INHIBITED MONOMERIC COMPOSITIONS OF POLYOL(ALLYL CARBONATE), METHOD FOR THEIR PREPARATION AND METHOD FOR THEIR POLYMERIZATION

Abstract: A composition comprising monomeric polyol(allyl car­ bonate) and a viscosity stabilizing amount of a polymeriza­ ton inhibitor chosen from the group consisting of dihydroxy atomatics, dioxy aromatics, derivatives thereof, and mix­ tures thereof in the composition. A method of inhibiting the thermally induced thickening of compositions containing monomeric polyol(allyl carbon­ ate) comprising providing a viscosity stabilizing amount of a polymerization inhibitor chosen from the group consisting of dihydroxy aromatics, dioxy aromatics, derivatives thereof, and mixtures thereof in the composition. A method of polymerizing a composition of polyol(allyl carbonate) monomer comprising providing a viscosity stabi­ lizing amount of a polymerization inhibitor chosen from the group consisting of dihydroxy aromatics, dioxy aromatics, derivatives thereof, and mixtures thereof in the compositions whereby to inhibit the thermally induced thickening thereof, and thereafter, without removing the polymerization inhibi­ tor, adding a free radical polymerization initiator to the composition and heating the composition whereby to polymerize the composition.

Description: DESCRIPTION INHIBITED MONOMERIC COMPOSITIONS OF POLYOL(ALLYL CARBONATE), METHOD FOR THEIR PREPARATION AND METHOD FOR THEIR POLYMERIZATION The present invention relates to inhibited monomeric compositions of polyol(allyl carbonate), method for their preparation and method for their polymerization. Polyol(allyl carbonate) monomers polymerize through sites of allylic unsaturation. The thermodynamics and kinetics of allyl polymerization indicate a high activation energy is required for the polymerization, and that a high degree of chain transfer and chain termination occurs. These have the practical effect of making allyl monomers, e.g., allyl carbonate monomers, relatively stable to high temperatures during shipping and storage. However, it has been found that compositions containing a major portion of uncatalyzed polyol(allyl carbonate) monomer, especially compositions thickened by having dispersed polymer therein, are subject to thickening. This is especially so at temperatures above about 45 degrees Centigrade. By compositions containing a major portion of uncatalyzed -polyol(allyl carbonate) monomer we mean compositions having the properties of the monomer. It has now been found that this tendency toward thermally induced thickening may be reduced or even eliminated by the addition of a dihydroxy aromatic compound, dioxy aromatic compound, or derivative thereof e.g. alkyl ethers or benzyl ethers, to the composition of polyol(allyl carbonate) monomer. In the accompanying drawings: Figure I is a graphical representation of the data in Examples I and II, showing the viscosity versus time behaviour of unhibited diethylene glycol bis(allyl carbonate) and diethylene glycol bis(allyl carbonate) inhibited with various levels of hydroquinone monomethyl ether. Figure II is a graphical representation of the data in Examples I and III, showing the viscosity versus time behaviour of unhibited diethylene glycol bis(allyl carbonate) and diethylene glycol bis(allyl carbonate) inhibited with various levels of tertiary butyl catechol. Figure III is a graphical representation of the data in Examples I and IV showing the viscosity versus time behaviour of uninhibited diethylene glycol bis(allyl carbonate) and diethylene glycol bis(allyl carbonate) inhibited with various levels of hydroquinone. Figure IV is a graphical representation of the data in Examples I and V showing the viscosity versus time behaviour of uninhibited