration which can be cut, machined, polished and finished to contact len~es or other prosthetic devices by the techniques well known in the art. The material should have increased softness after hydration and increased oxygen permeability.
Com~osition, Vol Percent Example YP Sil Si2 ~ TEGDM Properties ~ ........ ~ .
2 33 67 0 0 H, T, R
3 50 50 0 0 H, Op., R
4 45 25 30 0 H, T, R
40 50 10 0 H, T, R
6 3Q ~0 20 0 H, T) R
- 7 20 50 30 0 H, T~ R
8 30 50 15 5 H, T, R
; 20 9 35 35 3 H, T, R
. .
Properties before hydration~ H = hard~ T = trans-parent: Op - opaque~ and R = rigid The examples illustrate the hydrophilic properties f the novel copolymers.
A small piece of sample (about 0 1 cm width~ was cut ~rom the cylindrical rod prepared in the abo~a examples, followed by immerslng in water for-about 18 hours. The hydro-- philicity is expressed as percent of hydration which can be calculated by the following formulal ~ Hydration = ~W X 100 wherein ~W is the weight differenca of the sample after and before hydration and Wt is the weight of the sample be~ore hydra~ on. The app~oximats ~alue of the percent hydration o~
the cop~lymer i8 collected in the Table below ` !
;~
' .
15~ 3~
. ~
~ ;
_ Æxample ~ Sample #a ~OHydration_ 12 ~ 5 ` 14 13_ 6 8 b 0.5 16 - c aThe number indicates the Example number from which the sample was prepared.
bThe sample being prepared from the copolymar of 50~ by weight o~ Sil and 50% of MMA as taught in the patent to Gaylord, U. S. Patent NoO 3,808,178, CThe sample was prepared from the copolymer o~ 50~ by waight of Sil, 39% of MMA and 11% Or HEMA. ~he HEMA
was used to lmprove the wettability Or the copolymer as taught in the Gaylord patent.
;` Th~s example illustrate~ the increased ~o~tnes~
o~ the copolymers after hydration in this invention.
The hardness of the copolymer prepared in Example 4 before hydratlon i3 about 72 a~ measured by the portable hardncss ~ester, Model GYZ~ 936~ Barb~r-Colman Co.,~Ill.~
after hydration, ~t i8 abou~ lS~ wher~as ~he hardnes~ of hard ~5 lens material, PMMA, before hydration ~ about 90~ after hydra-tion it is still at about 90. ~he hardne~ of the copolymer containing the corre8ponding composition with that prepared in Exampie 4, i.e., 25~ of Sil and 75~ o~ MMA by volume as taught in U. S, Patent No. 3,808,178, be~ore hydration i8 about 80 after hydrat~on it i~ still at about 80, This example illustrates ~he gas p~rmeability of the copolymers in thi~ invention.
The oxygen permeability of the copol~er prepared in Exampl~ 6 i8 about 1~ 60~ ~, ¢ ~ ~m~l/100 itl2/~4 hrY/atm. in compa~ son to about 35 ~or hard len~ mater~al, PMMA, and about 15 for soft len8 matsrial, Poly HEMA, whlch are dc~cribed in 1 , - , ,,, ~
16. ~
,_ the Gaylord patent. The oxygen permeabilities of the copo-lymers illustrated in the Examples of the Gaylord patent are between 300 and 500 units only. ~hese oxygen permeability values were determined in accordance with ASTM D1434.
_ ..
These examples illustrate the preparations and properties of the copolymers containing different types of organosilicon compounds, e.g., Sil and Si2, and different types of the amide group containing monomers with heterocyclic and noncyclic structures, e.g., VP, N,N-dimethyl methacryl-amide (NNMA) and N,N-dimethylacrylamide (NNAA~.
The cyclindrical rods can be prepared from the comonomeric mixture as listed in the following table:
Compositi~n, ~ol. Percent Example # NNMA NNAA VP Sil 2 _ The copolymers thus prepared can be used in the practice of this invention.
Obviously many other modifications and variations 3Q of the composition of this novel copolymer prepared therefrom, are possible in light of the teachings given hereinabove.
It is, therefore, to be understood that, within the scope of the appended claims, the invention can be practiced other-wise than as specifically described.
