Title of Invention

A MONOMER MIX COMPOSITION AND A METHOD FOR THE PREPARATION THEREOF

Abstract The invention is the method of preparing macromer for use in making ophthalmic lenses comprising combining two or more monomers and using a macromer-forming catalyst, wherein the macromer- forming catalyst comprises triethylamine or bismuth.
Full Text MACROMER FORMING CATALYSTS
Background of the Invention
This invention relates to the use of macromer-forming catalysts in the formation of
macromers, especially the macromers used to make ophthalmic lenses.
Ophthalmic lenses such as contact lenses are often made in polymerization
processes which employ initiators. Acylphosphine oxides are a useful class of
initiators for free radical polymerizations, of the type frequently used to make
ophthalmic lenses. Bisacylphosphine oxides and their use are described in US
Patent No. 5,534,559 incorporated herein by reference. All of the patents and patent
applications listed herein are incorporated by reference. Unfortunately, the prior art
macromer-forming catalysts which are used in the preparation of the macromers,
which are used to make ophthalmic lenses, often adversely effect the stability of
these initiators and the use shelf life of the multicomponent formulations' which
contain them.
It is often desirable to prepare a mixture of materials together with one or more
macromers, one or more initiators and other additives that will ultimately form the
lens upon completion of curing. These types of mixes are referred to as the
"monomer mix" in this specification.
Stability of the initiator can effect the shelf life of the monomer mix. Increasing the
"shelf life" or stability of the monomer mix from that seen in the prior art is

desirable since it reduces the need to frequently prepare monomer mix lots (as
described below) and the possibility of introducing lot to lot and intra-lot variations
in lens production.
Unfortunately, in the prior art initiators tend to be unstable in a variety of
environments lessening their potential. EP 849,296 proposed a method of
stabilizing bisacylphosphine oxide initiators used in the production of urethane
(meth)acrylate polymers used for optical fiber coatings. The method involves
preparing a urethane (meth)acrylate oligomer using a tertiary amine catalyst and
then mixing with the photoinitiator and other coating formulation components.
There are also similar methods in the prior art of stabilizing monoacylphosphine
oxide photoinitiators in the presence of a tin compound used as a macromer-forming
catalyst in the urethane (meth)acrylate oligomer synthesis. U.S. Patent Application
No. 01/09076 teaches the use of tin catalysts with acetic acid.
Unfortunately, a tin catalyst such as dibutyl tin dilaurate (DBTDL) is not desirable
when applied to monomer mixes used to make ophthalmic lenses because of the
potentially deleterious effect it has on the photoinitiator and may have on various
other components of the monomer mix. This is particularly true where the
monomer mix is used to make silicone hydrogel lenses.
The prior art teaches the use of Lewis acid catalysts, including, but not limited to,
tin catalysts, such as DBTDL for the formation of macromers. The decrease in
initiator (especially photoinitiator, particularly bis-(2,6-dimethoxybenzoyl)-(2,4,4-

trimethylpentyl) phosphine oxide (DMBAPO)) concentration after mixing into a
monomer mix results in the production of lenses having unacceptable parameters
and physical attributes. Therefore, a new type of macromer-forming catalysts,
which does not effect initiator concentration, is desirable.
Summary of the Invention
The present invention involves the use of macromer-forming catalysts, which
catalyze the attachment of reactive polymerizable groups to a macromer, from
electrophilic compounds and macromer-precursor materials, ("Macromer-forming
Catalysts"), and which include, but are not limited to, tertiary amines, preferably
triethylamine ("TEA"), and bismuth catalysts, preferably bismuth carboxylates,
more preferably bismuth (111) 2-ethylhexanoate, in the macromer synthesis used in
the making of ophthalmic lenses. In one embodiment, the present invention relates
to composition of matter comprising:a macromer formed from an electrophilic
compound and a macromer-precursor material in the presence of a macromer-
forming catalyst; combined with a visible light photoinitiator, wherein the
macromer-forming catalyst is compatible with the photoinitiator.





Brief Description Of The AccornpanyingDrawing
Figure 1 is a graph showing the change in enthalpy of photopolymerization with
aging for three different monomer mixes, one with a triethylamine ("TEA")
catalyzed macromer, one with a DBTDL catalyzed macromer and one with a K-
KAT 348 bismuth carboxylate catalyzed macromer.
Detailed Description of the Invention
As used herein, macromer-forming catalysts are catalysts that catalyze the reaction
(preferably Lewis bases) but are compatible with visible light activated
photoinitiators, such that they do not adversely affect the concentration of the
photoinitiator after mixing into the monomer mix, maintaining a desired shelf life.
The macromer-forming catalysts include, but are not limited to, amines, pyridines,
sodium hydroxides, sulfuric acids, trifluoroacetic acids, bismuth salts and tertiary
amines.
The electrophilic compound has the following structure
RG-LG-PG
where RG comprises a reactive group, which may be selected from the group
comprising electrophilic functional groups including, but not limited to, isocyanate,
acid halide, acid anhydride, ester, epoxide, acetal, aldehyde, alkyl halide (preferably
an activated alkyl halide). LG comprises a divalent linking group, including, but
*
not limited to, an alkyl, aryl, ester or ether group or a covalent bond. PG comprises

a group that can polymerize under .free radical polymerization conditions, including,
but not limited to, a group comprising a vinyl or substituted vinyl group, preferably
activated by an adjoined ester, lactam or aryl group. Examples of the electrophilic
compounds include, but are not limited to, as 3-isopropenyl-,-dimethylbenzyl
isocyanate (TMI), vinylbenzyl chloride, allyl chloride, meth(acryloyl) chloride,
(meth)acrylic anhydride, methyl methacrylate, methacrylamidoacetaldehyde
dimethylacetal, 4-methacrylamidobtityraldehyde diethylacetal, glycidyl(peth)
acrylate, 2-isocyanatoethyl methacrylate, allyl isocyanate, vinyl isocyanate,
isomeric vinylbenzyl isocyanate or adduct of 2-hydroxyethyl methacrylate (HEMA)
with 2,4-toluene diisocyanate (TDI) or isophorone diisocyanate(IPDr), preferably
the 1:1 adduct. Mixtures of the above may also be used.
The macromer-precursor material comprises such reactive groups, including, but not
limited to, hydroxyl, amino, carboxyl, diol or thiol groups. The electrophilic
compound covalently bonds at the RG group with the macromer-precursor material,
forming a covalent bond, such as, without limitation, a urethane, urea, ester or ether
group.
The macromer-precursor may also comprise chemical groups that contribute to high
oxygen permeability such as siloxane groups such as polydimethylsiloxane groups,
or polyfluorinated groups. The macromer-precursor may also comprise hydrophilic
groups such as hydroxyls (in excess of those needed to react with the electrophile),
amide or ether groups such as polyethylene oxide groups. Such hydrophilic groups

may contribute to the formation of optically clear solutions of silicone and
hydrophilic monomers used in the monomer mix. In a preferred embodiment, the
macromer-precursor comprises a combination of silicone and hydroxyl groups, and
thus contributes to both the compatibility of the monomer mix, and the oxygen
permeability of the ultimate ophthalmic lens polymer. The macromer precursor
may have a molecular weight of from about 200 to about 2,000,000, more
preferably from about 800 to about 100,000, and most preferably from about 1000
to about 20,000.
One of the major benefits of using the claimed macromer-forming catalysts in the
macromer synthesis is that the initiator subsequently used in the polymerization
process is not adversely affected. Additionally, any of the macromer-forming
catalysts can be adjusted in amount to give acceptable reaction time in the
macromer formation.
The electrophilic compound and macromer-precursor material are exposed to a
macromer-forming catalyst in order to synthesize the macromer. The preferred
macromer-forming catalysts are TEA or bismuth (III) 2-ethylhexanoate.
The amount of macromer-forming catalysts containing bismuth used in the
macromer formation is about 0.02 mole % to about 2.0 mole % macromer-forming
catalysts relative to an electrophilic compound, such as TMI, preferably about 0.05
mole % to about 1.0 mole %, most preferably about 0.05 mole % to about 0.2 mole
%. Electrophilic compounds include monoisocyanates, diisocyanates and