diethylene glycol bis(allyl carbonate) and diethylene gycol bis(allyl carbonate) inhibited with various levels of quinone. It has now been found that the presence of low levels, e.g., less than 20 parts per million; of poly merization inhibitors e.g., dioxyaromatics and dihydroxy aromatics, substantially reduce,and even eliminate the tendency of compositions of polyol(allyl carbon ate) monomer to thicken. While the mechanism of the thickening of polyol(allyl carbonate) compositions is not fully understood, and while not wishing to be bound by this explanation, it is believed that thermally initiated polymerization may occur at sites of allyl unsaturation. It is possible that the presence of trace amounts of glycols, carbonates, allyl carbonates, glycol carbonates, and the like may enhance the postulated non-catalytic, thermal polymer ization. According to the present invention there is ¯¯provided a composition comprising monomeric polyol(allyl carbonate) and a viscosity stabilizing amount of a polymerization inhibitor chosen from the group consist ing of dioxyaromatics, dihydroxyaromatics, derivatives thereof and mixtures thereof. The invention also includes a method of inhibiting the thermally induced thickening of compositions containing monomeric poly(allyl carbonate) comprising providing a viscosity stabilizing amount of a polymerization inhibitor chosen from the group consistingof dihydroxy aromatics, dioxy aromatics, derivatives thereof, and mixtures thereof in the composition. - The invention further includes a method of polymerizing a composition of polyol(allyl carbonate) monomer comprising providing a viscosity stabilizing amount of a polymerization inhibitor chosen from the group consisting of dihydroxy aromatics,dioxy aromatics, derivatives thereof, and mixtures thereof in the composition where to inhibit the thermally induced thickening thereof, and thereafter,without removing the polymerization inhibitor, adding a free radical polymerization initiator to the composition and heating the composition whereby to polymerize the composition. As used herein, the term "polymerization inhibitor" refers to an additive to the monomeric polyol(ally carbonate) that reduces and even prevents uncatalyzed, thermal polymerization of diol bis(allyl carbonate) to form poly[polyol bis(allyl carbonate)] under conditions of storage that otherwise would permit thermal polymerization. The preferred, inhibitors are those which when added to the monomeric polyol(allyl carbonate) at concentrations of less than 20 parts per million, basis monomer,maintain the viscosity of iponomeric polyol bis(allyl carbonate) stored at a temperature of about 45 degrees Centigrade below twice the original viscosity after four months, below four times the original viscosity after six months, below eight times the original viscosity after eight months, and below sixteen times the original viscosity after ten months. More preferred inhibitors are those that, when present at the 5 parts per million level, maintain the viscosity within three times the original viscosity after ten,months of storage at 45 degrees Centigrade. Especially preferred are those inhibitors that, when present at the 5 parts per million level, maintain the viscosity within twenty percent of the original :value after ten months of storage at 45 degrees Centigrade. As used herein, the term'"uncatalyzed polymerization" includes the thickening of the poly(ally carbonate) upon stranding without the addition of free radical polymer ization initiator thereto. As used herein, the term "catalyzed polymerization" means the polymerization of the polyol (allyl carbonate) after the addition of free radial polymerization initiator thereto. The inhibitors of