Polyol(allyl carbonate) compositions and polymerizates prepared therefrom

Claim 2

A polymerizable liquid composition of substantially gel-free partially polymerized polyol(allyl carbonate) monomer characterized in having from 15 to 50 percent allylic utilization, a kinematic viscosity of from at least about 100 to about 100000 centistokes and a bulk density of from about 1.17 to about 1.23 grams per cubic centimeter.

Claim 3

The polymerizable composition of claim 1 wherein the polyol (allyl carbonate) monomer is represented by the graphic formula: wherein R 1 is an allyl radical represented by the graphic formula wherein R o is hydrogen, chlorine, bromine, or a C 1 - C 4 alkyl, R 2 is a polyvalent radical derived from an aliphatic or aromatic polyol containing from 2 to 5 hydroxy groups, and n is a whole integer from 2 to 5.

Claim 4

The polymerizable composition of claim 2 wherein R 1 is allyl, R 2 is derived from an aliphatic glycol containing from 2 to 10 carbon atoms or a bisphenol, and n is 2.

Claim 5

The polymerizable composition of claim 2 wherein R 1 is allyl, R 2 is derived from an alkylene glycol having from 2 to 4 carbon atoms, a poly (C 2 - C 4 ) alkylene glycol, or isopropylidene bis(para-phenol), and n is 2.

Claim 6

The polymerizable composition of claim 1 wherein the polyol(allyl carbonate) monomer is diethylene glycol bis(allyl carbonate).

Claim 7

The polymerizable composition of claim 5 wherein the diethylene glycol bis(allyl carbonate) has from 20 to 50 percent allylic utilization, and a kinematic viscosity of from 1000 to 40000 centistokes.

Claim 8

The polymerizable composition of claim 6 wherein the kinematic viscosity is from 1000 to 2000 centistokes.

Claim 9

The polymerizable liquid composition of claim 1 wherein there is present from 5 to 30 weight percent, basis the partially polymerized monomer of cure enhancing additive selected from the group consisting of: (1) monofunctional acrylate monomer, (2) polyfunctional acrylate monomer, (3) monofunctional monomer, and (4) mixtures thereof, said monofunctional monomer being different from said monofunctional acrylate monomer.

Claim 10

The polymerizable composition of claim 8 wherein: a) the polyol(allyl carbonate) monomer is represented by the graphic formula: wherein k 1 is an allyl radical represented by the graphic formula wherein R o is hydrogen, chlorine, bromine, or a C 1 - C 4 alkyl, R 2 is a polyvalent radical derived from an aliphatic or aromatic polyol containing from 2 to 5 hydroxy groups, and n is a whole integer from 2 to 5, b) the polyfunctional acrylate monomer is repre - sented by the graphic formula wherein R 5 is the organic residue of the C 2 -C 12 aliphatic polyol, R 5 (OH) i , R 4 is the acrylic acid moiety, CH 2 =C- , R' is hydrogen or a C 1 - C 4 R' alkyl, and i is a whole R' number from 2.to 5, c ) the monofunctional acrylate monomer is a C 1 - C 4 alkyl or C 5 - C 6 cycloalkyl ester of the acrylic and d) the monofunctional monomer is selected from the group consisting of C 1 - C 4 alkyl ester of unsaturated C 4 - C 6 dicarboxylic acids, vinyl esters of C 1 - C 3 saturated monocarboxylic acids and styrene.

Claim 11

The polymerizable composition of claim 9 wherein the cure enhancing additive is present in amounts of from 5 to 20 weight percent.

Claim 12

The polymerizable composition of claim 9 wherein the polyol(allyl carbonate) monomer is diethylene glycol bis(allyl carbonate), the polyfunctional acrylate monomer is selected from the group wherein R 4 is an acrylic acid or methacrylic acid moiety, R 5 is a C 2 - C 6 aliphatic polyol, and i is 2 or 3, the monofunctional acrylate monomer is selected from the group C 1 - C 2 alkyl or cyclohexyl esters of an acid selected from acrylic and methacrylic acid, and the monofunctional monomer is selected from the group C 1 - C 2 alkyl esters of maleic or fumaric acid, and vinyl acetate.

Claim 13

In a process for preparing a polymerizable liquid composition of substantially gel-free partially polymerized polyol(allyl carbonate) wherein the polyol(allyl carbonate) monomer is polymerized with a small amount of organic peroxide characterized by preparing a mixture of polyol(allyl carbonate) monomer and an organic solvent in which the monomer and homopolymer thereof is soluble, said solvent being non-reactive chemically with said monomer and homopolymer, and having a higher vapor pressure than said monomer, and polymerizing said monomer until from 15 to 50 percent of the allylic carbon-carbon linkages are consumed.