compounds with greater than 2 isocyanate groups, preferably a compound with at
least one isocyanate group and one polymerizable double bond, more preferably 2-
isocyanatoethyl methacrylate (DEM), most preferably TMI.
The amount of TEA used in the macromer formation is preferably about 0.1 mole %
to about 2.0 mole % relative to an electrophilic compound such as TMI, more
preferably about 1.32 mole % relative to TMI.
A macromer in the present invention is a product produced by the reaction of an
electrophilic compound and a macromer-precursor material in the presence of a
macromer-forming catalyst. A preferred LG group comprises a urethane linkage.
The urethane linkages in the macromer are formed as follows:
R1NCO + R2OH —> R1NHCOOR2
The macromer includes, but is not limited to, the following types of macromers:
linear ,-terrninated hydroxyl functional polymers, linear ,-terminated amino
functional polymers, linear a,co-terminated carboxylic acid functional polymers,
linear hydroxyl, amino, or carboxylic acid monofunctional polymers, hydroxyl,
amino, or carboxylic acid terminated star polymer (3-8 arms), pendant hydroxyl
functional polymers, pendant amino functional polymers, pendant carboxylic acid
functional polymers, any combination of pendant and chain terminated hydroxyl,
amino, or carboxylic acid functional polymers listed above.


The present invention involves a method of preparing macromer by reacting an
electrophilic compound and a macromer-precursor material in the presence of a
macromer-forming catalyst, for a reaction between the electrophilic compound and
the macromer-precursor material, preferably a condensation reaction. The
macromer-precursor material means a compound with at least one group capable of
reacting with an electrophilic compound and forming a condensation product, such
as urethane, ("reacting groups"), including, but not limited to, compounds with at
least one hydroxyl, amino, carboxyl, or thiol group. Preferred macromer-precursor
materials comprise hydroxyls and more preferred macromer-precursor materials are
comprised of or made from 2-hydroxyethyl acrylate, hydroxypropyl acrylate,
hydroxypropyl methacrylate, ethoxylatedhydroxyethyl methacrylate, polypropylene
glycol monomethacrylate, caprolactone acrylate, beta carboxyethyl acrylate,
hydroxyethyl vinyl ether, N-(2-hydroxyethyl) methacrylamide, 3,4-dihydroxybutyl
methacrylate, N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide, (3-
methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane
(SiGMA), acrylic acid, methacrylic acid, itaconic acid, HEMA, polyvinyl alcohol,
(PVA), glycerylmonomethacrylate, methyldi(trimethylsiloxy)sylylpropylglycerol
methacrylate, dextran, 2-hydroxyethylcellulose, and hydroxyrnethylcellulose,
mixtures thereof and polymers and copolymers thereof. Preferred macromer-
precursor materials comprise silicone. The macromer-precursor material may be
prepared as known in the prior art, preferably by group transfer polymerization,

such as those described in US Patent Nos. 5,244,981; 5,331,067; 5,314,960;
5,314,961; and 5,371,147.
Additionally, the present invention involves a macromer-forming composition
comprising an electrophilic compound and a macromer-precursor material, and a
macromer-forming catalyst. The macromer-forming reaction preferably takes place
substantially at one or more terminal reacting groups on the macromer-precursor
material and also at one or more pendant groups. Terminal reacting groups mean
reacting groups which are placed at the end of any chain, as distinct from pendant
groups located on a chain at positions other than either end. The macrorner may be
used in multicomponent formulations used to make medical devices such as
ophthalmic lenses, which may be made of silicone hydrogels.
Silicone hydrogels have high oxygen permeability making them particularly
desirable for use in ophthalmic lenses. Silicone hydrogels are preferably prepared
by polymerizing a mixture containing at least one silicone-containing monomer and
at least one hydrophilic monomer. Either the silicone-containing monomer or the
hydrophilic monomer may function as a crosslinking agent or a separate crosshnker
may be employed. Crosslinking agents are monomers having multiple
polymerizable moieties. The term "monomer mix" when used in this sense refers to
a material used in forming the ultimate polymeric ophthalmic lens system. The
crosslinking agent may have repeat chain units and still be considered a monomer.
Incorporating a crosslinking agent into the monomer mix may generate a cross-

linked network. There are numerous silicone-containing monomelic units
commonly used in the formation of silicone hydrogels. U.S. Pat. Nos. 3,808,178;
4,120,570; 4,136,250; 4,139,513; 4,139,692; 4,153,641; 4,740,533; 5,034,461;
5,070,215; 5,260,000; 5,310,779; 5,358,995; 5,710,302; 5,789,461; 5,776,999;
5,760,100; 5,849,811; 5,962,458 and 5,998,498 provide some useful examples.
Hydrophilic monomers that have previously been found useful for making silicone
hydrogels include, but are not limited to: unsaturated carboxylic acids, such as
methacrylic and acrylic acids; acrylic substituted alcohols, such as 2-
hydroxyethylmethacrylate and 2-hydroxyethylacrylate; vinyl lactams, such as N-
vinyl pyrrolidone; and acrylamides, such as methacrylamide and N,N-
dimethylacrylamide. Still further examples are the hydrophilic vinyl carbonate or
vinyl carbamate monomers disclosed in U.S. Pat. No. 5,070,215, and the
hydrophilic oxazolone monomers disclosed in U.S. Pat. No. 4,910,277 and each is
incorporated herein by reference.
Siloxane monomers that have previously been found useful for making silicone
hydrogels may be used in the present invention. Siloxane monomers include
silicone-containing monomer and macromer having a polymerizerable vinyl group,
preferably a methacryloxy group. Examples of silicone-containing monomers and
macromers include, but are not limited to, mono-alkyl terminated
polydimethylsiloxanes ("mPDMS") (mPDMS means mPDMS with a number
average molecular weight of between about 200 and about 10,000, preferably

between about 400 and about 2000 and most preferably between about 800 and
about 1200) such as monomethacryloxy propyl terminated polydimethylsiloxane,
which comprise at least two [-Si-O-] repeating units, SiGMA type monomers
(defined below) which comprise a polymerizable group having an average
molecular weight of about less than 2000 Daltons, a hydroxyl group and at least one
[-Si-O-Si-] group and TRIS type monomers which comprise at least one Si(OSiR)3
group, where R is a monovalent alkyl or aryl group. Examples of suitable
methacryloxypropyltris(trimethylsiloxy)silane (TRIS) monomers include
methacryloxypropyltris(trimethylsiloxy)silane.
Preferably, the rnPDMS type monomers comprise total Si and attached O in an
amount greater than 20 weight percent, and more preferably greater than 30 weight
percent of the total molecular weight of the silicone-containing monomer. Suitable
mPDMS monomers have the formula, wherein n = 5 to 15



where b = 0 to 100, where it is understood that b is a distribution having a mode
equal to a stated value, preferably 4 to 16, more preferably 8 to 10; R9 is a
polymerizable monovalent group containing at least one ethylenically unsaturated
moiety, preferably a monovalent group containing a styryl, vinyl, or methacrylate
moiety, more preferably a methacrylate moiety; each R10 is independently a
monovalent alkyl, or aryl group, which may be further substituted with alcohol,
amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent
alkyl or aryl groups, more preferably methyl; R11 is a monovalent alkyl, or aryl
group, which may be further substituted with alcohol, amine, ketone, carboxylic
acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups,
preferably a C1-10 aliphatic or aromatic group which may include hetero atoms, more
preferably C3-8 alkyl groups, most preferably butyl; and R12 is independently alkyl or
aromatic, preferably ethyl, methyl, benzyl, phenyl, or a monovalent siloxane chain
comprising from 1 to 100 repeating Si-0 units.
The mPDMS type monomers are disclosed more completely in 5,998,498, which is
incorporated herein by reference.