the present invention are characterized by substantially complete effectiveness in preventing thickening of diol bis(allyl carbonate) compositions at temperatures of at least 45 degrees Centigrade for time periods of at least ten months, at additive concentrations of 20 parts per million or less of inhibitor, basis diol bis(allyl carbonate), and generally from about 2 to about 20 parts per million. By "substantially complete effectiveness" is meant that the viscosity of the additive containing diol bis(allyl carbonate) monomer is within ten percent of the original viscosity after ten months exposure to temperatures of 45 degrees Centigrade. The inhibitors of the invention are further characterized by the ability to permit polymerization to normal physical properties, e.g. abrasion resistance, impact strength, Barcol hardness, optical clarity, yellowness, and dyeability, with normal cure cycles, polymerization initiators, and polymerization initiator concentrations. Exemplary of the inhibitors of the invention are the monoaromatics, e.g. the quinones, the hydroquinones, and catechols, the diaromatics, e.g. the napthoquinone, and the higher aromatics, exemplified by anthraquinone, and substituted anthraquinone. Examples of the prepared inhibitors are dihydroxy benzenes, derivatives thereof, dioxy benzenes, derivatives thereof, and mixtures thereof the oxygens occupying positions that are either ortho or para to each other. Exemplary dihydroxy benzenes and derivatives thereof are hydroquinone, EMI7.1 mono-tertiary butyl hydroquinone, EMI7.2 toluhydroquinone, EMI7.3 catechol, EMI7.4 tertiary butyl catechol, EMI8.1 and the hydroquinone ethers, EMI8.2 where Rmay be for example a methyl group, as inzthyl hydroquinone monomethyl ether EMI8.3 or R may be for example an ethyl group, as in hydroquinone monoethyl ether, EMI8.4 or an aromatic group as in hydroquinone benzyl ether, EMI9.1 Exemplary aloxy Denzenes ana derivatives thereof include quinone, i.e., para-quinone, EMI9.2 ortho-quinone, EMI9.3 and toluquinone EMI9.4 Particularly preferred are the dihydroxy benzenes and derivatives thereof, e.g., hydroquinone, catechol, mono-tertiary butyl hydroquinone, toluhydroquinone, tertiary butyl catechol, hydroquinone monomethyl ether, hydroquinone monoethyl ether, and hydroquinone benzyl ether. Especially preferred are hydroquinone and hydroquinone monomethyl ether. The disclosed method of combating the tendency of polyol(allyl carbonate) monomer compositions to gel or thicken on storage, e.g., at elevated temperatures, may be utilized with various polyol(allyl carbonate) monomer compositions, for example, diol bis(allyl: carbonates), triol tris(allyl carbonates), tetra kis(allyl carbonates), and higher polyol(allyl carbonates). Diol bis(allyl carbonate) monomers which may be inhibited by the method of this invention are normally linear, liquid allyl carbonates, and, most commonly, are aliphatic diol bis(allyl carbonates) e.g., glycol bis (allyl carbonate) compounds, in which the allyl' groups may be substituted at the 2 position with a halogen, notably chlorine or bromine, or a 1 to 4 carbon alkyl group, generally a methyl or ethyl group; and the glycol group may be an alkylene, alkylene ether, alkylene polyether, alkylene carbonate, or alkylene polyether group having from 2 to 10 carbons and oxygens. These diol bis(allyl carbonate) monomers are represented by the formula: EMI11.1 where R1 and R3 are allyl or substituted allyl groups, and R2 is derived from a diol HOR20H and R2 being a diol fragment selected from alkylene groups, alkylene ether groups, alkylene polyether groups, and alkylene polycarbonate groups.as defined below. R1 and R3 are independently represented by the formula: EMI11.2 where