CA1310788C - Hydrophilic oxygen permeable polymers - Google Patents

Hydrophilic oxygen permeable polymers

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Publication number
CA1310788C
CA1310788C CA000588088A CA588088A CA1310788C CA 1310788 C CA1310788 C CA 1310788C CA 000588088 A CA000588088 A CA 000588088A CA 588088 A CA588088 A CA 588088A CA 1310788 C CA1310788 C CA 1310788C
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Prior art keywords
weight percent
methacrylate
carbon atoms
composition
acrylate
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Expired - Lifetime
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CA000588088A
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French (fr)
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Ronald E. Bambury
Dong Joon Choo
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Bausch and Lomb Inc
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Bausch and Lomb Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/36—One oxygen atom
    • C07D263/42—One oxygen atom attached in position 5
    • 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
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • 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
    • 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

ABSTRACT OF THE DISCLOSURE Polymeric materials comprising novel wetting agents such as 2-isopropenyl-4,4-dimethyl-2-oxazolin-5-one, 2-vinyl-4,4-dimethyl-2-oxazolin-5-one, and the like.

Description

07~
HYDROPHILIC QXYGEN PERMEABLE POLYMERS

TITLE

Field Qf Invention This in~ention relates to polymeric materials useful in biomedical devices, especially contact lenses, which are the product of reac~ing mixture comprising o~azolones.

Back~round A number of types of polymeric materials are known to be useful in con~act lens manufacture. In general contact lens 1~ materials can be thought to fall into one of the following classifications: soft hydrophilic, soft, non-hydrophilic, and a more recent development, hard gas permeable. Gas permeable ma~ials typically comprise polymeric materials formed by ~op~l~merizing polyorganosilosane monomers with various other 1~ monomers. These polymeric materials possess high o~ygen permeabilities which make them particularly attractive as contact lens materials. In general, they are not as hydrophilic as the soft hydrophilic materials, and thus they are not as easily ~wetted~. These soft, non-hydrogels are illustrated by the following patents:
U.S. Patent No. 4,153,641 disclosas acrylate functional ~ldcapped polyorganosilo~anes which can be polymerized to form high oxygen permeable polymeric networks, or which can be ~op~lymerized with other monomers to form high oxygen permeable copolymers. Specific comonomers disclosed include low esters o~ acrylic acid, a methacrylic acid, styryls and N-vlnyl Qyrrolidinone.
U~S~ Patent No. 4,208,506 discloses soft contact lenses m~de rom polymers and copolymers comprising polyparaffinsilo~ane polymers and copolymers formed by polymerizing a polyparaffinsilosane monomer alpha, o~ega ta~minally bonded through divalent hydrocarbon groups to pol~merized, free radical polymerizably activated, unsaturated groups forming a polymer in a crosslinked netwo~k.
3~ Additionally, specific comonomers are disclosed which include lower esters of acrylic and methacrylic acid, styryls and 1 3 1 07~3 N-vinyl pyrro1iainone which may be copolymerized with the above-described polypara~finsilo~ane monomer to form a copolymer.
U.S~ Patent No. 4~3~ 72 discloses polysiloxanyl alkyl ~sters of acrylic and methacrylic acids and its copolymerization with alkyl esters of acrylic, methacrylic acids and~or itaconat~ esters to produce highly permeable contact lens material. The copolymer preferably includes a crosslin~ing agent and hydrophilic monomer. Contact lenses manufactured from the material are easily machined and polished into hard or semi-hard contact lenses having e~cellent dimensional stability.
U.S. patent No. 4,330,383 discloses improved contact lens materials are obtained from copolymers containing a siloxanyl alkyl ester vinyl monomer by esposing the materials to high energy radiation thereby reducing the amount of unreacted monomer and residual contaminants.
U.S. Patent No. 4,327,203 discloses articles for biomedical applications made from a polymer formed by polymerizing (a) one or more polysiloxane monomers alpha, omega terminally bonded thro~yh divalent hydrocarbon groups to an activated, unsaturated group with (b) a cycloalkyl modulus modifier, e.g.
tertiary butylcyclohesyl methacrylate, menthyl acrylate or methylisopentyl cyclooctyl acrylate, and (c~ a tear film stabilizer. The products are useful as hard contact lenses.
U.S. Patent ~o. 4,341,889 discloses the modulus modifier above can be tertiary butyl styrene. U.S. Patent No. 4,355,147 discloses the modulus modiier above can be a polycyclic acrylate or methacrylate such as isobornyl methacrylate, 3a adamantyl acrylate or isopinocamphyl methacrylate.
U.S. Patent ~o. 4,652,622 discloses polymeric materials comprised o~ mo~omeric polysilo~anes end capped with activated unsaturated groups, a modulus modi~ier and small amounts of an internal w~tting agent such as N-alkenoyltrialkylsilyl aminate.