Preferably in the SiGMA type monomer silicone and its attached oxygen comprise
about 10 weight percent of said monomer, more preferably more than about 20
weight percent. Examples of SiGMA type monomers include monomers of
Formula I

Wherein the substituents are as defined in US 5,998,498, which is incorporated
herein by reference.
Specific examples of suitable SiGMA type monomers include 2-propenoic acid, 2-
methyl-2-hydroxy-3-[3-[l,3,3,3-tetramethyl-l-
[trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester

and(3-methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane


Additional suitable hydroxyl-functionalized silicone containing monomers are
disclosed in U.S. Patent 4,235,985; 4,139,513 and 4,139,692.
In the present invention, the macromer is the reaction product of an electrophilic
compound and a macromer-precursor material in the presence of a macromer-
forming catalyst. The macromer-forming catalysts include, but are not limited to,
tertiary amines and bismuth catalysts.
Bismuth catalysts include, but are not limited to, bismuth carboxylates, bismuth
trioxide (also called dibismuthtrioxide) Bi2O3, bismuth ortho-hydroxide Bi(OH)3,
bismuthyl hydroxide BiO(OH), bismuth nitrate (BiO)NO3, and preferably, bismuth
carbonate (BiO)2CO3. Bismuth carboxylates preferably have a carboxylate portion
comprising a C2-C30, saturated or unsaturated carboxyl terminated hydrocarbon or
inertly substituted hydrocarbon chain. By inertly substituted, it is meant that the
hydrocarbon chain contains no substituent group which undesirably effects the
catalytic behavior of the macromer-forming catalyst. Preferably the carboxylate
portion is from about 6 to about 22 carbon atoms. Suitable carboxylate groups
include, but are not limited to, the ions of fatty acids, as well as branched
carboxylates such as neodecanoic acid, and Versatic 911 Acid. Preferred bismuth
catalysts include bismuth(IH) 2-ethylhexanoate (75-79%), CAS#: [67874-71-9],


which is produced by King Industries, and compositions containing bismuth
carboxylates. These bismuth catalysts can be used singly or as a mixture of two or
more components. When bismuth catalysts are used, the time for the reaction
between the electrophilic compound and the macromer-precursor material is about 3
hours.
Tertiary amines include, but are not limited to, tertiary amines having one nitrogen
atom in a molecule including, but not limited to, aliphatic amines (including, but not
limited to, tri-C1-6alkylamine such as TEA and tributylamine, 13-
(dimethylamino)propionitrile), alicyclic amines (including, but not limited to, di-C1-
6-alkyl-C3-10cycloalkylamines inclusive of N,N-dimethylcyclohexylamine and N,N-
diethylcyclohexylamine; N,N-dicyclohexylmethylamine), certain heterocyclic
amines (including, but not limited to, N-methylmorpholine, N-ethylmorpholine, N-
(2-hydroxyethyl)morpholine), aromatic amines (including, but not limited to, N,N-
dimethyl-p-toluidine), tertiary amines having two nitrogen atoms in a molecule
including, but not limited to, aliphatic amines (including, but not limited to,
N,N,N,'N'-tetramethyl ethylenediamine, N,N,N',N'-tetramethyl propane-1,3-
diamine, N,N,N',N'-tetramethyl hexane-l,6-diamine, bis(N,N-dimethylaminoethyl)
ether, bis(2-dimethylaminoethyl) ether, ethylene glycol bis(3-dimethylaminopropyl)
ether), alicyclic amines (including, but not limited to, N'-cyclohexyl-N,N-
dimethylformamidine), heterocyclic amines (including, but not limited to, N,N'-
dimethylpiperazine, trimethylpiperazine, 1,2-piperidinoethane,
bis(aminopropyl)piperazine, N-methyl-N'-2-hydroxyethyl)piperazine, N-(N',N'-

dimethylaminoethyl)morpholine) bis(morpholinoethyl ether, bis(2,6-
dimethylmorpholinoethyl) ether, 1,2-dimethylimidiazole, N-methylimidazole, 1,4-
diazine, diazabicylo[2.2.2.]-octane (DABCO), l,4-diazabicyclo[3.3.0]oct-4-en, 1,5-
diazabicyclo[4.3.0]nona-5-en (DBN), l,8-diazabicyclo]5.4.0]undece-7-en (DBU)
and its phenol salt and octylic acid salt), tertiary amines having three nitrogen atoms
in a molecule including, but not limited to, aliphatic amines (including, but not
limited to, N,N,N',N',N"-pentamethyl diethylenetriamine, N,N,N',N\N'-
pentamethyl dipropylenetriamine, tetramethyl guanidine), alicyclic amines
(including, but not limited to, N-cyclohexyl-N',N',N",N"-tetramethyl guanidine),
heterocyclic amines (including, but not limited to, N-methyl-N'-(2-
dimethylamino)ethylpiperazine, 1,5,7-triazabicyclo[4.4.0]dece-5-en), tertiary
amines with four nitrogen atoms in a molecule including, but not limited to,
aliphatic amines (including, but not limited to, 1,1,4,7,10-10-hexamethyl
triethylenetramine), heterocyclic amines (including, but not limited to, 1,3,5-
tris(N,N-dimethylpropyi)hexahydro-l ,3,5-triazine). These tertiary amines can be
used singly or as a mixture of two or more components. When tertiary amine
catalysts are used, the time for the reaction between the monoisocyanate and the
macromer-precursor material is about 24 to about 72 hours.
In a preferred embodiment, a macromer comprises the reaction product of a
protected HEMA, including, but not limited to, 2-(trimethylsiloxy) ethyl
methacrylate (TMS-HEMA); methylmethacrylate (MMA); TRIS; mPDMS; and
TMI. Other compounds optionally used in the macromer synthesis include, but are

not limited to, tetrahydrofuran (THF), moisture scavengers (including, but not
limited to, bis(dimethylamino)-methylsilane), p-xylene, other catalysts (including,
but not limited to, tetrabutylammonium 3-chlorobenzoate), initiators, and inhibitors.
A preferred embodiment of the present invention includes the following compounds
in the macromer synthesis: bis(dimethylamino)-methylsilane, a solution of
tetrabutylammonium 3-chlorobenzoate (TBACB) in THF, p-xylene, MMA, HEMA,
methyltrimethylsilyl dimethylketene acetal, mPDMS, TR1S, methanol,
dichloroacetic acid, TMI and bismuth(III) 2-ethylhexanoate as a macromer-forming
catalyst.
Other preferred monomers which may be used in the monomer mix include, but are
not limited to, TRIS; N,N-dimethyl acrylamide (DMA);
tetraethyleneglycoldimethacrylate (TEGDMA), mPDMS and HEMA.
The electrophilic compound and macromer-precursor material are exposed to a
macromer-forming catalyst in order to synthesize the macromer. The condensation
reaction of the electrophilic compound and the macromer-precursor material is
catalyzed by the macromer-forming catalyst. When the electrophilic compound is
an isocyanate, and the reactive groups on the monomer-precursor are hydroxyls, the
basic reaction is conducted in the presence of a macromer-forming catalyst as
follows:
R1NCO + R2OH —> R1NHCOOR2