RO may be hydrogen, halogen, or a 1 to 4 carbon alkyl group. Specific examples of R1 and R3 are allyl, 2-chloroallyl, 2-bromallyl, 2-iodoallyl, 2-fluoroallyl, 2-methall-yl, 2-ethylallyl, 2-isopropylallyl 2-n-propylallyl, and 2-n-bt làllyl groups. Most commonly, R1 and R3 are allyl groups, H2C = CH - CH2-. Such compounds and methods for making them are disclosed in U.S. Patents 2,370,567 and 2,403,113. Specific examples of R2 are alkylene groups such as ethylene, trimethylene, methylethylene, tetrameth ylene, ethylethylene, pentamethylene, hexamethylene, 2-methylhexamethylene, octamethylene, and decamethylene groups, alkylene ether groups such as -CH2-O-CH2-, -CH2,CH2-O-CH2CH2-, -CH2-O-CH2-CH2-, and -CH2CH2CH2- O-CH2CH2CH2-, alkylene polyether groups such as -CH2CH2 -O-CH,CH2-O-CH,CH2 O-CH,CH,D-CH2CH2-, and -CH2-O-CH2- groups, and alkylene carbonate groups such as CH2CH2 -O-CO-O-CH2CH2 and -CH2CH2 - O-CH2CH2- O-CO-O-CH2 CH2-OCH2CH2- groups. Most commonly, R2 is -CH2CH2 - or CH2CH2-O-CH2 CH2 -. Specific examples of diol bis(allyl carbonate) monomers in which the method herein contemplated is useful are ethylene glycol bis (2-chloroallyl carbonate), diethylene glycol bis(2-methyallyl carbonate), triethylene glycol bis(allyl carbonate), propylene glycol bis(2-ethylallyl carbonate), 1,3propanedoil bis(allyl carbonate), 1,3-butanedoil bis(allyl carbonate), 1,4-butanedoil bis(2-bromallyl carbonate), dipropylene glycol bis(allyl carbonate), trimethylene glycol bis (2-ethylallyl carbonate), and pentamethylene glycol bis(allyl carbonate). Commercially important diol bis(allyl carbonate) monomers which may be inhibited or stabilized by the method herein contemplated are: EMI12.1 Alternatively, the method of this invention is useful in inhibiting thermal polymerization in aromatic biseallyl carbonates), e.g., bisphenol-A bis(allyl carbonates and ethoxylated bis phenol-A-bis(allyl carbonate). Triol tris(allyl carbonates) which may be inhibited by the method of this invention are represented by the formula EMI13.1 where R4 is an organic moiety chosen from the group consisting of moieties derived from polyols and extended polyols, most frequently a triol or extended triol where the hydroxyl groups of the precursor polyol R4(OH) n are non-vicinal. While the functionality is shown as tris functionality, it is to be understood that in higher polyols n is greater than 2, e.g., above about 2.2, representing a mixture of diols and higher polyols, to about 8 representing a derivative of trimeric pentaerythritol. By "non-vicinal" it is meant that the hydroxyl groups are not on adjacent carbons. Specific triol precursors useful in'preparing the tris(allyl carbonate) materials useful in this invention are triols with primary or secondary hydroxyl groups. Triols having primary hydroxyl groups are preferred precursors. One such class of triols are l,l,l-trimethylol alkanes. Also useful are extended trimethylol alkane tris(allyl carbonate) monomers such as lactone extended trimethylol alkanes and alkyl oxide extended trimethylol alkanes,. By and "extended triol" is meant the reaction product having terminal hydroxyl groups of the triol and a suitable reactant, i.e., one that reacts with a triol to form another triol e.g., an alkyl oxide or a lactone. Typical lactone extended trimethylol alkanes include S-caprolactone extended trimethylol methane, ±-caprolactone extended trimethylol ethane, ±-caprolactone extended trimethylol propane, and -caprolactone extended trimethylol butane. Typical alkyl oxide extended triols include ethylene oxide extended trimethylol methane, ethylene oxide extended trimethylol ethane, ethylene oxide extended trimethyl ol propane, ethylene oxide extended trimethylol butane, propylene