!`~ `
. .. , ~. . .... ~ ~ . .. .
... . ~ .. . : . .
. ` . . ... ..
, ' . ' ' " ; ' ., ''., ' ' ~ ' ' . , " , ., , .. , ' . ' ,,
; 20 9 35 35 3 H, T, R
. .
Properties before hydration~ H = hard~ T = trans-parent: Op - opaque~ and R = rigid The examples illustrate the hydrophilic properties f the novel copolymers.
A small piece of sample (about 0 1 cm width~ was cut ~rom the cylindrical rod prepared in the abo~a examples, followed by immerslng in water for-about 18 hours. The hydro-- philicity is expressed as percent of hydration which can be calculated by the following formulal ~ Hydration = ~W X 100 wherein ~W is the weight differenca of the sample after and before hydration and Wt is the weight of the sample be~ore hydra~ on. The app~oximats ~alue of the percent hydration o~
the cop~lymer i8 collected in the Table below ` !
;~
' .
15~ 3~
. ~
~ ;
_ Æxample ~ Sample #a ~OHydration_ 12 ~ 5 ` 14 13_ 6 8 b 0.5 16 - c aThe number indicates the Example number from which the sample was prepared.
bThe sample being prepared from the copolymar of 50~ by weight o~ Sil and 50% of MMA as taught in the patent to Gaylord, U. S. Patent NoO 3,808,178, CThe sample was prepared from the copolymer o~ 50~ by waight of Sil, 39% of MMA and 11% Or HEMA. ~he HEMA
was used to lmprove the wettability Or the copolymer as taught in the Gaylord patent.
;` Th~s example illustrate~ the increased ~o~tnes~
o~ the copolymers after hydration in this invention.
The hardness of the copolymer prepared in Example 4 before hydratlon i3 about 72 a~ measured by the portable hardncss ~ester, Model GYZ~ 936~ Barb~r-Colman Co.,~Ill.~
after hydration, ~t i8 abou~ lS~ wher~as ~he hardnes~ of hard ~5 lens material, PMMA, before hydration ~ about 90~ after hydra-tion it is still at about 90. ~he hardne~ of the copolymer containing the corre8ponding composition with that prepared in Exampie 4, i.e., 25~ of Sil and 75~ o~ MMA by volume as taught in U. S, Patent No. 3,808,178, be~ore hydration i8 about 80 after hydrat~on it i~ still at about 80, This example illustrates ~he gas p~rmeability of the copolymers in thi~ invention.
The oxygen permeability of the copol~er prepared in Exampl~ 6 i8 about 1~ 60~ ~, ¢ ~ ~m~l/100 itl2/~4 hrY/atm. in compa~ son to about 35 ~or hard len~ mater~al, PMMA, and about 15 for soft len8 matsrial, Poly HEMA, whlch are dc~cribed in 1 , - , ,,, ~
16. ~
,_ the Gaylord patent. The oxygen permeabilities of the copo-lymers illustrated in the Examples of the Gaylord patent are between 300 and 500 units only. ~hese oxygen permeability values were determined in accordance with ASTM D1434.
_ ..
These examples illustrate the preparations and properties of the copolymers containing different types of organosilicon compounds, e.g., Sil and Si2, and different types of the amide group containing monomers with heterocyclic and noncyclic structures, e.g., VP, N,N-dimethyl methacryl-amide (NNMA) and N,N-dimethylacrylamide (NNAA~.
The cyclindrical rods can be prepared from the comonomeric mixture as listed in the following table:
Compositi~n, ~ol. Percent Example # NNMA NNAA VP Sil 2 _ The copolymers thus prepared can be used in the practice of this invention.
Obviously many other modifications and variations 3Q of the composition of this novel copolymer prepared therefrom, are possible in light of the teachings given hereinabove.
It is, therefore, to be understood that, within the scope of the appended claims, the invention can be practiced other-wise than as specifically described.
!`~ `
. .. , ~. . .... ~ ~ . .. .
... . ~ .. . : . .
. ` . . ... ..