1 3 1 07~

Detailed DescriRtion of the Invention The invention relates to polymeric materials which are particularly useful in contact lenses formed by polymerizing a misture comprising:
a compound represented ~y the general formula ,~
Rl N \ ~ o R3 ~ R4 where Rl and R2 independently denote a hydrogen atom or a lower alkyl radical with one to si~ carbon atoms, and R3 and R4 independently denote alkyl radicals with one to six carbon atoms or a cycloalkyl radical with 5 or 6 carbon atoms.

1~ Speci~ic e~amples of these compounds include 2-isopropenyl-4,4-dimethyl-~~o~a~olin-5-one (IPDMO), ~-vinyl-4,4-dimethyl-2-oxazolin-5-one (VDMO~, spiro-4'-(~' isopropenyl-2'-o~azolin-5-one~ cyclohexane (IPCO), cyclohe~ane-spiro~4'-(2' Vinyl-2' o~azol-5'-one) (VCO), and 1~ 2-(-1-propenyl)-4,4-dimethyl-o~azol-5-one (PDMO~.
These compounds have two important features which make them par~icularly preferred comonomers with acrylate or methacrylate ~unctional pol~silo~ane monomers: (1) They are relatively nonpolar and ara thus highly compatible with polysilo~ane ~a mon~m~rs thus forming optically clear monomer mi~tures and polymers, and ~2~ They are converted to highly polar amino acids upon mild hydrolysis. Thus they can be copolymerized into a hydrophobic polymeric matris and then hydrolyzed to render the matri~ substantially hydrophilic.

13tO7~

These compounds are prepared by the general reaction sequence:

J\
O R3 R9 NaOH R2 \/ \j3 R2 ~/ Cl + H2N COOH H~0 J t Rl 0C Rl COOH
~I~ (II) Il \
Cl COC2Hs ~ o Hexane Rl ~ ~ O
/\

The first step being a Shotten-Bauman acylation of an amino acid. The polymerizable functionality is introduced by using either acryloyl or methacryloyl chloride. The second step ~nvolves a ring closure with a chloroformate to yield the desired osazalone. The product is isolated and purified by the usual procadures o organic chemistry.
The compounds can be copolymerized with hydrophobic 1~ polysilo~ane monomers to form polymeric materials which have hlyh o~ygen permea~ilities~ Th~se polymeric materials may then be hydrolyzed in order to convert the o~azolone components into 1 3 1 07()~3 amino acids. In general, the hydrolysis step will follow the general reaction of:

R2 R2 o ~ H+ ~
Rl N ~Lo + H20 ~ Rl NH O
~ or O~~ ll R3 R4 R3 ~ ~ OH

This reaction occurs mainly on the surface of the polymeric material and renders said surface hydrophilic. This hydrophilic surface is substantive due to the fact that the polymer network has been previously reacted with the carbon-carbon double bond between the Rl and R~ radicals (the schematic reaction above shows the double bond unreacted).
Thus the above compounds can be referred to as wetting agents.
1~ These wetting agents are far superior to state of the art internal wetting agents by virtue of their mis~bility with polysilo~ane monomers. Thus, they can be copolymerized in greater proportion than the state of the art wetting agents yielding materials which have hydrophilic surfaces.
1~ Particularly useful hydrophobic monomers which can be copolymerized with the above wetting agents are acrylate or methacrylate functional endcapped polysiloxanes represented by the general formula:
~ CN2 -- --t 1i o ~ (CH2 Y
- R6 ~ m 1 3 1 07~3 Where A denotes an acrylate or methacrylate radical, R5 and R6 independently denote alkyl radicals with one to si~ carbon atoms or phenyl radicals, ~ and y are on the averag~ one to si~, and m is at least one. In general the oxygen permeability o.f the copolymers will increase as the degree of polymerization of the polysilo~ane monomer increases. However, as the degree of polymerization of the monomer increases, the copolymeric matri~ will become more elastomeric. Toughening agents can be added to the prepolymerization mi~ture to add strength to the 1~ polymeric material.
Toughening agents are selected from the group comprising tertiary butyl styrene, cycloalkyl toughening agents, ~luorinated methacrylate toughening agents, and polycyclic toughening agents.
The end-caps of the polymers used in the present invention besides being methacryl functional may also be end capped with any activated unsaturated group. The term ~activated unsaturated group" refers to a group which has a substituent which functions through resonance to increase the free radical ~a stability or activity of the double bond, thereby facilitating free radical polymerization of the monomer. These activated unsaturated qroups become polymerized to form a polymer with a crosslinked three-dimensional network. Preferably the dctivating groups present are such that the monomers lend thamselves to polymerization under mild conditions, such as ambient temperature. Preferred activating groups include:
2-cyanoacrylosy, acrylonitryl, acryloamin;do, acryloxy, mathacrylo~y, styryl and N-vinyl-2-pyrrolidinone-~-yl where x may be 3, 4 or 5. The most preferred activating groups are m~th~rylosy and acrylo~y.

