JPH028205A - Patial polymerized monomer-containing composition having high allylic utilization degree - Google Patents

Abstract

PURPOSE: To provide composition which has specific allylic availability, is liquid, and is not gelled, by including it of partly-polymerized monomer such as bis (allylic carbonate) monomer of 4,4'-(alkylidene)bis(phenol).

CONSTITUTION: At least one kind of bis(allylic carbonate)monomer of 4,4'-(alkylidene)bis(phenol) and/or at least one kind of bis(allylic carbonate) monomer of 4,4'-phenilenebis(alkylidene) is polymerized using radical initiator such as di-n-propyl peroxide carbonate in solvent such as preferably methylene chloride. Thus, the composition which contains the partly-polymerized monomer, has allylic availability of more than 50%, preferably 60-80%, and is adequate for an opthalmologic lens, especially.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION Bis(allylic carbonate) monomers are often radically polymerized to produce rigid polymers.

Many of these monomers, when unpigmented, form rigid polymers that exhibit high transparency to visible light, are substantially rigid, and exhibit refractive indices that are sufficient for many, if not all, ophthalmic applications. arise. For these reasons, such monomers are useful as precursors for optical lenses (particularly ophthalmic lenses), lens blanks, sunglass lenses, surface protectors, filters, flat or curved lenses, coatings, and other optical elements. Provide use as a.

One problem with the polymerization of bis(allylic carbonate) monomers is the relatively high shrinkage of the material that occurs during the course of polymerization. For example, the shrinkage rate during homopolymerization of diethylene glycol bis(allyl carbonate) monomer is approximately 12.5%.

Such high degrees of shrinkage are particularly problematic where polymerizable bis(allylic carbonate) monomer compositions are polymerized in the substantially closed molds typical of many casting operations. Although not wishing to be limited by theory, it is believed that much, if not all, of the shrinkage is due to conversion of the allylic group to a portion of the polymer.

As used herein, the term "shrinkage"
) 1 is (D p - D m)/D p [D p is 2
The density of the final thermosetting polymer at 5°C, Dm is 25
Density of the cast composition in °C. ]. ``The term percent shrinkage J refers to shrinkage multiplied by 100.

One method to reduce the degree of shrinkage during casting operations is to form a liquid prepolymer from bis(allylic carbonate) monomer, load the prepolymer into a mold (and optionally add an initiator), and then There are methods of polymerizing polymers to form rigid polymers. Since some of the allylic groups are converted before loading into the mold, shrinkage that occurs during polymerization in the mold is reduced. This prepolymerization technique has had some success in dealing with shrinkage problems.

Gelation is the main reason why it is difficult to further reduce shrinkage with the prepolymerization route. Early prepolymerization techniques generally required only a small fraction of the total available allyl groups to be utilized before gelation occurred. For example, when forming prepolymers from diethylene glycol bis(allyl carbonate) monomer, gelation was typically observed after about 12% of the allylic groups were utilized. Further improvement efforts have been made to achieve prepolymers of diethylene glycol bis(allyl carbonate) monomers with up to 17% allylic availability prior to gelation; see, for example, JP-A-51-9188.

A major advance in the art of forming poly(alkylic carbonate)-functional prepolymers was published in U.S. Patent Application No. 5
No. 49,850 (filed Nov. 9, 19B3) and co-pending U.S. patent application Ser. No. 690.411 (filed Jan. 10, 1985). Insert the entire text of this statement here.

According to the methods of U.S. Pat. No. 549,850 and U.S. Pat. It is soluble. Preferably, the initiator used to effect the polymerization is also soluble in the solvent. A solution made of poly(allylic carbonate)-functional monomer 1 solvent and preferably an initiator is partially polymerized by heating the solution to the polymerization temperature. The polymerization reaction is continued until the allylic utilization is 12% or more. Allylic utilization is controlled by adjusting the amount of initiator added to the solution, the temperature at which the partial polymerization is carried out, and the ratio of solvent to poly(allylic carbonate)-functional monomer. Generally, the higher the amount of initiator used, the higher the allylic utilization.

The higher the polymerization temperature, the lower the allylic utilization. For a given amount of initiator at a constant temperature, increasing the ratio of solvent to monomer will reduce allylic utilization.