The preferred macromer-forming catalysts are tertiary amines or bismuth catalysts,
most preferably TEA or bismuth (III) 2-ethylhexanoate.
In a preferred embodiment, the TEA catalyst is introduced in liquid form to the
electrophilic compound and macromer-precursor material, which react to form the
macromer.
In another preferred embodiment, the bismuth catalyst is introduced in liquid form
to the electrophilic compound and macromer-precursor material which react to form
the macromer.
In another preferred embodiment, the macromer-forming catalyst is present with the
reactants perfluoropolyether Fombline ® ZDOL (from Ausimont S.p.A. Milan),
isophorone diisocyanate, ,-hydroxypropyl-terminated polydimethylsiloxane KF-
6001 from Shin-Etsu and 2-isocyanatoethyl methacrylate. The resultant macromer
is used to produce contact lenses by subsequently reacting the macromer, TRIS and
DMA with an initiator. The resultant macromer and subsequent reaction is similar
to that disclosed in Examples Bl and B5 of U.S. Patent No. 5,760,100 except that in
the present invention, TEA or bismuth catalyst is used instead of DBTDL and
different initiators may be used.
In another preferred embodiment, the bismuth catalyst is present with the reactants,
a polyvinyl alcohol and an isocyanate, which react to form a polyvinyl alcohol

derivative macromer. The polyvinyl alcohol derivative macromer, preferably
having at least about 2000 number molecular weight, include, but are not limited to,




The isocyanate has the following formula:

The polyvinyl alcohol derivative macromer is reacted in a subsequent reaction to
produce ophthalmic lens material. The polyvinyl alcohol derivative macromer and
subsequent reaction is similar to that disclosed in U.S. Patent Nos. 4,665,123; 4,
978,713; 4,720,187; and 4,670,506, except that in the present invention, bismuth
catalyst is used and different initiators may be used in the subsequent reaction.
In another preferred embodiment, the macromer-forrning catalyst is removed from
the reaction product produced by the electrophilic compound and the macromer-
precursor material. The removal of the macromer-forrning catalyst may be effected
by purification techniques, including, but not limited to, extraction, crystallization,
precipitation, distillation, evaporation, and other purification methods. The removal
of the macromer-forrning catalyst may occur before, during or after the addition of
an initiator to the reaction product produced by the electrophilic compound and the
macromer-precursor material. In a preferred embodiment, the macromer-forrning
catalyst is removed prior to the addition of the initiator. In the prior art, DBTDL
catalyzed macromer contains about 15 to about 105 ppm tin, following macromer
synthesis and purification. In comparison, the present invention of bismuth

catalyzed macromer contains less than about 9 ppm bismuth, following macromer
synthesis and purification.
The macromers may then be used in medical devices, such as ophthalmic lenses.
The process of making ophthalmic lenses proceeds by combining the components of
a monomer mix together with the initiators and stabilizers described herein
according to well known methods of lens formation such as photoinitiated casting in
lens molds.
The preferred components of the monomer mix used to make the silicone hydrogel
lenses of this invention includes macromer, and photoinitiator (which is added to the

monomer mix before the mix is placed in a lens mold for lens production), and
optionally additional monomers. In certain embodiments, the monomer mix further
comprises at least one ultraviolet absorbing compound. Suitable ultraviolet
absorbing compounds are known in the art, and fall into several known classes
which include, but are not limited to benzophenones, benzotriazoles, triazines,
substituted acrylonitriles, salicyclic acid derivatives, benzoic acid derivatives, nickel
complexes, cinnamic acid derivatives, chalcone derivatives, dypnone derivatives,
crotonic acid derivatives, or any mixtures thereof. Other additives may also be
present and include, but are not limited to, stabilizers, reactive dyes, organic and
inorganic pigments, dyes, photochromic compounds, release agents, antimicrobial
compounds, mold lubricants, wetting agents, and combinations thereof. For
example, the monomer mix may include but is not limited to siloxanes and

acrylic/methacrylic acid and derivatives, polyvinyl monomers, typically di- or tri-
vinyl monomers, such as di- or tri(meth)acrylates of diethyleneglycol,
triethyleneglycol, tetraethyleneglycol, butyleneglycol and hexane-l,6-diol;
divinylbenzene. In a preferred embodiment, the siloxane component is a

polydimethyl siloxane. It is combined with a hydrophilic monomer such as DMA,
N-vinylpyrrolidone (NVP), hydroxyethyl methacrylate or acrylate derivative.
In another preferred embodiment, the monomers comprise mPDMS such as
monomethacryloxypropyl terminated polydimethyl siloxane and a macromer
comprising the reaction product of HEMA, MMA, TRIS, mPDMS and TMI.
Additionally preferred monomers include, but are not limited to, TRIS; DMA; and
TEGDMA. Other monomers and crosslinking agents known in the art for making
silicone hydrogels can also be used.
Suitable photoinitiators for use in the present invention are those which are activated
by exposure to visible light. The photoinitiators of this invention are those having
the following structure:
Structure I


wherein, R1, R2, and R3 are each independently H or a C1-12 substituted or
unsubstituted alkyl, cycloalkyl, or aromatic moiety provided that at least one of R1,
R2 and R3 has the following structure:
Structure H
and is attached to the P at the acyl carbon, and wherein, R4-R8 are independently, H
or a C1-3 substituted or unsubstituted alkyl or alkoxy moiety.
In each case, where an R1-R8 group is substituted, the substituent can comprise a
hydroxy or C1-4 alkyl, alkoxy, alkenyl, or alkynyl group. Substitution with hetero
atoms such as nitrogen, sulfur, and halo atoms is possible but is not favored.
It is preferred that R1 and R2 are both Structure II moieties with R4 and R8
substituents. It is most preferred that R4 and R8 are methoxy groups. It is further
preferred in this embodiment that R3 is a C1-10 alkyl, alkoxy, or alkenyl group
substituted with C1-2 alkyl groups; most preferably a substituted pentyl group. In a

preferred embodiment, both R1 and R2 are Structure II where R4, R6 and R8 may be
methyl and R3 may be phenyl (e.g. Irgacure 819).
A preferred embodiment has the following structure:
Structure III

In a preferred embodiment, R1 and R2 are both Structure II moieties with R4 and R8
being methoxy groups; R1 is a trimethyl pentyl group.
These photoinitiators can be used alone or in combination with other initiators,
including, but not limited to, benzoin methyl ether, 1-hydroxycyclohexyl phenyl
ketone (commercially available as "Irgacure® 184"); 2-benzyl-2-n-dimethylamino-
l-(4- morpholinophenyl)-l-butanone (commercially available as "Irgacure® 369");
1- hydroxycyclohexyl phenyl ketone (50% by weight) plus
benzophenone(commercially available as "Irgacure® 500"); 4-(2- hydroxyethoxy)
phenyl-(2-hydroxy propyl)ketone (commercially available as "Irgacure® 2959"); 2-
hydroxy-2-methyl-l-phenyl-propan-l-one (HMPP); 2,2-dimethoxy-2-

phenylacetophenone (BDK) (commercially available as "Irgacure® 651"); bis (nl-
2,4- cyclopentadien-1-yl), Titanium bis (eta. 5-2, 4-cyclopentadien-l-yl)bis[2,6-
difluoro-3-(lH-pyrrol-l-yl)phenyl](CGI-784);;2-hydroxy-2-methyl-l-phenyl-
propan-1-one (HMPP) (commercially available as "Darocur® 1173"); or mixtures
thereof.
The following examples compare the ophthalmic lenses prepared from the present
invention to those prepared according to the prior art. Notably, the lenses prepared
according to the present invention are acceptable for use and are equivalent to the
reference lenses.
Example 1
The following is an example of the present invention's macromer synthesis.
Table 1