, ' . ' ' " ; ' ., ''., ' ' ~ ' ' . , " , ., , .. , ' . ' ,,
Claims (14)
1. A composition of matter specially adapted for use as a prosthetic device having the characteristics of increased hydrophilicity, softness after hydration and oxygen permeability, said composition being a copolymer of comonomers consisting essentially of:
(A) about 15 to about 65% by weight of at least one amide group containing monomer being selected from a group consisting essentially of:
(a) heterocyclic amide group containing monomers consisting essentially of:
(1) N-(olefin containing group)-2-pyrrolidone, (2) N-(olefin containing group)-2-piperidone, (3) N-(olefin containing group)-2-imidazolidone, and (4) N-(olefin containing group) succinimide, wherein said olefin containing group is selected from a group consisting essentially of vinyl, acryloxy, methacryloxy, acrylato-alkyl, methacrylatoalkvl, acrylamidoalkyl and methacrylamidoalkyl groups, wherein the alkyl group contains from one to 4 carbon atoms, and (b) noncyclic amide group containing monomers consist-ing essentially of N-alkyl acrylamide, N-alkyl methacrylamide, N,N-dialkyl acrylamide and N,N-dialkyl methacrylamide, wherein the alkyl group is individually selected from a group consisting of unsubstituted and substituted monovalent hydrocarbon radicals having from one to 6 carbon atoms, and (B) about 10 to about 75% by weight of at least one organosilicon compound, wherein the essential consti-tuent units of each molecular compound have the formulas:
M, and N, wherein the molar ratio of M to N is within a range of from about 1 to 99 to about 99 to 1;
R is selected from a group consisting of hydrogen and methyl group; R' and R", which may be the same or different, are monovalent hydrocarbon groups selected from a group consisting of C1-C4 alkyl groups, cyclohexyl groups and phenyl groups; n is an integer of from one to four inclusive; a is an integer of from 0 to 2 inclusive and b is an integer of from zero to three inclusive.
(A) about 15 to about 65% by weight of at least one amide group containing monomer being selected from a group consisting essentially of:
(a) heterocyclic amide group containing monomers consisting essentially of:
(1) N-(olefin containing group)-2-pyrrolidone, (2) N-(olefin containing group)-2-piperidone, (3) N-(olefin containing group)-2-imidazolidone, and (4) N-(olefin containing group) succinimide, wherein said olefin containing group is selected from a group consisting essentially of vinyl, acryloxy, methacryloxy, acrylato-alkyl, methacrylatoalkvl, acrylamidoalkyl and methacrylamidoalkyl groups, wherein the alkyl group contains from one to 4 carbon atoms, and (b) noncyclic amide group containing monomers consist-ing essentially of N-alkyl acrylamide, N-alkyl methacrylamide, N,N-dialkyl acrylamide and N,N-dialkyl methacrylamide, wherein the alkyl group is individually selected from a group consisting of unsubstituted and substituted monovalent hydrocarbon radicals having from one to 6 carbon atoms, and (B) about 10 to about 75% by weight of at least one organosilicon compound, wherein the essential consti-tuent units of each molecular compound have the formulas:
M, and N, wherein the molar ratio of M to N is within a range of from about 1 to 99 to about 99 to 1;
R is selected from a group consisting of hydrogen and methyl group; R' and R", which may be the same or different, are monovalent hydrocarbon groups selected from a group consisting of C1-C4 alkyl groups, cyclohexyl groups and phenyl groups; n is an integer of from one to four inclusive; a is an integer of from 0 to 2 inclusive and b is an integer of from zero to three inclusive.
2. The composition of Claim 1, wherein said amide group contain-ing monomer being selected from a group consisting essential-ly of N-vinyl-2-pyrrolidone, N-(2'-methacrylatoethyl)-2-pyrrolidone, N-vinyl-2-piperidone, N-(2'-methacrylatoethyl)-2-piperidone, N-alkyl acrylamide, N-alkyl methacrylamide, N, N-dialkyl acrylamide, N,N-dialkyl methacrylamide and mixture thereof.
3. The composition of Claim 1, wherein there is about 20 to about 55% by weight of at least one amide group containing monomer and about 20 to about 55% by weight of at least one organosili-con compound.
4. The composition of Claim 3, wherein said prosthetic device is a contact lens device.
5. The composition of Claim 4, wherein there is about 25 to about 45 parts by weight of at least one amide group contain-ing monomer.