However, if the ratio of solvent to monomer is increased at a given temperature, and the amount of initiator used is also increased sufficiently, the reaction will typically have a higher allylic utilization without gel formation than systems containing small amounts of solvent. bring degree.

In preferred embodiments of U.S. Pat. 5 m12/g (monomer weight) and a polymerization temperature of 28°C to about 100°C are used. The degree of allyl utilization is nuclear magnetic resonance (NMR) and infrared (IR).
It may be controlled by spectroscopic methods. The solvent in the resulting composition can be removed using known techniques (e.g. evaporation) leaving behind a viscous liquid consisting of a solution of the poly(allylic carbonate)-functional prepolymer in the poly(allylic carbonate)-functional monomer. 1on) or distillation). The solution is typically at least about 100 centistokes to about 100 centistokes, typically about 100 centistokes, at 25°C.
Kinematic viscosity (measured with a capillary viscometer) of 0 to 40,000 centistokes, more typically about 500 to 2.000 centistokes and about 1°17 to about 1.23 g at 25°C.
It is a syrup-like liquid with a bulk density of /c+++''.

The solution further has an allylic utilization of 12% or more, preferably at least 15-50%, as measured by infrared spectroscopy or nuclear magnetic resonance spectroscopy;
A particularly preferred example is characterized by an allyl utilization of about 20 to 50%.

U.S. Patent Application No. 549,850 and U.S. Patent Application No. 690,411 disclose that the steps described therein are poly(allylic carbonate)-functionalized with an (allylic carbonate) functionality of 2 to 5, preferably 2. This shows that it can be applied to chemical monomers. Both aliphatic diol bis(allylic carbonate) monomers and bisphenol bis(allylic carbonate) monomers are mentioned.

Most notably with respect to U.S. Pat. The technology for generation is described. This represents a major advance in poly(allylic carbonate)-functional prepolymer technology.

SUMMARY OF THE INVENTION Contrary to what the known art indicates regarding allylic utilization, a substantially gel-free prepolymer with an allylic utilization of greater than 50% is provided by the type of bis(allylic carbonate) monomer used in its preparation. It has now been discovered that it can be generated by paying particular attention. The substantial absence of gelation is truly surprising when one considers that essentially more than half of the allylic groups in the bis(allylic carbonate)-functional system have reacted.

Therefore, in one embodiment of the present invention, at least one bis(allylic carbonate) monomer of (a) 4,4°-(alkylidene)bisphenol],
Phenylenebis(alkylidene)]bis[phenol]
a bis(allylic carbonate) monomer or a mixture thereof, comprising: (b) an allylic utilizat of the composition;
) is greater than 50%, and is a liquid, polymerizable, gel-free composition containing partially polymerized monomers.

Frequently the allic utilization is at least 51%.

In most cases, the degree of allic utilization is at least about 55%,
Preferably it is at least about 60%. Frequently, allic utilization ranges from 51% to about 80%. Allylic utilization in the range of about 55 to about 80% is preferred, particularly about 60 to about 80%.

At least one partially polymerized 4,4°-(alkylidene)bis[phenol] and/or 4°4'-
[Bis(allylic carbonate) of at least IN of phenylene bis(alkylidene) cobis[phenol]
The monomers may be substituted or unsubstituted with one or more minor substituents, or some may be unsubstituted and some substituted. When one or more substituents are used, they may be the same or different, or one may be different from and the same as one or more others. Examples of substituents that may be used include halogen, lower alkyl, and lower alkokene. Halogen is most commonly fluorine, chlorine, or bromine; chlorine and bromine are the preferred halogen groups. Lower alkyl generally contains 1 to about 4 carbon atoms; methyl and ethyl are preferred lower alkyl groups.

Methoxy and ethoxy are preferred alkoxy groups.

When substitutions are used, the number, nature and position of the substituents must be such that they do not interfere with the production of the prepolymer compositions of the present invention.