oxide extended trimethylol methane, propylene oxide extended trimethylol methane, propylene oxide extended trimethylol ethane and propylene oxide extended trimethylol butane. The preferred polyols meeting these requirements have the general formula R4(OH)n where n is greater than 2 up to about 8 and generally is about 3.R4 can be, for example, EMI15.1 where RA is H, -CH3, -CH2CH3, SCH2CH2CH3 or -±H2CH2CH3, and 11, 12 and 13 are each integers from o to 5 and the sum of 11 + 12 + 13 is 2 or more and generally from 2 to 8, although values as high as 15 are possible. The value of m depends on the lactone utilized to extend the polyol and is generally 4 or 5. The chain extending lactone may be for example a delta lactone having the formula EMI15.2 which can be substituted with hydrogen, methyl groups, or ethyl groups. According to a still further exemplification, the chain extending lactone group can be an epsilon lactone having the formula: EMI16.1 where R5 is hydrogen, a methyl group, or an ethyl group and where R5 can be on any of the carbons other than the carbonyl carbon. One exemplary triol is Union Carbide Corporation NIAXPCP-0301 brand epsilon-caprolactone extended trimethylol propane. According to a still further exemplification, R4 can be EMI16.2 where RA is as defined previously, 11, 12 and 13 are integers from 0 to 5 anddthe sum of 11 + 12 + 13 is 2 or more and generally from 2 to 8, although values as high as about 15 are possible, and X is H or CH3. The chain extenders may be ethylene oxide groups as exemplified by Upjon ISONOL 93 ethylene oxide extended trimethylol propane. Alternatively, the extenders may be propylene oxide groups as in BASF=Wyandotte PLURACOL TP brand propoxylated trimethylol propane. According to a still further exemplification, R4(OH)3 may be an extended glycerol, for example, ethylene oxide extended glycerol having the general formula: EMI17.1 or propylene oxide extended glycerol having the formula: EMI17.2 or a lactone extended glycerol having the formula: EMI17.3 where m and .11, 12 and 13 are as defined above. Typical propoxylated glycerines are DOW VORANOL 2025 brand propoxylated glycerine having a molecular weight of about 260 grams per gram mole, DOW VORANOL 2070 brand propoxylated glycerine having a molecular weight of about 700 grams per gram mole, and BASF-Wyandotte PLURACOL GP730 brand propoxylated glycerine having a molecular weight of about 730 grams per mole. While the compositions are referred to as being monomeric compositions of polyol(allyl carbonate), it is to be understood that they may be compositions of polyol(allyl carbonate) monomer having polymers dispersed therein, e.g., as described in the U.S. Patent No. 4346197 (U.K. Patent Application No. 38363/81) or with polymer and colorants dispersed therein, as described in European Patent Application NoR 82306167.6, or with polymer and multifunctional acrylate monomers dispersed therein, as described in copending U.S. Application Serial No. 362,705, -filed March 29, 1982, of Carl W. Eads and Ronald L. Haynes for MONOMERIC COMPOSITION OF A DIOL BIS (ALLYL CARBONATE), A DISPERSED POLYMER, AND A MULTIFUNCTIONAL ACRYLATE MONOMER AND POLYMERS PREPARED THEREFROM. The inhibitors herein contemplated are effective to substantially prevent the uncatalyzed thickening of the polyol(allyl carbonates) at low concentrations of additive. Moreover, the concentration of additive is low enough to avoid inhibition of the free radical catalyzed polymerization of polyol(allyl carbonate). The polymerization of the polyol(allyl carbonate) composition is initiated by the creation of active centers, e.g., free radicals. Useful polymerization initiators are organic peroxy initiators. Examples of organic peroxy