1 3 1 07~

The cycloalkyl toughening agents are described and defined in U.S. Patent No . 4, 327,203. These agents ar~ a cycloalkyl acrylate or methacrylate of the formula O E
Il I
,C--O--C--C=C~

(CH2)n' wherein E is either hydrogen or methyl D is branched or normal alkyl having 3 to 6 carbon atoms, preferably 3 to 4 carbon atoms Z is either hydrogen or methyl and n is an integer from 3 to 8 and preferably from 4 to 6.

1~ Illustrative of the foregoing cycloalkyl toughening agents are the following: Menthyl methacrylate, menthyl acrylate, tertiarybutylcyclohe~yl methacrylate, isopropylcyclopentyl acrylate, tertiarypentylcycloheptyl methacrylate, tertiarybutylcyclohexyl acrylate, isohe~ylcyclopentyl acrylate 1~ and methylisopentyl cyclooctyl acrylate.
The polycyclic toughening agents are described and defined in U.S. Patent No. 4,355,147. These agents are a polycyclic acrylate or methacrylate selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl -~a acrylate, dicyclopentadienyl methacrylate, adamantyl acrylate, adamantyl methacrylate isopinocamphyl acrylate and ~opinocamphyl methacrylate.
Illustrative of the fluorinated methacrylate toughening ag~nts are: octa1uoropentylmethacrylate, trifluoromethylmethacrylate, pentafluoroethyl methacrylate, and the like.

1 31 07g~

The toughening agent may be present in an amount from go to 10 parts by weight per 10 to 90 parts by weight of the above-described monomers. More preferably the modifier is present in the amount of 70 to 10 parts, more preferably yet the modifier is 45 to 15 parts.
The polymeric mat~rials of the prssent invention are ~ormed by: (1) mi~inq the monomers together; (2) adding a polymerization initiator; (3) subjecting the monomer/initiator misture to a source of ultraviolet or actinic radiation and la curing said mi~ture to a solid or elastomeric state.
Typical polymerization initiators include free radical generating polyme.ization initiators of the type illustrated by acetyl pero~ide, lauroyl pero~ide, decanoyl pero~ide, coprylyl pero~ide, ~enzoyl peroxide, tertiary butyl 1~ pero~ypivalate, diisopropyl peroxycarbonate, tertiary butyl peroctoate, and ~,d~-azobis-isobutynnitrile. VltraYiolet ~ree radical initiators illustrated by dietho~yacetophenone can also be used. The curing process will of course depend upon the initiator used and the physical ch2racteristics of 2~ the comonomer mi~ture such as viscosity. In any event, the level of initiator employed will vary within the range of 0.01 to 2 weight percent of the mi2ture of monomers.
Typical formulations will comprise 1 to 98 weight percent polysilo~ane monomer, 1 to 50 weight percent of the novel w~tting agents, and 1 to 80 weight percent toughening agent.
Pre~erably, the composition will comprise 60 to 95 weight percent polysilo~ane monomer, 4 to 20 weight percent tough~ning agent and 1 to 20 weight percent of the novel w~tting agent.