TMS-HEMA, MMA, mPDMS (about 800 to about 1000MW), TRIS, p-xylene and
tetrahydrofuran (THF) were dried over preactivated 4A molecular sieve, and THF,
mPDMS, and TRIS were passed through aluminum oxide column before use.
To a dry container in a dry box under nitrogen was added bis(dimethylamino)-
methylsilane, a 1M solution of tetrabutylammonium 3-chlorobenzoate (TBACB) in
THF, p-xylene, MMA (1.4 eqv. relative to initiator), TMS-HEMA (8.5 eqv. relative

to photoinitiator) and THF. The above mixture was charged to a dry flask equipped
with a thermocouple and a condenser connected to a nitrogen source.
To the reaction mixture was injected methyltrimethylsilyl dimethylketene acetal
while stirring and purging with nitrogen. The reaction was allowed to exotherm to
about 65°C and then after the temperature of the solution dropped, a solution of
TBACB in dry THF (0.4 M) was fed in slowly throughout the rest of the reaction.
Then in step 2, a mixture of TMS-HEMA (2.1 eqv. to initiator), mPDMS (3.3 eqv.
to initiator), TRIS (7.9 eqv. to initiator) and bis(dimethylamino)-methylsilane,
prepared in dry box, was added under nitrogen.
The reaction mixture was again allowed to exotherm to approximately 42°C and
then allowed to cool to 32°C. The solution was stirred at 32°C by using a
temperature controller and heating equipment for about five hours. In step 3, a
mixture on of TMS-HEMA (8.5 eqv. to initiator), MMA (1.4 eqv. relative to
initiator) and bis(dimethylamino)-methylsilane was added and the whole mixture
allowed to exotherm to 46 - 49°C. After the mixture reacted about two hours, 270 g
of THF was added to reduce the viscosity and the solution was stirred for additional
30 minutes.
In step 4, a mixture of water, methanol and dichloroacetic acid was addqd and the
mixture was refluxed for five hours to de-block the protecting groups. The solvents
were then removed by distillation and toluene was added to aid in removal of
residual water until a vapor temperature reached 110°C

A solution of TMI and 0.2 mole % bismuth catalyst K-KAT 348 relative to TMI
was added to the above solution in toluene. The whole mixture was stirred at 1100C
for three hours and the disappearance of the isocyanate peak was monitored by IR.
The toluene was removed under reduced pressure at around 45°C to give a raw
macromer.
Purification procedures were employed to remove high molecular weight species.
The raw macromer was re-dissolved in acetone (2:1 w / w acetone to macromer) and
the acetone solution was set overnight to allow high molecular weight species to
separate. The top clear phase was filtered through a PTFE membrane by pressure
filtration. The filtrate was slowly charged into water (4:1 v / v water to filtrate) and
the macromer was precipitated out. The macromer was collected and dried using a
vacuum oven at 45 - 65°C under reduced pressure until there was no weight change.
Further purification to remove low molecular weight species was also ddne by re-
precipitation of the macromer from the mixture of acetone and acetonitrile (1:5 v /
v).
Example 2
A bismuth catalyst and a TEA catalyst were each separately used to synthesize the
macromer (as described in Example 1), which was later used to make ophthalmic
lenses. The lenses were made via direct molding, using a closed mold under
conventional molding conditions. These lenses were compared.

The lenses were optically clear. The bismuth catalyst macromer has at least a 10-
week shelf-life at 55°C. The TEA catalyzed macromer has at least a 30-week shelf-
life at 55°C.
The results of this study are noted in the table below.
Table 2
Standard deviations are noted in the parentheses.

Example 3
Another study compared the ophthalmic lenses made using TEA catalyst and
DBTDL catalyst in the macromer formation described in Example 1. The DBTDL
catalyzed macromer also uses acetic acid in the formation process as described in
U.S. Patent Application Serial No. 01/09076. The elastic modulus values for lenses
from DBTDL-catalyzed macromer were comparable to the modulus for lenses from
TEA-catalyzed monomer, but the DBTDL-catalyzed macromer lenses were

unacceptable to wear because they were misshapen and had torn or jagged edges-
Acceptable modulus values are about 30 to about 200 psi, more preferably about 35
to about 150 psi, and most preferably about 38 to about 100 psi. Water content
values and Dk [units = x 10-9 (cm/sec)(mL (VmL x mm Hg)] values show little or
no dependency on macromer-forming catalyst used in the macromer synthesis.
Table 3 reflects the measurements of relevant characteristics for the average of 8
batches using TEA-catalyzed macromer in monomer mixes and the average of 3
batches using DBTDL-catalyzed macromer in monomer mixes.
Table 3: Modulus. Elongation. Percent Water Content and Dk Values for lenses
made from monomer mixes containing TEA and DBTDL-catalyzed macromer
Standard deviations are noted in the parentheses

Example 4
A monomer mix was made from macromer, which was made as described in
Example 1, by combining the following: 17.98 % (wt) macromer from Example 1,

28.0%mPDMS (MW 800-1000), 14.0% TRIS, 26.0% DMA, 5.0% HEMA, 1.0%
TEGDMA, 2.0% Norbloc (2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-
benzotriazole), 0.02% Blue HEMA (product of the base-promoted displacement of
one chloride of Reactive Blue # 4 dye by hydroxyethyl methacrylate), 5.0% PVP
(K90), and 1.0% CGI 1850 (1:1 (wt) blend of 1-hydroxycyclohexyl phenyl ketone

and bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine oxide) blended
with the diluent 3,7-dimethyl-3-octanol in a ratio of 80 parts (wt) of the blend with
20 parts (wt) diluent.
The enthalpy of photopolymerization was measured using a TA Instruments
differential photocalorimeter with a mercury vapor lamp, with the sample at 70°C
under a nitrogen atmosphere. The enthalpy of photopolymerization was measured
as a function of monomer mix storage time at 55°C. The results are shown in Figure
1, showing monomer mixes made using macromer made using the procedure of
Example 1 with the following macromer-forming catalysts: TEA, DBTDL (with
acetic acid) or K-KAT 348 bismuth carboxylate catalyst. The enthalpy values are
the average of two measurements each.
Enthalpy values for monomer mixes made using TEA or K-KAT 348 are
statistically equivalent and do not exhibit a decrease over time as compared to
monomer mixes made using DBTDL in the prior art. Without being limited to the
mechanism, the degradation of the enthalpy values for the monomer mixes made
using DBTDL represents degradation of the visible-light photoinitiator.