Claim 14

In a process for preparing a polymerizable liquid composition of substantially gel-free partially polymerized polyol(allyl carbonate) wherein the polyol(allyl carbonate) monomer is polymerized with a small amount of organic peroxide characterized by preparing a mixture of polyol(allyl carbonate) monomer and an organic solvent in which the monomer and homopolymer thereof is soluble, said solvent being non-reactive chemically with said monomer and homopolymer, and having a higher vapor pressure than said monomer, and polymerizing said monomer until from 15 to 50 percent of the allylic carbon-carbon linkages are consumed.

Claim 15

The process of claim 12 wherein the polyol(allyl carbonate) monomer is represented by the graphic formula: wherein R 1 is an allyl radical represented by the graphic formula wherein R is 0 hydrogen, chlorine, bromine, or a C l - C 4 alkyl, R 2 is a polyvalent radical derived from an aliphatic or aromatic polyol containing from 2 to 5 hydroxy groups, and n is a whole integer from 2 to 5.

Claim 16

The process of claim 12 wherein the organic solvent is a halogenated C 1 - C 2 hydrocarbon.

Claim 17

The process of claim 12 wherein the solvent is removed from the monomer and partially polymerized monomer.

Claim 18

The process of claim 12 wherein the polyol(allyl carbonate) monomer is diethylene glycol bis(allyl carbonate), the organic solvent is a chlorinated C 1 - C 2 hydrocarbon, the organic initiator is used in amounts of from 0.1 to 1.5 weight percent, based on the monomer, and the polymerization temperature is from 28°C to 100 o C.

Claim 19

The process of claim 16 wherein the ratio of organic solvent to monomer is from about 0.5 to 5 milliliters of solvent to one gram of monomer.

Claim 20

The process of claim 17 wherein the solvent is selected from the group consisting of methyl chloride, methylene chloride, ethyl chloride, ethylene dichloride, 1,1,2-trichloro-1,2,2-trifluoroethane and mixtures of such solvents.

Claim 21

A process for preparing a polymerizable liquid composition of gel-free partially polymerized polyol(allyl carbonate), which comprises (a) preparing a mixture of polyol(allyl carbonate) monomer and an organic solvent selected from C l - C 2 chlorinated solvents, the ratio of solvent to monomer being from 0.5 to 5 milliliters of solvent per gram of monomer, said polyol(allyl carbonate) being represented by the graphic formula: wherein R 1 is allyl, R 2 is derived from an alkylene glycol of from 2 to 4 carbon atoms, a poly (C 2 - C 4 ) alkylene glycol, or isopropylidene bis(para-phenol), and n is 2, (b) -polymerizing said monomer with from 0.5 to 1.5 weight percent of peroxydicarbonate ester initiator until from 20 to 50 percent of the allylic carbon-carbon linkages are consumed.

Claim 22

A process for preparing a polymerizable liquid composition of gel-free partially polymerized polyol(allyl carbonate), which comprises (a) preparing a mixture of polyol(allyl carbonate) monomer and an organic solvent selected from C l - C 2 chlorinated solvents, the ratio of solvent to monomer being from 0.5 to 5 milliliters of solvent per gram of monomer, said polyol(allyl carbonate) being represented by the graphic formula: wherein R 1 is allyl, R 2 is derived from an alkylene glycol of from 2 to 4 carbon atoms, a poly (C 2 - C 4 ) alkylene glycol, or isopropylidene bis(para-phenol), and n is 2, (b) -polymerizing said monomer with from 0.5 to 1.5 weight percent of peroxydicarbonate ester initiator until from 20 to 50 percent of the allylic carbon-carbon linkages are consumed.

Claim 23

The process of claim 19 wherein the peroxydicarbonate ester is selected from di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di- secondary butyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, dicetylperoxydicarbonate, dicyclohexyl peroxydicarbonate, di(4-tertiarybutyl cyclohexyl) peroxydicarbonate and mixtures thereof.

Claim 24

The process of claim 20 wherein the polyol(allyl carbonate) is diethylene glycol bis(allyl carbonate).

Claim 25

The process of claim 19 wherein the solvent is removed from the monomer and partially polymerized monomer, thereby resulting in a gel-free liquid polymerizable composition.