1 31 07"~

EXAMPLES

A~ Synthesis of 2-isopropenYl-4.4-dimethyl-2-o~azolin-5-one ~IPDM0) 1. MethacrYloy~ion: In a 500 ml 3-neck round bottom -' flask equipped with a mechanical stirrer, thermometer and an addition funnel, 51.5 grams (0.5 mole) of c~ -aminoisobutyric acid (Aldrich) and 40 grams (1 mole) of ~aOH were dissolved in - 150 ml of H2O~ The reaction flask was cooled to 0~-5C
with MeOH-ice bath and 0.5 mole of methacryloyl chloride 1~ ~distilled, Aldrich) was added dropwise while the temperature o~ the reaction mi~ture kept below 0C. After stirring for an ~dditional hour, the reaction mi~ture was acidified with conc2ntrated HCl to a pH o~ about 3 to precipitate out the intermediate, which was then filtered, washed with cold H2O
1~ and air dried. Further drying was accomplished in vacuum oven at 80C overnight to obtain 44.9 grams (0.26 mole; 53%~
n-methacryloyl-o~-aminoisobutyric acid (MAIBA), which was suitable for IPDMO synthesis. m.p. 157-159C~
2. Cycliza~ion: SYnthesis of IPDMO: In a 500 ml drY
~a 3-neck round bottom flash, 0.26 mole of MAIBA was dispersed in 300 ml of dry hesane and allowed to react with 0.26 mole of alkylchloroformate with mechanical stirring by dropwise addition of triethylamine (0.52 mole) while the temperature of the reaction mi~ture was maintàined at 95~ 50C. During the addition, the copious evolution of carbon dioxide and the ~ormation of white precipitate of TEA-HCl were observed. The raa~tion mi~ture was stirred for an additional two hours.
~ter cooling to room temperature, wh;te precipitate was ~lltered of and he~ane evaporated off yielding an oil. Pure ~3 IP~MO was obtained after two times of recrystallization in heYane at dry ice-acetone temperature. Yield was 29 grams ~3~). ;

1 31 07~

B. Synthesis of 2-vinyl-4,4-dimethvl-2-o~azolin-5-One (VDMO) 1. Acrylolation was achieved by adopting a procedure similar to step 1 of the synthesis of IPDMO e~cept acryloyl chloride was used in place of methacryloyl chloride. The intermediate n-acryloyl-d-aminobutyric acid (AAIBA) was produced.
2. AAIBA was reacted with triethylamine and ethyl chloroformate in a fashion similar to step 2 of the synthesis of IPDMO to produce VDMO.

C. Synthesis of Spiro-4~-(2~-isopropenyl-2-oxazolin-5~-one) ~yclohexane (IPCO) The synthetic method used to synthesize IPDMO was followed escept l-amino-l-cyclohe~ane carboxylic acid was used in place ofc~ -aminoisobutyric acid.

D. ~y~hesis of_Spiro-4'-(2'-vinYl-2'-o~azQlin-5'-one2 Cyclohe~ane (VCO~
The synthetic method employed in the synthesis of VDMO was used e~cept l-amino-l-cyclohe~ane carbo~ylic acid was used in place ofc~ -aminoisobutyric acid.

~3 E. Synthesis of 2-(1-propenYll-4,4-dimethyl-oxazolin-5-one (PDMO) The method employed in the synthesis of YDMO was employed e~cept crotonyl chloride was used in place of methacryloyl chlo~ide and O~-aminoisobutyric acid was used.

1 3 1 07~

F. SYnthesis and Characterization of PolYmeric Materials 1. Polydimethylsiloxane Based Materials Methacrylate end capped polydimethylsilo~ane (PD~S) with an avera~e degree of polymerization of about 180 was S compounded with isobornylmethacrylate (IBOMA) and VDMO in the weight proportion of 85/5/5 ~PDMS/IBOMA~VDMO). The mi~ture was stirred, a free radical initiator was added and polymerized by e~posure to ultraviolet radiation. The resultant polymeric material was characterized for modulus, 1~ tensile strength, elongation, oleic acid uptake, and oxygen parmeability (DK). The material was purified by extraction with toluene and also the internal wetting agent (VDMO) was hydrolyzed in the polymeric material by boiling in buffered saline solution for 20 minutes. Both the toluene e~tracted 1~ sample and toluene estracted/hydrolyzed sample were characterized. The results of these tests are reported in Table 1.