Example 5
A monomer mix was made from the following: 17.98 % (wt) macromer from
Example 1 but made with DBTDL in place of K-KAT 348 bismuth carboxylate
catalyst, 28.0% mPDMS (MW 800-1000), 14.0% TRIS, 26.0% DMA, 5.0%
HEMA, 1.0% TEGDMA, 2.0% Norbloc (2-(2'-hydroxy-5-
methacrylyloxyethylphenyl)-2H-benzotriazole), 0.02% Blue HEMA (product of the
base-promoted displacement of one chloride of Reactive Blue # 4 dye by
hydroxyethyl methacrylate), 5.0% PVP (K90), and 1.0% CGI 1850 (1:1 (wt) blend
of 1-hydroxycyclohexyl phenyl ketone and bis(2,6-dimethoxybenzoyl)-2,4-4-
trimethylpentyl phosphine oxide) blended with the diluent 3,7-dimethyl-3-octanol in
a ratio of 80 parts (wt) of the blend with 20 parts (wt) diluent.
Immediately after this monomer mix was made, contact lenses were made by curing
in plastic molds under irradiation for 30 minutes with visible light fluorescent bulbs
(Philips TL 20W/03T fluorescent bulbs) at 45°C. The molds were opened and the
lenses were released in 60% IP A in water, then soaked at least one hour each in
100%, 75%, 50% and 25% (v/v) PA in water. The resulting lenses were round and

symmetrical, and had smooth optical surfaces.
After storing the monomer mix for four days at 56°C ("aged monomer mix"), a
second set of lenses were made using the same process. These lenses made from
aged monomer mix were asymmetrical, and had rough and unacceptable optical
surfaces.





In contrast, lenses made with the same process from a monomer mix with a bismuth
catalyzed macromer (as described in Example 1) were symmetrical and had smooth
optical surfaces even when made from a monomer mix stored for 4 weeks or longer
at 56°C.
It is understood that while the invention has been described in conjunction with the
detailed description thereof, that the foregoing description is intended to illustrate
and not limit the scope of the invention, which is defined by the scope of the
appended claims. Other aspects, advantages, and modifications are evident from a
review of the following claims.


WE CLAIM:
A monomer mix composition comprising
(a) a macromer, wherein the macromer comprises a
reaction product of an electrophilic compound
and a macromer-precursor material comprising
silicone in the presence of a macromer-forming
catalyst comprising bismuth; and
(b) a visible light photoinitiator, wherein the
macromer-forming catalyst is compatible with
the photoinitiator.
The composition as claimed in claim 1 wherein said
macromer-forming catalyst is selected from the group
consisting of bismuth carboxylates, bismuth trioxide
Bi2O3, bismuth ortho-hydroxide Bi(OH)3, bismuthyl
hydroxide BiO(OH), bismuth nitrate (BiO)NO3, and
bismuth carbonate (BiO)2CO3.
The composition as claimed in claim 1 wherein the
macromer-forming catalyst comprises bismuth (III)2-
ethylhexanoate.

The composition as claimed in claim 1 wherein the
macromer-forming catalyst is in liquid form.
The composition as claimed in claim 1 wherein the
electrophilic compound is selected from the group
consisting of 3-isopropenyl-,-dimethylbenzyl
isocyanate vinylbenzyl, chloride, allyl chloride,
meth (acryloyl) chloride, (meth)acrylic anhydride,
methyl methacrylate, methacrylamidoacetaldehyde
dimethylacetal, 4-methacrylamidobutyraldehyde
diethylacetal, glycidyl (meth) acrylate, 2-
isocyanatoethyl methacrylate, allyl isocyanate,
vinyl isocyanate, isomeric vinylbenzyl isocyanate of
hydroxyethyl methacrylate, adduct of hydroxyethyl
methacrylate and 2,4-toluene diisocyanate, adduct of
2-hydroxyethyl methacrylate and isophorone
diisocyanate, and mixtures thereof.
The composition as claimed in claim 1 wherein the
electrophilic compound comprises 3-isopropenyl-,-
dimethylbenzyl isocyanate.

The composition as claimed in claim 1 wherein the
electrophilic compound comprises 2-isocyanatoethyl
methacrylate.
The composition as claimed in claim 1 wherein the
macromer-precursor material comprises at least one
monomer selected from the group consisting of 2-
hydroxyethyl acrylate, hydroxypropyl acrylate,
hydroxypropyl methacrylate, ethoxylated hydroxyethyl
methacrylate, polypropylene glycol monomethacrylate,
caprolactone acrylate, beta carboxyethyl acrylate,
hydroxyethyl vinyl ether, N-(2-hydroxyethyl)
methacrylamide, 3,4-dihydroxybutyl methacrylate, N-
hydroxymethyl acrylamide, N-hydroxymethyl
methacrylamide, 2-t-butylaminoethyl methacrylate,
acrylic acid, methacrylic acid, itaconic acid,
hydroxyethyl methacrylate, polyvinyl
acrylate,polyvinyl alcohol,
glycerylmonomethacrylate,
methyldi(trimethylsiloxy)sylylpropylglycerol
methacrylate, 2-hydroxyethylmethacrylate, dextran,
hydroxypropylcellulose, 2-hydroxyethylcellulose, and
hydroxymethylcellulose; mixtures thereof and
polymers and copolymers made therefrom.

The composition as claimed in claim 1 wherein the
macromer-precursor material has at least 2 reactive
groups.
The composition as claimed in claim 1 wherein the
macromer precursor comprises isocyanate reacting
groups, the electrophilic compound comprises
electrophilic functional groups and the molar ratio
of the electrophilic functional groups to the
isocyanate-reacting groups is at a molar ratio of
1:2, wherein the macromer precursor comprises at
least 2 isocyanate-reacting groups.
The composition as claimed in claim 1 wherein the
macromer precursor comprises isocyanate-reacting
groups, the electrophilic compound comprises
electrophilic functional groups and the molar ratio
of the electrophilic functional groups to the
isocyanate-reacting groups is at a molar ratio of
1:8, wherein the macromer precursor comprises at
least 8 isocyanate-reacting groups.

The composition as claimed in claim 1 wherein the
macromer precursor comprises isocyanate-reacting
groups, the electrophilic compound comprises
electrophilic functional groups and the molar ratio
of the electrophilic functional groups to the
isocyanate-reacting groups is at a molar ratio of
1:1 to 0.001:1.
The composition as claimed in claim 1 wherein the
macromer prescursor comprises isocyanate-reacting
groups, the electrophilic compound comprises
electrophilic functional groups and the molar ratio
of the electrophilic functional groups to the
isocyanate-reacting groups is at a molar ratio of
1:1 to 0.05:1.
The composition as claimed in claim 1 wherein the
macromer precursor comprises isocyanate-reacting
groups, the electrophilic compound comprises
electrophilic functional groups and the molar ratio
of the electrophilic functional groups to the
isocyanate-reacting groups is at a molar ratio of
1:1 to 0.1:1.

The composition as claimed in claim 3 wherein the
macromer-forming catalyst is present at about 0.02
mole% to about 2.0 mole% relative to the
electrophilic compound.
The composition as claimed in claim 1 wherein the
macromer-forming catalyst is present at about 0.1
mole% to about 2.0 mole% relative to the
electrophilic compound.
The composition as claimed in claim 1 wherein the
photoinitiator comprises bis-(2,6-dimethoxybenzoyl)-
(2,4,4-trimethylpentyl)phosphine oxide.
The composition as claimed in claim 1 wherein the
photoinitiator comprises bis-(2,4,6-
trimethybenzoyl)-phenylphosphine oxide.
The composition as claimed in claim 1 wherein the
photoinitiator comprises a phosphine oxide.
The composition as claimed in claim 1 wherein the
reaction product is substantially produced in about
3 hours.