Each alkylidene group independently contains at least one carbon atom and may be branched or unbranched. Often, each alkylidene independently contains 1 to about 5 carbon atoms. Examples of suitable alkylidene groups are methylene, ethylidene, propylidene, 1-methylethylidene (i.e. isopropylidene), butylidene, ! -methylpropylidene, 2-methylpropylidene, and 2-ethylpropylidene. l-methylethylidene is preferred.

4.4°-[phenylenebis(alkylidene)]bis[
The central phenylene group of the bis(allylic carbonate) monomer of [phenol] is 1,2-phenylene, 1,3-
It may be phenylene or 1,4-phenylene.

A preferred phenylene group is 1,3-phenylene.

The monomers may be known or prepared by procedures well known in the art.

For example, U.S. Patent No. 2,370,567.2.455.
652.2,455,653 and 2,587°437
(insert full text here).

The first method involves reacting the appropriate allylic alcohol with phosgene to form the corresponding allylic chloroformate, producing the desired 4.4°-(alkylidene)bis[phenol] and/or 4.4°-[ Phenylene bis (
alkylidene)] bis[phenol]. 2
The second method uses 4,4°-(alkylidene)bis[phenol] and/or 4°4°-[phenylenebis(
alkylidene)]bis[phenol] is reacted with phosgene to form a bischloroformate, which is then reacted with a suitable allylic alcohol. In the third method, 4.4°−
(alkylidene)bis[phenolco and/or 4
．． 4'-[phenylenebis(alkylidene)]bis[phenol], the appropriate allylic alcohol, and phosgene are mixed together and reacted. In all these reactions, the proportions of the reactants are approximately stoichiometric, except that phosgene is used in substantial excess, and if desired,
In the second method an excess amount of allylic alcohol is used. The temperature of the chloroformate formation reaction is preferably about 1
It is less than 00℃. Typical temperatures for chloroformate formation reactions range from about 10°C to about 20°C. The carbonate forming reaction is usually carried out at about the same temperature, although higher temperatures may be used. A suitable acid acceptor, such as pyridine, tertiary amine, alkali metal hydroxide or alkaline earth metal hydroxide, may be used if desired. The reaction is usually a liquid phase reaction.

Preferably they are carried out in the absence of external solvents, although external solvents may be used when desired or necessary to solubilize one or more reactants. Examples of suitable external solvents used include benzene, toluene, xylene, chlorobenzene, O-dichlorobenzene, O-chlorotoluene, acetone, methylene chloride, chloroform, perchloroethylene, trichloroethylene and carbon tetrachloride. The pressure at which the reaction is carried out may vary over a wide range, but is usually around ambient pressure or slightly higher depending on the pressure drop through the equipment.

It will be appreciated that one of the bisphenolic compounds described above or a mixture of such bisphenolic compounds may be used to form the bis(allylic carbonate) monomer.

If mixtures are used, each may be one of the group 4,4'-(alkylidene)bis[phenol] and each one of the group 4,4°-[phenylenebis(alkylidene)]bis[phenol]. or one or more from one group and one or more from another group.

Bisphenolic compounds that may be used to prepare bis(allylic carbonate) monomers each have the formula
OH-A-OH(r) [wherein A is alkylidene containing an elementary atom and R is each independently hydrogen, halogen, lower alkyl containing 1 to about 4 carbon atoms, methoxy or ethoxy and n The value of is 0 or l. May be expressed as ko.

When the value of n is 1, preferably A is a formula or a formula, where each Q independently represents 1 to about 5 carbons [Q, R
and n has the same meaning as formula ■. ] Represented by

Preferably, the value of 1 is 0, in which case A is the formula [Q and R have the same meaning as the formula ■. ] Represented by

Examples of bisphenol compounds that can be used are 4.4
'-(methylene)bisphenol], 4,4゛-(1
-methylethylidene)bis[phenolco, 4゜4'-
(1-methylethylidene)bis[2,6-dichlorophenol], 4,4°-(1-methylethylidene)bis[
2,6-dibromophenol], 4,4゛(l-methylpropylidene)bis[phenol], 4゜4°-[1,
4-phenylenebis(1-methylethylidene)]bis[
phenol], 4,4'-[1,3-phenylenebis(
1-methylethylidene)]bis[phenol].