PolYdimethYlsilo~ane Based Ma~ç~

Modulus Tensile Elonqation Oleic ~qfmm2) ~/mm2) % ~ DK
95~5~5(PDMS
~IBOMA n DMO) 107 94 127 4.7 200 toluane e~tracted 521 142 35 4.~ 200 ~t~actad~
hydrolyzed 908 199 37 6.0 200 1 3 1 07~

ComParison with Prior Art Polymeric Materials The polymeric material from Example F was immersed in a buffered solution for a period of time under con~rolled cPnditions~ As a control polymeric material combining the S wetting agents described by U.S. Patent No. 4,652,622 was subjected to the same conditions and the wettability of each sample was monitored. The polymeric material of the present invention maintains its wettability to a greater degree than the state of the art wetting agent (the control).

Claims (8)

What is claimed is:
1. A composition formed by polymerizing a mixture comprising:
a) Siloxane monomer represented by the formula where A denotes an acrylate or methacrylate radical, R5 and R6 independently denote alkyl radicals with one to six carbon atoms or phenyl radicals, x and y are on the average one to six, and m is at least one; and an internal wetting agent represented by the general formula where R1 and R2 independently denote a hydrogen atom or a lower alkyl radical with one to six carbon atoms, and R3 and R4 independently denote alkyl radicals with one to six carbon atoms or a cycloalkyl radical with 5 or 6 carbon atoms.
2. A composition formed by polymerizing the mixture:
a) 1 to 98 weight percent siloxane monomer represented by the formula where A denotes an acrylate or methacrylate radical, R5 and R6 independently denote alkyl radicals with one to six carbon atoms or phenyl radicals, x and y are on the average one to six, and m is at least one; and b) 1 to 50 weight percent of an internal wetting agent represented by the general formula where R1 and R2 independently denote a hydrogen atom or a lower alkyl radical with one to six carbon atoms, and R3 and R4 independently denote alkyl radicals with one to six carbon atoms or a cyclohexyl radical.
3. The composition of claim 2 where said mixture further comprises from 1 to 80 weight percent of a toughening agent.
4. The composition of claim 3 where said toughening agent is selected from the group consisting of tertiary butyl styrene,-cycloalkyl acrylate or methacrylate toughening agents, fluorinated methacrylate toughening agents, and polycyclic acrylate or methacrylate toughening agents.
5. The composition of claim 3 which comprises:
60-95 weight percent of the siloxane monomer (a); 1-20 weight percent of said internal wetting agent; and 4-20 weight percent of a toughening agent.
6. The composition of claim 4 which comprises:
60-95 weight percent of the siloxane monomer (a); 1-20 weight percent of said internal wetting agent; and 4-20 weight percent of a toughening agent.
7. The composition of claim 1, 2, 3, 4, 5 or 6 where the compound is 2-vinyl-4,4-dimethyl-2-oxazolin-5-one.
8. The composition of claim 1, 2, 3, 4, 5 or 6 where the compound is 2-isopropenyl-4,4-dimethyl-2-oxazolin-5-one.
CA000588088A 1988-02-09 1989-01-12 Hydrophilic oxygen permeable polymers Expired - Lifetime CA1310788C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/153,901 US4910277A (en) 1988-02-09 1988-02-09 Hydrophilic oxygen permeable polymers
US153,901 1988-02-09

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EP (1) EP0328340B1 (en)
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AT (1) ATE87633T1 (en)
AU (1) AU614812B2 (en)
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CA (1) CA1310788C (en)
DE (1) DE68905627T2 (en)
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BR8900373A (en) 1989-09-26
IE890113L (en) 1989-08-09
EP0328340B1 (en) 1993-03-31
JPH01310324A (en) 1989-12-14
DE68905627D1 (en) 1993-05-06
IE62360B1 (en) 1995-01-25
US5534605A (en) 1996-07-09
ES2055034T3 (en) 1994-08-16
JP3067024B2 (en) 2000-07-17
HK84295A (en) 1995-06-09
US4910277A (en) 1990-03-20
MX163686B (en) 1992-06-12
EP0328340A2 (en) 1989-08-16
AU614812B2 (en) 1991-09-12
DE68905627T2 (en) 1993-09-23
US5357013A (en) 1994-10-18
AU2878489A (en) 1989-08-10
EP0328340A3 (en) 1989-12-13
ATE87633T1 (en) 1993-04-15

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