polymerization initiators are isobutyryl peroxide, di(2-ethylhexyl) peroxydicarbonate; acetyl cyclohexane sulfonyl peroxide; dicsec-butyl) peroxydicarbonate, diisopropyl peroxydicarbonate;: 2,4dichlorobenzoyl peroxide, t-butyl peroxypivalate; decanoyl peroxide, lauroyl peroxide, propionyl peroxide; 2,5-dimethyl -2,5-bis(2-ethyl hexylperoxy) hexane, acetyl peroxide; succinic acide peroxide; t-butyl peroxyoctoate; benzoyl peroxide; p-chlorobenzoyl peroxide; t-butyl peroxyisobutyrate; t-butyl peroxymaleic acid; bis(l-hydroxycyclo hexyl) peroxide, l-hydroxy-l'-hydroperoxy dicyclohexyl peroxide; t-butyl peroxyisopropyl carbonate; 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane; t-butyl peroxyacetate; methyl ethyl ketone peroxides; di-t-butyl diperoxyphthalate and t-butyl peroxybenzoate. According to one exemplification of the invention, 20 part per million of hydroquinone mono-methyl ether, basis monomeric composition, is added to industrial diethylene glycol bis-(allyl carbonate) monomer containing from about 80 to about 90 weight percent diethylene glycol bis(allyl carbonate) monomer, balance impurities in the monomer, e.g., diethylcne glycol, diethylene glycol mono allyl carbonate, oligomeric compounds, diallyl carbonate, diethylene glycol polycarbonate, or diethylene glycol carbonate. The initial viscosity of the composition is from about 15 to about 20 centistokes. After ten months of storage at 45 degrees Centigrade the viscosity of the composition is still about 15 to about 20 centistokes. Thereafter the composition is polymerized by the addition of 3.5 weight percent isopropyl peroxydicarbonate to the composition, and heating from about 27 degrees Centigrade to about 100 degrees Centigrade over a period of sixteen to twenty four hours. The resulting polymerizate is a rigid solid. The following Examples are illustrative. Example I A test was conducted to determine the effect of heat on a monomeric composition of diethylene glycol bis(allyl carbonate). A four ounce narrow mouth, screw top bottle was filled with PPG Industries, Inc. CR-39 diethylene glycol bis(allyl carbonate). The screw top was loosely fitted to allow for pressure relief, and the sample was placed in an air circulating oven at 45 degrees Centigrade. The sample was removed periodically for viscosity measurement. the viscosities shown in Table I, below, were obtained. Table I Viscosity of Uninhibited Diethylene Glycol Bis(Allyl Carbonate) Time Viscosity (months) (centistokes) 0 18.0 4 38.1 6 78.7 8 156 10 350 After ten months the composition was polymerized by adding 3.5 weight percent isopropyl peroxidicarbonate to a portion of the sample, and placing the portion of the sample between two four inch by seven inch by 1/4 inch glass molds separated by a 1/4 inch rubber gasket. The portion of the sample was cured according to the cure cycle shown in Table II. Table II Time-Temperature Sequence for Diisopropyl Peroxydicarbonate Cure Cumulative Time (hours) Temperature, C 0 42 4 44 6 45 8 47 10 48 12 50 14 52 16 54.5 18 57 20 61 22 69 23 79 23.6 84 24 98 24.1 100 The resulting sheet has 3.9 percent yellowness, and a 15 second Barcol hardness of 35-29. Example II A series of tests were conducted to determine the effect of various levels of hydroquinone monomethyl ether on a monomeric composition of ethylene glycol bis(allyl carbonate). A composition was prepared containing 20 parts per million of hydroquinone monomethyl ether, balance PPG Industries, Inc. CR-39 diethylene glycol bis(allyl carbonate). The samples were then diluted with PPG Industries, Inc., CR-3 diethylene glycol bis(ally carbonate) to give samples containing, respectively, 2 parts per million, 5 parts. per million, and 10 parts per million of