The monomeric composition prepared by the above process is mainly of the formula [A has the same meaning as in formula 1 and R8 is each independently hydrogen or methyl. ] Consists of one or more bis(allylic carbonate)-functional monomer compounds represented by the following. Often both Ro groups are the same, preferably both hydrogen.

Because of the nature of the process by which monomeric compositions are prepared, monomeric compositions include a few of the related types. In the case of a monomeric compound represented by formula (■), the related species are each represented by the formula or formula or formula [R has the same meaning as formula (■), A each independently has the same meaning as formula I, i is 2 j is an integer from θ to about 5, and k is an integer from 0 to about 5. ].

The reaction mixture may be purified to be essentially free of related species, but this is rarely done. Although the reaction mixture may contain only one related species,
Usually contains a mixture of different related species. Typically, the total associated species obtained together will comprise from about 0.5% to about 3% by weight of the reaction mixture, free of external solvents.

Similarly, a compound of the formula (II) or a group of such compounds may be separated from the reaction mixture, but this is also rarely done.

Bis(allylic carbonate) monomer of 4,4'-(alkylidene)bis[phenol] as used herein, 4.4°-[phenylenebis(alkylidene)
] Bis(allylic carbonate) monomer of bis[phenol] or terms of similar names are meant to include all related species which may be included therein as well as the principal monomeric compounds listed. It means.

4. Bis(allylic carbonate) monomer of 4°-(alkylidene)bis[phenol] and/or 4
, 4°-[phenylenebis(alkylidene)]bis[phenol] by partially polymerizing the bis(allylic carbonate) monomer to utilize more than half of the allylic groups without resulting in substantial gelation. A polymerized monomer composition is prepared. Such “significantly gel-free”
ree) J and [substantial gelation (signj r
By "not resulting in 1 cant gelation" is meant that the composition contains less than about 5% by weight gel, based on the initial bis(allylic carbonate) monomer. Often, the compositions will contain less than about 2% gel by weight based on the initial bis(allylic carbonate) monomer. Preferably there is no gel in the composition.

The liquid, polymerizable, substantially gel-free, partially polymerized monomer compositions of the present invention may be conveniently prepared by solution polymerization. The bis(allylic carbonate) monomer is soluble in the solvent, and the partially polymerized monomer is also soluble in the solvent. Preferably also a solvent soluble initiator is included in the reaction mixture. The resulting solution containing bis(allylic carbonate) monomer, solvent, and preferably initiator is partially polymerized by heating the reaction mixture to the polymerization temperature. Polymerization continues until the allylic utilization is greater than 50%, ie, more than 50% of the ethylenic unsaturation initially provided by the monomers has been consumed.

Allylic utilization is controlled by adjusting the amount of initiator present in the solution, the temperature at which the partial polymerization is carried out, and the ratio of solvent to bis(allylic carbonate) monomer. Generally, the higher the amount of initiator used, the higher the allylic utilization. The higher the polymerization temperature, the lower the allylic utilization. - With a certain amount of initiator at a constant temperature, a higher ratio of solvent to monomer will result in lower allylic utilization. However, if the ratio of solvent to monomer is increased at a given temperature, and the amount of initiator used is also increased sufficiently, the reaction will typically have a higher allylic utilization without gel formation than systems containing small amounts of solvent. bring degree.

Polymerization is terminated when the desired allylic utilization is reached.

This may be accomplished by lowering the temperature of the reaction mixture to a value that terminates the polymerization reaction for all practical purposes, by adding inhibitors that destroy the radicals necessary for further polymerization, or both.

After the polymerization reaction is finished, the solvent is preferably removed. This is accomplished by known techniques (eg evaporation, stripping or distillation) which leave a solution of the poly(allylic carbonate)-functional polymer in the bis(allylic carbonate) monomer.

This solution is essentially free of solvents used during the polymerization process. Essentially solvent-free solutions typically at 25°C
It is a syrupy liquid having a kinematic viscosity of at least about 100 to about 100°,000 centistokes. Often, kinematic viscosities range from about 1000 to about 90,000 centistokes at 25°C. Often the kinematic viscosity at 25°C ranges from about 5000 g o, o o centistokes. The density of the essentially solvent-free solution typically ranges from about 1.17 to about 1.23 g/cm'' at 25°C.The essentially solvent-free solution can be further analyzed using an infrared spectrometer or a nuclear magnetic 5 as measured by resonance spectrometer
It is characterized by having an allic utilization degree of 0% or more.