A monomer mix composition comprising
a macromer, wherein the macromer comprises a
reaction product of an electrophilic compound and a
macromer-precursor material comprising silicone in
the presence of a macromer-forming catalyst
comprising bismuth catalysts; and
a visible light photoinitiator wherein the macromer-
forming catalyst is removed after the reaction
between the electrophilic compound and the macromer-
precursor material.
The composition as claimed in claim 21 wherein the
electrophilic compound is selected- from the group
consisting of 3-isopropenyl-,-dimethylbenzyl
isocyanate, vinylbenzyl chloride, allyl chloride,
meth (acryloyl) chloride, (meth) acrylic anhydride,
methyl methacrylate, methacrylamidoacetaldehyde
dimethylacetal, 4-methacrylamidobutyraldehyde
diethylacetal, glycidyl (meth) acrylate, 2-
isocyanatoethyl methacrylate, allyl isocyanate,
vinyl isocyanate, isomeric vinylbenzyl isocyanate of
hydroxyethyl methacrylate, adduct of 2-hydroxyethyl
methacrylate and 2,4-toluene diisocyanate, adduct of

2-hydroxyethyl methacrylate and isophorone
diisocyanate, and mixtures thereof.
The composition as claimed in claim 21 wherein the
electrophilic compound comprises 3-isopropenyl-,-
dimethylbenzyl isocyanate.
The composition as claimed in claim 21 wherein the
electrophilic compound comprises 2-isocyanatoethyl
methacrylate.
The composition as claimed in claim 21 wherein the
macromer-precursor material comprises one or more
monomer of the group consisting of hydroxyethyl
acrylate, hydroxypropyl acrylate, hydroxypropyl
methacrylate, ethoxylated hydroxyethyl methacrylate,
polypropylene glycol monomethacrylate, caprolactone
acrylate, beta carboxyethyl acrylate, hydroxyethyl
vinyl ether, N-(2-hydroxyethyl) methacrylamide, 3,4-
dihydroxybutyl methacrylate, N-hydroxymethyl
acrylamide, N-hydroxymethyl methacrylamide, 2-t-
butylaminoethyl methacrylate, acrylic acid,
methacrylic acid, itaconic acid, 2-hydroxyethyl
methacrylate,polyvinyl acrylate, polyvinyl alcohol,

glycerylmonomethacrylate,
methyldi(trimethylsiloxy)sylylpropylglycerol
methacrylate, hydroxyethylmethacrylate, dextran,
hydroxypropylcellulose, 2-hydroxyethylcellulose, and
hydroxymethylcellulose, mixtures thereof and
polymers and copolymers therefrom.
The composition as claimed in claim 21 wherein the
photoinitiator comprises bis-(2,6-dimethoxybenzoyl)-
(2,4,4-trimethylpentyl) phosphine oxide.
The composition as claimed in claim 21 wherein the
photoinitiator comprises bis-(2,4,6-
trimethybenzoyl)-phenylphosphine oxide.
The composition as claimed in claim 21 wherein the
photoinitiator comprises a phosphine oxide.
The composition as claimed in claim 21 wherein the
reaction product is substantially produced in about
3 hours.
A method of preparing a monomer mix comprising:

combining an electrophilic compound and a macromer-
precursor material;
using a macromer-forming catalyst for a reaction
between the electrophilic compound and the macromer-
precursor material, wherein the macromer-forming
catalyst is compatible with a visible light
photoinitiator; and
preparing a monomer mix comprising a reaction
product of the electrophilic compound and the
macromer-precursor material, and the photoinitiator.
The method as claimed in claim 30 wherein the
macromer-precursor material comprises silicone.
The method as claimed in claim 30 wherein the
macromer-forming catalyst comprises a Lewis base.
The method as claimed in claim 30, wherein said
macromer-forming catalyst is selected from the group
consisting of amines, pyridines, sodium hydroxides,
sulfuric acids, trifluoroacetic acids, bismuth
salts, and tertiary amines.

The method as claimed in claim 30 wherein said
macromer-forming catalyst is selected from the group
consisting of bismuth carboxylates, bismuth trioxide
Bi2O3, bismuth ortho-hydroxide Bi(OH)3, bismuthyl
hydroxide BiO(OH), bismuth nitrate (BiO)N03, and
bismuth carbonate (BiO)2C03.
The method as claimed in claim 30 wherein the
macromer-forming catalyst comprises bismuth.
The method as claimed in claim 30 wherein the
macromer-forming catalyst comprises bismuth (III) 2-
ethylhexanoate.
The method as claimed in claim 30 wherein the
macromer-forming catalyst comprises at least one
tertiary amine.
The method as claimed in claim 30 wherein the
macromer-forming catalyst comprises triethylamine.
The method as claimed in claim 30 wherein the
macromer-forming catalyst is in liquid form.

The composition as claimed in claim 30 wherein the
electrophilic compound is selected from the group
consisting of 3-isopropenyl-a,a-dimethylbenzyl
isocyanate, vinylbenzyl chloride, allyl chloride,
meth (acryloyl) chloride, (meth) acrylic anhydride,
methyl methacrylate, methacrylamidoacetaldehyde
dimethylacetal, 4-methacrylamidobutyraldehyde
diethylacetal, glycidyl (meth) acrylate, 2-
isocyanatoethyl methacrylate, allyl isocyanate,
vinyl isocyanate, isomeric vinylbenzyl isocyanate of
hydroxyethyl methacrylate, adduct of 2-hydroxyethyl
methacrylate and 2,4-toluene diisocyanate, adduct of
2-hydroxyethyl methacrylate and isophorone
diiocyanate and mixtures thereof.
The method as claimed in claim 30 wherein the
electrophilic compound comprises 3-isopropenyl-a,a-
dimethylbenzyl isocyanate.
The method as claimed in claim 30 wherein the
electrophilic compound comprises 2-isocyanatoethyl
methacrylate.

The composition as claimed in claim 30 wherein the
macromer-precursor material is selected from the
group consisting of hydroxyethyl acrylate,
hydroxypropyl acrylate, hydroxypropyl methacrylate,
ethoxylated hydroxyethyl methacrylate, polypropylene
glycol monomethacrylate, caprolactone acrylate, beta
carboxyethyl acrylate, hydroxyethyl vinyl ether, N-
(2-hydroxyethyl) methacrylamide, 3,4-dihydroxybutyl
methacrylate, N-hydroxymethyl acrylamide, N-
hydroxymethyl methacrylamide, 2-t-butylaminoethyl
methacrylate, acrylic acid, methacrylic acid,
itaconic acid, 2-hydroxyethyl methacrylate,
polyvinyl acrylate, polyvinyl alcohol,
glycerylmonomethacrylate,
methyldi(trimethylsiloxy)sylylpropylglycerol
methacrylate, hydroxyethylmethacrylate, dextran,
hydroxypropylcellulose, 2-hydroxyethylcellulose, and
hydroxymethylcellulose, mixtures thereof and
polymers and copolymers thereof.
The composition as claimed in claim 30 wherein the
macromer-precursor material has at least 2 reactive
groups.

The composition as claimed in claim 30 wherein the
molar ratio of electrophilic compound functional
groups to the isocyanate-reacting functional groups
is at a molar ratio of 1:2, wherein the isocyanate-
reacting group comprises at least 2 isocyanate-
reacting functional groups.
The composition as claimed in claim 30 wherein the
molar ratio of electrophilic compound functional
groups to the isocyanate-reacting functional groups
is at a molar ratio of 1:8, wherein the isocyanate-
reacting group comprises at least 8 isocyanate-
reacting functional groups.
The composition as claimed in claim 30 wherein the
molar ratio of electrophilic compound functional
groups to the isocyanate-reacting functional groups
is at a molar ratio of 1:1 to 0.001:1.
The composition as claimed in claim 30 wherein the
molar ratio of electrophilic compound functional
groups to the isocyanate-reacting functional groups
is at a molar ratio of 1:1 to 0.05:1.