hydroquinone monomethyl ether. The four samples were then stored and tested as described in Example I, above. The results shown in Table III, below, were obtained: Table III Viscosity of Hydroquinone Monomethyl Ether Inhibited Diethylene Glycol Bis(Allyl Carbonate) Amount of Hydroquinone Viscosity Monomethyl Ether (centistokes) (parts per million) 2 5 10 20 Time 0 17.8 17.7 17.9 17.6 (months) 4 21.8 17.7 17.7 17.6 6 26.3 18.0 17.4 17.6 8 37.4 17.8 17.9 17.8 10 54 17.9 17.9 17.7 The above viscosities are shown graphically in Figure 1, with the viscosities of the uninhibited material. After ten months a portion of each sample was polymerized as described in Example I, above. The results obtained in Table IV, below, were obtained. Table IV Effect of Hydroquinone Monomethyl Ether on Properties of Polymerized Product Amount of Hydroquinone Monomethyl Ether parts per-million) 2 5 10 20 Yellowness 4.1 3.6 4.2 4.3 (percent) Barcol Hardness 35-29 34-28 34-28 35-29 (15 second) Example III The procedure of Example II, above, was repeated, with tertiary butyl catechol substituted for the hydroquinone monomethyl ether. The samples has the viscosities shown in Table V, below: Table V Viscosity of Tertiary-Butyl Catechol Inhibited Diethylene Glycol Bis(Allyl Carbonate) Amount of Tertiary-Butyl Viscosity Catechol (centistokes) (parts per million) ¯ 2 5 10 20 Time 0 17.8 17.8 18.2 18.0 (months) 4 17.8 17.7 17.7 17.8 6 24.4 17.9 17.6 17.9 8 3?.1 17.7 17.8 17.9 10 54.0 17.5 17.7 17.6 The data of Table V and Table I of Example I are represented in Figure 2. The polymers cast from the samples after ten months of storage had the properties shown in Table VI below: Table VI Effect of Tertiary-Butyl Catechol on Properties of Polymerized Product Amount of (parts per million) 2 5 10 20 Yellowness 4.0 4.0 4.2 4.5 (percent) Barcol Hardness 35-29 36-29 36-30 36-30 (15 second) Example IV The procedure of Example. II, above, was repeated, with hydroquinone substituted for the hydroquinone monomethyl ether. The samples had the viscosities shown in Table VII below: Table VII Viscosity of Hydroquinone Inhibited Diethylene Glycol Bis(Allyl Carbonate) Amount of Hydroquinone (parts per million) 2 5 10 20 Time 0 17.7 17.6 18.0 17.6 (months) 4 22.2 18.0 20.0 17.6 6 26.8 18.2 17.4 17.4 8 33.3 19.2 18.8 17.6 10 40.9 20.0 18.0 ' 17.4 The data of Table VII and Table I of Example I are presented in Figure 3. The polymers cast from the samples after ten months of storage has the properties shown in Table VIII below: Table VIII Effect of Hydroquinone on Properties of Polymerized Product Amount of Hydroquinone warts ejmjillion per - - 10 20 Yellowness 3.8 3.7 4.0 4.2 (percent) Barcol Hardness 35-29 35-29 35-29 35-29 (15 second) Example V The procedure of Example II, above, was repeated with quinone substituted for the hydroquinone monomethyl ether. The samples has the viscosities shown in Table IX below: Table IX Viscosity of Quinone Inhibited Diethylene Glycol Bis(Allyl Carbonate) Viscosity Amount of Quinone (centistokes) (parts per million) 2 5 10 20 Time 0 17.8 18.1 17.9 18.1 (months) 4 32.4 27.2 19.9 17.9 6 48.9 35.3 22.9 17.9 8 --- 46.4 27.0 18.1 10 113.8 57.9 31.0 19.0 The data of Table IX and Table I of Example 1 are presented in Figure 4. The polymers cast from the samples afte ten months of storage had the properties shown in Table X below: Table X Effect of Quinone on Properties of Polymerized Product Amount of Quinone parts per million) 2 5 10 20 Yellowness 4.4 4.1 4.7 4.9 (percent) Barcol Hardness 35-29 35-29 35-29 35-29 (15 second) While the invention has been described with respect to specific exemplifications, embodiments, and examples, the scope is not to be limited thereby, but only by the claims appended hereto.