Organic solvents useful in carrying out solution polymerizations are those that do not chemically react with the monomers and the resulting polymer, have a substantially lower boiling point, i.e., a higher vapor pressure, than the monomers so that they can be easily separated from the monomers by distillation; It serves as a solvent for the bis(allylic carbonate) monomer (and preferably also for the initiator) and the resulting liquid aromatic-containing poly(allyl carbonate) functional polymer. Useful solvents include halogenated ones, such as chlorinated CI"""C, and hydrocarbon solvents, such as methyl chloride, methylene chloride, ethyl chloride, ethylene chloride, 1,1.2-)lichloro1.2 .2-) trifluoroethane, and mixtures thereof. Methylene chloride is preferred for its high vapor pressure, low boiling point, ease of separation, and relatively low toxicity.

The amount of solvent used in the partial polymerization step must be sufficient to dissolve all of the monomers and dissolve all of the resulting polymer. Generally about 0.5 to 5 aye (solvent)7
g (monomer). Larger amounts of solvent can be used without deleterious effects. Less agitating solvents often result in the formation of insoluble, infusible, and difficult to process gels when more than 50% allylic utilization is made.

The concentration of initiator useful for partial polymerization must satisfy the desired range of allylic utilization for the conditions used; It can be changed within a range of %. Higher amounts of initiator can leave the initiator in the product or result in the formation of a gel that is infusible, insoluble, and difficult to process. Initiators useful for carrying out solution polymerization of bis(allylic carbonate) monomers are radical initiators, such as organic peroxides and azo catalysts, and are well known. Preferred radical initiators are organic peroxy compounds such as peroxy esters, diacyl peroxides, peroxy dicarbonates and mixtures of these peroxy compounds.

Examples of peroxy compounds include; peroxydicarbonate esters (e.g., di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-n-butyl peroxydicarbonate, di-5
ec-butyl peroxydicarbonate, diisobutyl peroxydicarbonate, di(2-ethylhexyl)
peroxydicarbonate, diacetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate and isopropyl 5ec-butyl peroxydicarbonate); diacetyl peroxide (e.g. diacetyl peroxide , dibenzoyl peroxide, dilauroyl peroxide and diisobutyl peroxide): peroxy esters (e.g. tert-butyl perpivalate, t-butyl peroctoate and tert-butyl peroxide) It will be done.

A single peroxy compound or a mixture of peroxy compounds may be used if desired.

Solution polymerizations are generally conducted at temperatures of about 288C to about 100C for about 1 to about 24 hours. The time and temperature depend on the initiator and its concentration and the solvent:monomer ratio used.

In many cases, polymerizable compositions are injectable. By pouring such pourable polymerizable compositions into a suitable mold and allowing the composition to polymerize to form a solid thermosetting polymer in the desired shape, cast lenses, lens blanks, and ponds can be manufactured, among other things. Useful for shaped objects.

Although partially polymerized heptamer compositions polymerize to form rigid polymers, more often the compositions are combined with one or more other materials prior to such polymerization.

Therefore, another aspect of the invention is (aX i )4
.

at least one bis(allylic carbonate) monomer of 4°-(alkylidene)bis[phenol], 4,
4°-[phenylenebis(alkylidene)cobis[phenol] A composition comprising partially polymerized monomers that are at least one bis(allylic carbonate) monomer of [phenylenebis(alkylidene)cobis[phenol] or a mixture thereof, the composition comprising: (a) a liquid, polymerizable, substantially gel-free, partially polymerized monomer-containing composition having an allyl utilization greater than 50%; and (b) a liquid, polymerizable formulation of one or more other substances.

Preferably, when polymerization of the polymerizable composition is initiated by thermally generated radicals, the polymerizable formulation includes an initiator. Thermal initiators that can be used in the present invention vary over a wide range, but are generally thermally decomposable and generate radical pairs. One or both radical pair moieties are useful for initiating addition polymerization of ethylenically unsaturated groups in known manner.