The method as claimed in claim 30 wherein the molar
ratio of electrophilic compound functional groups to
the isocyanate-reacting functional groups is at a
molar ratio of 1:1 to 0.1:1.
The method as claimed in claim 36 wherein the
macromer forming catalyst is present at about 0.02
mole% to about 2.0 mole% relative to the
electrophilic compound.
The composition as claimed in claim 38 wherein the
macromer-forming catalyst is present at about 0.1
mole% to about 2.0 mole % relative to the
electrophilic compound.
The method as claimed in claim 30 further comprising
removing the macromer-forming catalyst from the
electrophilic compound and the hydroxy-containing
material, after the reaction.
The composition as claimed in claim 30 wherein the
initiator comprises a bis-(2,6-dimethoxybenzoyl)-
(2,4,4-trimethylpentyl)phosphine oxide.

The composition as claimed in claim 30 wherein the
photoinitiator comprises bis-(2,4,6-
trimethybenzoyl)-phenylphosphine oxide.
The method as claimed in claim 30 wherein the
initiator comprises phosphine oxide.
The method as claimed in claim 30 wherein the
reaction product is substantially produced in about
3 hours.
An ophthalmic device comprising the composition as
claimed in claim 1, or 21.
A medical device comprising the composition as
claimed in claim 1 or 21.
A contact lens comprising the composition as claimed
in claim 1 or 21.
A silicone hydrogel lens comprising the composition
as claimed in claim 1 or 21.

61. A method of preparing a macromer, the method
comprising:
(a) reacting in tetrahydrofuran and p-xylene, bis
(dimethylamino)-methylsilane, a solution of
tetrabutylammonium 3-chlorobenzoate,
methylmethacrylate, (trimethylsiloxy)ethyl
methacrylate, and methyltrimethylsilyl
dimethylketene acetal to form reaction product
(a);
(b) reacting reaction product (a) with
(trimethylsiloxy)ethyl methacrylate, mono-alkyl
terminated polydimethylsiloxanes, TRIS and
methacryloxypropyltris (trimethylsiloxy) silane
to form reaction product (b);
(c) reacting reaction product (b) with
(trimethylsiloxy)ethyl methacrylate, and
methylmethacrylate, bis (di methylamino)-
methylsilane, to form reaction product (c);

(d) reacting reaction product ( c ) in methanol
with water and dichloroacetic acid; to form a
macromer precursor and
(e) reacting said macromer precursor with 3-
isopropenyl-a,a-dimethylbenzyl isocyanate, in
the presence of bismuth (III) 2-ethyl
hexanoate; to form a macromer and
adding bis- (2,6-dimethoxybenzoyl)-(2, 4, 4-
trimethylpentyl) phosphine oxide to said
macromer for a subsequent reaction.
A monomer mix composition comprising:
a macromer comprising components formed from
reaction of a mixture comprising methylmethacrylate,
(trimethylsiloxy)ethyl methacrylate,
methyltrimethylsilyl dimethylketene acetal, mono-
alkyl terminated polydimethylsiloxanes,
methacryloxypropyltris (trimethylsiloxy)silane, and
3- isopropenyl-a,a-dimethylbenzyl isocyanate in the
presence of a bismuth (III)2-ethyl hexanoate; and
bis-(2,6-dimethoxybenzoyl)-(2,4,4-
trimethylpentyl)phosphine oxide.

A composition of matter comprising:
a macromer formed from an electrophilic compound
and a macromer-precursor material comprising
silicone in the presence of macromer-forming
catalyst comprising bismuth; and
a visible light photoinitiator, wherein the
macromer-forming catalyst is compatible with the
photoinitiator.
The composition as claimed in claim 63 further
comprising at least one additional component
comprising siloxane monomers, hydrophilic monomers
and mixtures thereof.
The composition as claimed in claim 64 wherein said
additional component is selected from the group
consisting of unsaturated carboxylic acids, vinyl
lactams, acrylamides, acrylic acids, acrylic
substituted alcohols, hydrophilic vinyl carbonate
monomers, vinyl carbamate monomers, hydrophilic
oxazolone monomers, silicone-containing monomer
having a polymerizerable vinyl group and silicone
containing macromer having a polymerizable vinyl

group, mixtures thereof and polymers and copolymers
thereof.
The compositions as claimed in claim 64, wherein
said additional component is selected from the group
consisting of methacrylic acid, 2-
hydroxyethylmethacrylate, 2-hydroxyethylacrylate, N-
vinyl pyrrolidone, methacrylamide, N,N-
dimethylacrylamide, mono-alkyl terminated
polydimethylsiloxanes, SiGMA type monomers, TRIS
type monomers, mixtures thereof and polymers and
copolymers thereof.
The composition as claimed in claim 64 wherein said
additional component comprises at least one silicone
containing monomer selected from the group
consisting of methacryloxypropyltris
(trimethylsiloxy)silane; 2-propenoic acid, 2-methyl-
2-hydroxy-3-[3-[1,3,3,3-tetramethyl-l-
[trimethylsilyl)oxy]disiloxanyl]propoxy]propyl
ester; (3-methacryloxy-2-
hydroxypropyloxy)propyltris(trimethylsiloxy) silane;
and mixtures thereof.

68. The composition as claimed in claim 1 wherein
macromer-precursor material comprises at least one
reactive group selected from the group consisting of
hydroxyl, amino, carboxyl, diol,thiol groups and
combinations thereof.

The invention is the method of preparing macromer for use in making ophthalmic lenses comprising combining two or more
monomers and using a macromer-forming catalyst, wherein the macromer-
forming catalyst comprises triethylamine or bismuth.

Documents:

1941-KOLNP-2004-FORM-27.pdf

1941-kolnp-2004-granted-abstract.pdf

1941-kolnp-2004-granted-assignment.pdf

1941-kolnp-2004-granted-claims.pdf

1941-kolnp-2004-granted-correspondence.pdf

1941-kolnp-2004-granted-description (complete).pdf

1941-kolnp-2004-granted-drawings.pdf

1941-kolnp-2004-granted-examination report.pdf

1941-kolnp-2004-granted-form 1.pdf

1941-kolnp-2004-granted-form 18.pdf

1941-kolnp-2004-granted-form 2.pdf

1941-kolnp-2004-granted-form 26.pdf

1941-kolnp-2004-granted-form 3.pdf

1941-kolnp-2004-granted-form 5.pdf

1941-kolnp-2004-granted-reply to examination report.pdf

1941-kolnp-2004-granted-specification.pdf

1941-kolnp-2004-granted-translated copy of priority document.pdf


Patent Number 230110
Indian Patent Application Number 1941/KOLNP/2004
PG Journal Number 09/2009
Publication Date 27-Feb-2009
Grant Date 25-Feb-2009
Date of Filing 16-Dec-2004
Name of Patentee JOHNSON & JOHNSON VISION CARE INC.
Applicant Address 7500 CENTURION PARKWAY, SUITE 100, JACKSONVILLE IL
Inventors:
# Inventor's Name Inventor's Address
1 FRANK F. MOLOCK 1543 WILDFERN DRIVE, ORANGE PARK, FL 32073
2 MICHAEL R. CLARK 8771 CANOPY OAKS DRIVE, JACKSONVILLE, FL 32256
3 ANNIE C. MAIDEN 1558 HOPE VALLEY DRIVE, JACKSONVILLE, FL 32221
4 XIAOPING LIN 8980 ADAMS WALK DRIVE, JACKSONVILLE, FL 32257
5 CARRIE L. CAISON 1581 BEECHER LANE, ORANGE PARK, FL 32073
6 ROBERT LOVE 563 VALLEY VIEW DRIVE, HYRUM, UTAH 84319
PCT International Classification Number C08F 2/48
PCT International Application Number PCT/US2003/019700
PCT International Filing date 2003-06-23
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10/183,765 2002-06-25 U.S.A.