Claims: CLAIMS 1. A composition comprising monomeric polyol(allyl carbonate) and a viscosity stabilizing amount of polymerization inhibitor chosen from the group consisting of dihydroxy aromatics, dioxy aromatics, derivatives thereof, and mixtures thereof in the composition. 2. A composition according to claim 1, wherein the polymerization inhibitor is chosen from the group consisting of dihydroxy benzenes, dioxy benzenes, derivatives thereof, and mixtures thereof. 3. A composition according to claim 1 or 2, wherein the polymerization inhibitor is chosen from the group!consisting of hydroquinone, mono-tertiary butyl hydroquinone, toluhydroquinone, catechol, tertiary butyl catechol, hydroquinone monomethyl ether, hydroquinone monoethyl ether, hydroquinone benzyl ether, quinone, para-quinone, toluquinone, and mixtures thereof. 4. A composition according to claim 1, 2 or 3, wherein the composition contains from about 2 to about 20 parts per million of polymerization, inhibitor, basis polyol(allyl carbonate). 5. A composition according to any of claims 1 to 4, wherein the composition has a viscosity increase of less than ten percent at 45 degrees Centigrade measured over an interval of 10 months. 6. A composition comprising monomeric polyol (allyl carbonate) and a viscosity stabilizing amount of a polymerization inhibitor substantially as herein described with reference to and as illustrated in any of the Examples. 7. A method of inhibiting the thermally induced thickening of compositions containing monomeric polyol(allyl carbonate) comprising providing a viscosity stabilizing amount of a polymerization inhibitor chosen from the group consisting of dihydroxy aromatics, dioxy aromatics, derivatives thereof, and mixtures thereof in the composition. 8. A method according to claim 7, wherein the polymerization inhibitor is chosen from the group consisting of dihydroxy benzenes, dioxy benzenes, derivatives thereof, and mixtures thereof. 9. A method according to claim 7 or 8, wherein the polymerization inhibitor is chosen from the group consisting of hydroquinone, mono-tertiary butyl hydroquinone, toluhydroquinone, catechol, tertiary butyl cateckol, hydroquinone monomethyl ether, hydroquinone monoethyl ether, hydroquinone benzyl ether, quinone, para-quinone, toluquinone, and mixtures thereof. 10. A method according to claim 7, 8 or 9, wherein the composition contains from about 2 to about 20 parts per million of polymerization inhibitor, basis polyol(allyl carbonate). 11. A method according to any of claims 7 to 10, wherein the composition has a viscosity increase of less than ten percent at 45 degrees Centigrade measured over an interval of 10 months. 12. A method of inhibiting the thermally induced thickening of compositions containing monomeric polyol(allyl carbonate) substantially as herein described with reference to and as illustrated in any of the Examples. 13. A method of polymerizing a composition of polyol(allyl carbonate) monomer comprising providing a viscosity stabilizing amount of a polymerization inhibitor chosen from the group consisting of dihydroxy aromatics, dioxy aromatics,-erivatives thereof, and mixtures thereof in the composition whereby to inhibit the thermally induced thickening thereof, and thereafter, without removing the polymerization inhibitor, adding a free radical polymerization initiator to the composition and heating the composition whereby to polymerize the composition. 14. A method according to claim 13, wherein the polymerization inhibitor is chosen from the group consisting of dihydroxy benzenes, dioxy benzenes, derivatives thereof, and mixtures thereof. 15. A method according to claim 13 or 14, wherein the polymerization inhibitor is chosen from the group consisting of hydroquinone, mono-tertiary butyl hydroquinone, toluhydroquinone, catechol, tertiary butyl catechol, hydroquinone monomethyl ether, hydroquinone monoethyl ether hydroquinone benzyl ether, quinone, para-quinone, toluquinone, and mixtures thereof. 16. A method according to claim 13, 14 or 15, wherein the composition contains from about 2 to about 20 parts per million of polymerization inhibitor, basis polyol(allyl carbonate). 17. A methodiaccording to any of claims 13 to 16, wherein,prior to the addition of the free radical polymerization initiator, the composition of polyol(allyl carbonate) monomer has a viscosity increase of less then ten percent at 45 degrees Centigrade measured over an interval of 10 months. 18. A method of polymerizing a composition of .monomeric polyol(allyl carbonate) substantially as herein described with reference to and as illustrated in any of the Examples.

Inventors: LEATHERMAN, IVAN ROGER
Applicants: PPG INDUSTRIES, INC.
Application year: 1983
Main classification: C07C69
IPC codes: C09K15, C08F2, C08F18, C07C68