A preferred thermal initiator is a peroxy initiator.

A variety of different peroxy initiators may be used.

Examples of such peroxy initiators include: peroxydicarbonate esters (e.g., di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-n-butylperoxydicarbonate, di-butylperoxydicarbonate, dicarbonate,
Diisobutylperoxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, diacetylperoxydicarbonate, dicyclohexylperoxydicarbonate, di(4-tert-butylcyclohexyl)peroxydicarbonate and isopropyl 5
ec-butylperoxydicarbonate); monoperoxycarbonates (e.g. tert-butyl peroxyisopropyl carbonate and tert-amyl peroxyisopropyl carbonate); diacetyl peroxide (e.g. diacetyl peroxide, dibenzoyl peroxide, dilauroyl peroxide); oxide and diisobutyryl peroxide); peroxy esters such as tert-butyl perpivalate, tert-butyl peroctoate and tert-butyl perneodecanoate.

One or more initiators may be used as desired.

When used, the amount of initiator present in the polymerizable formulation may vary over a wide range. Typically, the weight ratio of initiator to total ethylenically unsaturated material present in the formulation is about 0.5:
It is in the range of 100 to 7:100. Often the weight ratio ranges from about Igloo to about 5:100. Approximately 1.5
:100 to about 2.5:100 are preferred.

It will be appreciated by those skilled in the art that the most preferred weight ratio will depend on the nature and proportions of the various ethylenically unsaturated materials present in the formulation as well as the nature of the initiator used (its active oxygen content).

other ethylenically unsaturated compounds (e.g. acrylates,
methacrylate, methacrylate, haloacrylate)
, vinyl-functional compounds, other allylic-functional compounds, alkyl- or halogen-substituted allylic-functional compounds, and/or esters of ethylenically unsaturated dicarboxylic acids may be present in the polymerizable formulation. .

When other ethylenically unsaturated compounds are present, they usually comprise from about 1 to about 50% by weight of the polymerizable formulation. Often they will be from about 2 to about 25% by weight of the polymerization formulation. About 5 to about 20% by weight is preferred.

Other materials present in the polymerization formulation include mold release agents and dyes.

The list of other substances listed above is by no means exhaustive.

These and other elements may be used in amounts customary for their customary purposes so long as they do not interfere with the formation of solid, crosslinked polymers.

In many cases, the polymerizable formulation will consist of from about 50 to about 99.5 weight percent of the partially polymerized monomer composition.

Often, the polymerizable formulation will consist of about 70 to about 98 weight percent of the partially polymerized monomer composition. About 80 to about 95% by weight is preferred. Preferably, the partially polymerized monomer composition used in the polymerizable formulation is essentially free of the solvent in which the monomer composition is formed.

In the polymerizable formulation, the ethylenically unsaturated material should be in the form of a solution in the proportions used. Insoluble materials, such as pigments, may be present, although this is not preferred.

The polymerizable formulations of the present invention are typically prepared by mixing various components. The mixture may be heated when desired to promote dissolution of the components. However, if an initiator is present during heating, the temperature usually must be maintained below the temperature at which polymerization begins.

It is preferred to heat without an initiator, and to cool the resulting solution and then incorporate the initiator and other ingredients that readily go into solution.

The formulations of the present invention may be radically polymerized by conventional techniques to polymerize (allylic carbonate)-containing formulations to form solid, crosslinked polymers.

Preferably, polymerization is accomplished by heating the radical initiator-containing polymerizable formulation to an elevated temperature. Typically, polymerization is conducted at temperatures ranging from about 8°C to about 100°C. Often post-cured. That is, the formulation is heated for more than the time believed necessary to substantially fully polymerize the formulation. Post-curing is often performed at temperatures above about IOθ°C at which thermal decomposition provides an undesirable degree of yellowness (e.g., about 125°C).
°C) at a lower temperature for a sufficient time to achieve a substantially constant or maximum Barcol hardness.