6. The compositon of Claim 5, wherein said amide group containing monomer is N-vinyl-2-pyrrolidone.
7. The composition of Claim 5, wherein said amide group containing monomer is N-(2'-methacrylatoethyl)-2-pyrroli-done.
8. The composition of Claim 5, wherein said amide group containing monomer is N,N-dimethyl methacrylamide.
9. A composition of matter specially adapted for use as a prosthetic device having the characteristics of increased hydrophilicity, softness after hydration and oxygen permeabili-ty, said composition being a copolymer of comonomers consist-ing essentially of:
(A) about 15 to about 65% by weight of at least one amide group containing monomer being selected from a group consisting essentially of:
(a) heterocyclic amide group containing monomers consisting essentially of:
(1) N-(olefin containing group)-2-pyrrolidone, (2) N-(olefin containing group)-2-piperidone, (3) N-(olefin containing group)-2-imidazolidone, and (4) N-(olefin containing group) succinimide, wherein said olefin containing group is selected from a group consisting essentially of vinyl, acryloxy, methacryloxy, acrylatoalkyl, methacryla-toalkyl, acrylamidoalkyl and methacrylamidoalkyl groups, wherein the alkyl group contains from one to 4 carbon atoms, and (b) noncyclic amid group containing monomers consisting essentially of N-alkyl acrylamide, N-alkyl methacrylamide, N,N-dialkylacrylamide and N,N-dialkylmethacrylamide, wherein the alkyl group is individually selected from a group consisting of unsubstituted and substituted monovalent hydrocarbon radicals having from one to 6 carbon atoms;
(B) about 10 to about 75% by weight of at least one organo-silicon compound, wherein the essential constituent units of each molecular compound have the formulas:
M, and N, wherein the molar ratio of M to N is within a range of from about 1 to 99 to about 99 to 1; R is selected from a group consisting of hydrogen and methyl group;
R' and R", which may be the same or different, are monovalent hydrocarbon groups selected from a group consisting of C1-C4 alkyl groups, cyclohexyl groups and phenyl groups; n is an integer of from one to four inclusive; a is an integer of from 0 to 2 inclusive and b is an integer of from zero to three inclusive; and (C) about 0.1 to about 65% by weight of at least one ester of a C1-C20 alkanol and an acid selected from a group consisting of acrylic and methacrylic acids.
(A) about 15 to about 65% by weight of at least one amide group containing monomer being selected from a group consisting essentially of:
(a) heterocyclic amide group containing monomers consisting essentially of:
(1) N-(olefin containing group)-2-pyrrolidone, (2) N-(olefin containing group)-2-piperidone, (3) N-(olefin containing group)-2-imidazolidone, and (4) N-(olefin containing group) succinimide, wherein said olefin containing group is selected from a group consisting essentially of vinyl, acryloxy, methacryloxy, acrylatoalkyl, methacryla-toalkyl, acrylamidoalkyl and methacrylamidoalkyl groups, wherein the alkyl group contains from one to 4 carbon atoms, and (b) noncyclic amid group containing monomers consisting essentially of N-alkyl acrylamide, N-alkyl methacrylamide, N,N-dialkylacrylamide and N,N-dialkylmethacrylamide, wherein the alkyl group is individually selected from a group consisting of unsubstituted and substituted monovalent hydrocarbon radicals having from one to 6 carbon atoms;
(B) about 10 to about 75% by weight of at least one organo-silicon compound, wherein the essential constituent units of each molecular compound have the formulas:
M, and N, wherein the molar ratio of M to N is within a range of from about 1 to 99 to about 99 to 1; R is selected from a group consisting of hydrogen and methyl group;
R' and R", which may be the same or different, are monovalent hydrocarbon groups selected from a group consisting of C1-C4 alkyl groups, cyclohexyl groups and phenyl groups; n is an integer of from one to four inclusive; a is an integer of from 0 to 2 inclusive and b is an integer of from zero to three inclusive; and (C) about 0.1 to about 65% by weight of at least one ester of a C1-C20 alkanol and an acid selected from a group consisting of acrylic and methacrylic acids.