For example, when following the curing cycle shown in Table 2 below:
The polymer is heated at +00° for an additional 1-4 hours or more.
You may leave it as C. While not wishing to be limited by theory, the additional 1 to 4 hours of post-cure accounts for 83% of the peroxide initiator remaining unreacted at the end of a standard 18-hour cure cycle primarily due to initiation and chain termination reactions. Believed to cause ~99.9% decomposition. Additionally, an additional 1-4 hours of curing often increases Barcol hardness by about 5-8 units.

In many cases, polymerizability follows the shape of the final solid polymerized material in the polymerization. For example, the formulation is poured onto a flat surface;
It is heated to cause polymerization, thereby forming a plate or coating.

Further illustratively, the polymerizable formulation is placed in a mold (e.g., a glass mold), and the mold is heated to effect polymerization to form a shaped article (e.g., a lens blank or lens). .

In a more particularly preferred embodiment, the formulation is poured into a lens mold and polymerized therein to create an ophthalmic lens.

In another particularly preferred embodiment, the formulation is poured into a lens blank mold where it polymerizes to form the lens blank.

Various curing cycles or time-temperature sequences may be used during the polymerization. Typically, the curing cycle used will vary depending on several factors, such as the size of the cast, the nature of the initiator, and the reactivity of the ethylenically unsaturated material. Several standard curing cycles have been identified for casting ophthalmic lenses or lens blanks, and these are shown in Tables 1-
4. These standard cure cycles are useful in forming polymers according to the present invention, however, they are only exemplary and others may be used.

Table 1 Table 3 OO (End of Cycle) Table 2 (End of Cycle) (End of Cycle) Table 4 Standard Cumulative Curing Cycle Time for Tertiary Butyl Peroxy Isopropyl Carbonate Oven Temperature, °C (End of Cycle) Typically, thermosetting polymers It has a Percoll degree of at least 155 seconds of O. Often the Barcol hardness is at least about 15, preferably at least about 25. As used herein, 155 seconds Percoll is ASTM test method D2583-8 using a Barcoll indenter and using a scale reading 15 seconds after the indenter point is forced into the specimen.
1.

The present invention will be explained in more detail in the following examples, but should not be construed as being limited to these examples only. All parts and percentages herein are by weight unless otherwise noted.

Example ■ The solution is 4.4°-(1-methylethylidene)bis[phenol] bis(allyl carbonate) monomer 150
g, methylene chloride (450 m+2) and diisopropyl peroxydicarbonate (3 g). The solution was poured into a glass bottle.

The bottle was flushed with argon for 3 minutes, sealed, and placed in a 70°C water bath for 18 hours. I took the bottle out of the water bath and opened it. Hydroquinone monomethyl ether 0.0015
A solution in which polymerization was inhibited (inhibited solution) was prepared by mixing a methylene chloride solution in which g was dissolved with the material in the bottle. The methylene chloride solvent was removed from the two portions of the suppression solution under vacuum on a rotary evaporator to produce two product samples of gel-free, essentially methylene chloride-free, liquid, polymerizable partially polymerized monomer compositions. Infrared spectroscopy of the initial bis(allyl carbonate) monomer and the two product samples showed that the allylic utilization of the two product samples was 65.52% and 64.12%, respectively.
%.

Example ■ The solution is 4,4°-[1,3-phenylenebis(1methylethylidene)]bis[phenol] bis(allyl carbonate) monomer 50g1 methylene chloride 150g
It was prepared by mixing m12 and 0.75 g of diisopropyl peroxydicarbonate. The solution was poured into a glass bottle. The bottle was flushed with argon for 3 minutes, sealed, and placed in a 70°C water bath for 18 hours. I took the bottle out of the water bath and opened it.

A suppressor solution was prepared by mixing a methylene chloride solution in which 0.0005 g of hydroquinone monomethyl ether was dissolved with the bottle material. The methylene chloride solvent was removed from the two portions of the suppression solution under vacuum on a rotary evaporator to produce a gel-free and essentially methylene chloride-free sample. Infrared spectroscopy of the initial bis(allyl carbonate) monomer and the two product samples revealed that the allylic utilization of the two product samples was 5, respectively.
It showed that they were 7.54% and 59.23%.

Example ■ The solution was 50 g of 4.4°-[1,3-phenylenebis(!-methylethylidene)]bis[phenolcobis(allyl carbonate) monomer, 15 g of methylene chloride.
01(2) and 1.25 g of diisopropyl peroxydicarbonate. The solution was poured into a glass bottle. The bottle was purged with argon for 3 minutes, sealed, and placed in a 70"C water bath overnight. .The bottle was removed from the water bath and opened.Hydroquinone mono 4 thyl ether 0
．． An inhibitory solution was made by mixing 0005g with the bottle material. The methylene chloride solvent was removed from the two portions of the suppression solution under vacuum on a rotary evaporator to produce two product samples that were gel-free and essentially methylene chloride. Infrared spectroscopic analysis of the initial bis(allyl carbonate) monomer and the two product samples showed that the allylic utilization of the two product samples was 79.36% and 78.64%, respectively.

Although certain embodiments of the invention have been described in particular detail, this should not be taken as a limitation on the scope of the invention except insofar as the details are included in the claims.

Patent Applicant: PPG Industries, Inc.

Claims (1)

[Scope of Claims] 1. (a) At least one bis(allyl) of 4,4'-(alkylidene)bis[phenol]
ic) monomer, at least one bis(allylic carbonate) monomer of 4,4'-[phenylenebis(alkylidene)]bis[phenol] or a mixture thereof; (b) the allyl utilization of the composition;
A liquid, polymerizable, gel-free partially polymerized monomer-containing composition having a tilization of greater than 50%. 2. The composition of claim 1, wherein the allyl utilization is at least 51%. 3. The composition of claim 1, wherein the allyl utilization is at least about 55%. 4. The composition of claim 1, wherein the allyl utilization is at least about 60%. 5. The composition of claim 1, wherein the allyl utilization ranges from 51% to about 80%. 6. The composition of claim 1, wherein the allyl utilization ranges from about 55% to about 80%. 7. The composition of claim 1, wherein the allyl utilization ranges from about 60% to about 80%. 8. The monomer has the formula: OH-A-OH [where A is a ▲ mathematical formula, chemical formula, table, etc. ▼ However, each Q is independently an alkylidene containing 1 to about 5 carbon atoms, R is each independently hydrogen,
halogen, lower alkyl containing 1 to about 4 carbon atoms,
The value of methoxy or ethoxy and n is 0 or 1. ] One or more bisphenol compounds represented by bis(
2. The composition of claim 1, wherein the composition is an allylic carbonate monomer. 9. The composition according to claim 8, wherein Q is 1-methylethylidene. 10. The composition according to claim 8, wherein the bis(allylic carbonate) monomer is a bis(allyl carbonate) monomer. 11. The composition of claim 1 which is essentially solvent free. 12, monomer is 4,4'-(1-methylethylidene)
Bis[phenol], 4,4'-(1-methylethylidene)bis[2,6-dichlorophenol], 4,4'-
(1-methylethylidene)bis[2,6-dibromophenol] and 4,4'-[1,3-phenylenebis(
12. The composition according to claim 11, wherein the monomer is at least one bis(allyl carbonate) monomer of a bisphenol compound selected from [1-methylethylidene]]bis[phenol]. 13, monomer is 4,4'-(1-methylethylidene)
12. The composition of claim 11, which is a bis(allyl carbonate) monomer of bis[phenol]. 14. The composition according to claim 11, wherein the monomer is a bis(allyl carbonate) monomer of 4,4'-[1,3-phenylenebis(1-methylethylidene)]bis[phenol]. 15, (a) (i) at least one bis(allylic carbonate) monomer of 4,4'-(alkylidene)bis[phenol], of 4,4'-[phenylenebis(alkylidene)]bis[phenol]; A composition comprising partially polymerized monomers that are at least one bis(allylic carbonate) monomer or a mixture thereof, the composition comprising: (ii) an allylic utilization rate of the composition;
(a) a liquid, polymerizable, gel-free, partially polymerized monomer-containing composition having a utilization of greater than 50%; and (b) a wavy, polymerizable formulation of one or more other materials. 16. The formulation of claim 15 which is essentially solvent free. 17. The formulation of claim 16, wherein the one or more other substances are at least one thermal initiator. 18. The formulation of claim 17, wherein the thermal initiator is a peroxy initiator.