10. The composition of Claim 9, wherein there is about 20 to about 55% by weight of at least one amide group containing monomer and about 20 to about 55% by weight of at least one organosilicon compound, the said amide group containing monomer is selected from a group consisking essentially of N-vinyl-2-pyrrolidone, N-(2'-methacrylatoethyl)-2-pyrrolidone, N-vinyl-2-piperidone, N-alkyl acrylamide, N-alkyl methacryla-mide, N,N-dialkyl acrylamide, N,N-dialkyl methacrylamide and mixture thereof.
11. A composition of matter specially adapted for use as a contact lens device having the characteristics of increased hydrophilicity, softness after hydration and oxygen permeability, said composition being a copolymer of comonomers consisting essentially of:
(A) about 20 to about 45% by weight of at least one amide group containing monomer being selected from a group consisting essentially of M-vinyl-2-pyrrolidone, M-(2'-methacrylato-ethyl)-2-pyrrolidone, N-methyl acrylamide, N-methyl metha-crylamic.e, N,N-dimethyl acrylamide and N,N-dimethyl methacrylamide;
(B) about 10 to about 50% by weight of at least one organosilicon compound, wherein the essential constituent units of each molecular compound have the formulas:
M, and N, wherein the molar ratio of M to N is within a range of about 1 to 99 to about 99 to 1; R is selected from a group consisting of hydrogen and methyl group; R' and R", which may be the same or different, are monovalent hydrocarbon groups selected from a group con-sisting of C1-C4 alkyl groups, cyclohexyl groups and phenyl groups; n is an integer of from one to four inclusive; a is an integer of from 0 to 2 inclusive and b is an integer of from zero to three inclusive; and (C) 0 to about 35% by weight of at least one ester of a C1-C20 alkanol and an acid selected from a group consisting of acrylic and methacrylic acids.
(A) about 20 to about 45% by weight of at least one amide group containing monomer being selected from a group consisting essentially of M-vinyl-2-pyrrolidone, M-(2'-methacrylato-ethyl)-2-pyrrolidone, N-methyl acrylamide, N-methyl metha-crylamic.e, N,N-dimethyl acrylamide and N,N-dimethyl methacrylamide;
(B) about 10 to about 50% by weight of at least one organosilicon compound, wherein the essential constituent units of each molecular compound have the formulas:
M, and N, wherein the molar ratio of M to N is within a range of about 1 to 99 to about 99 to 1; R is selected from a group consisting of hydrogen and methyl group; R' and R", which may be the same or different, are monovalent hydrocarbon groups selected from a group con-sisting of C1-C4 alkyl groups, cyclohexyl groups and phenyl groups; n is an integer of from one to four inclusive; a is an integer of from 0 to 2 inclusive and b is an integer of from zero to three inclusive; and (C) 0 to about 35% by weight of at least one ester of a C1-C20 alkanol and an acid selected from a group consisting of acrylic and methacrylic acids.
12. The composition of Claim 1, 9 or 11, wherein said organosilicon compound is prepared from the reaction of ?-methacryloxypropyltrimethoxysilane with trimethylacetoxy-silane, pentamethylacetoxydisiloxane or heptamethylace-toxytrisiloxane.
13. A composition of Claim 1, 9 or 11, wherein said copolymer of comonomers comprises:
(1) ?-methacryloxypropyltrimethoxysilane;
(2) trimethylacetoxysilane, pentamethylacetoxyd.isiloxane, or heptamethylacetoxytrisiloxane; and (3) N-vinyl-2-pyrrolidone, N,M-dimethylmethacrylamide, or N,N-dimethylacrylamide.
(1) ?-methacryloxypropyltrimethoxysilane;
(2) trimethylacetoxysilane, pentamethylacetoxyd.isiloxane, or heptamethylacetoxytrisiloxane; and (3) N-vinyl-2-pyrrolidone, N,M-dimethylmethacrylamide, or N,N-dimethylacrylamide.
14. A composition of Claim 1, 9 or 11, wherein said copolymer of comonomers comprises:
(1) ?-methacryloxypropyltrimethoxysilane;
(2) trimethylacetoxysilane, pentamethylacetoxydisiloxane;
or heptamethylacetoxytrisiloxane;
(3) N-vinyl-2-pyrrolidone, N,N-dimethylmethacrylamide, or N,N-dimethylacrylamide; and (4) methyl methacrylate.
(1) ?-methacryloxypropyltrimethoxysilane;
(2) trimethylacetoxysilane, pentamethylacetoxydisiloxane;
or heptamethylacetoxytrisiloxane;
(3) N-vinyl-2-pyrrolidone, N,N-dimethylmethacrylamide, or N,N-dimethylacrylamide; and (4) methyl methacrylate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/925,640 US4343927A (en) | 1976-11-08 | 1978-07-17 | Hydrophilic, soft and oxygen permeable copolymer compositions |
| US925,640 | 1986-10-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1118938A true CA1118938A (en) | 1982-02-23 |
Family
ID=25452020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000331869A Expired CA1118938A (en) | 1978-07-17 | 1979-07-16 | Hydrophilic, soft and oxygen permeable copolymer compositions |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4343927A (en) |
| EP (1) | EP0016138B1 (en) |
| JP (1) | JPS646215B2 (en) |
| AT (1) | ATE5260T1 (en) |
| CA (1) | CA1118938A (en) |
| DE (1) | DE2966386D1 (en) |
| WO (1) | WO1980000253A1 (en) |
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| US3004950A (en) * | 1958-12-05 | 1961-10-17 | Dow Chemical Co | Copolymers of certain organosilicon monomers and n-vinyl cyclic carbamates |
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| US3808178A (en) * | 1972-06-16 | 1974-04-30 | Polycon Laboratories | Oxygen-permeable contact lens composition,methods and article of manufacture |
| CA1011019A (en) * | 1973-04-04 | 1977-05-24 | Herman S. Schultz | Hydrophilic copolymer of n,n-(c1-c2alkyl) acrylamide |
| US3937680A (en) * | 1973-05-29 | 1976-02-10 | Global Vision, Inc. | Hydrophilic gel terpolymers from hydrophilic n-vinyl monomers, hydroxyalkyl acrylates or methacrylates and polymerizable unsaturated carboxylic acids |
| NZ177276A (en) * | 1974-05-06 | 1978-04-03 | Bausch & Lomb | Separated interpenetrating hydrophilic and hydrophobic polymeric network: contact lens |
| US4099859A (en) * | 1974-12-02 | 1978-07-11 | High Voltage Engineering Corporation | Contact lens having a smooth surface layer of a hydrophilic polymer |
| JPS5916324B2 (en) * | 1975-09-08 | 1984-04-14 | アソシエイテツド・ペ−パ−・インダストリ−ズ・リミテツド | Antistatic turntable mat for record player |
| 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 |
| US4153641A (en) * | 1977-07-25 | 1979-05-08 | Bausch & Lomb Incorporated | Polysiloxane composition and contact lens |
| JPS5455455A (en) * | 1977-10-12 | 1979-05-02 | Toyo Contact Lens Co Ltd | Contact lens |
| JPS5466853A (en) * | 1977-11-08 | 1979-05-29 | Toyo Contact Lens Co Ltd | Soft contact lens |
| US4138382A (en) * | 1978-05-01 | 1979-02-06 | Dow Corning Corporation | Hydrophilic, water-swellable, crosslinked, copolymer gel and prosthesis employing same |
-
1978
- 1978-07-17 US US05/925,640 patent/US4343927A/en not_active Expired - Lifetime
-
1979
- 1979-06-14 JP JP54501186A patent/JPS646215B2/ja not_active Expired
- 1979-06-14 WO PCT/US1979/000441 patent/WO1980000253A1/en unknown
- 1979-06-14 DE DE7979900856T patent/DE2966386D1/en not_active Expired
- 1979-06-14 AT AT79900856T patent/ATE5260T1/en not_active IP Right Cessation
- 1979-07-16 CA CA000331869A patent/CA1118938A/en not_active Expired
-
1980
- 1980-02-25 EP EP79900856A patent/EP0016138B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0016138B1 (en) | 1983-11-09 |
| JPS646215B2 (en) | 1989-02-02 |
| ATE5260T1 (en) | 1983-11-15 |
| EP0016138A4 (en) | 1980-11-28 |
| WO1980000253A1 (en) | 1980-02-21 |
| JPS55500418A (en) | 1980-07-10 |
| DE2966386D1 (en) | 1983-12-15 |
| US4343927A (en) | 1982-08-10 |
| EP0016138A1 (en) | 1980-10-01 |
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