Compositions containing 1,1-di-carbonyl-substituted alkene compounds for preparing polymers having enhanced glass transition temperatures
The disclosure relates to compositions containing 1,1-di-carbonyl-substituted alkene compounds capable of preparing polymers having glass transition temperatures above room temperature. The present teaching also relates to polymers prepared 1,1-di-carbonyl-substituted alkene compounds which exhibit glass transition temperatures of 60° C. The disclosure also relate to methods for enhancing the glass transition temperatures of polymers prepared from 1,1-di-carbonyl-substituted alkene compounds.
1. A composition comprising one or more 1,1-dicarbonyl-substituted alkene compounds wherein each carbonyl group independently has a hydrocarbyl group bonded to the carbonyl groups by a direct bond, a heteroatom, and the hydrocarbyl groups are selected such that homopolymers prepared from the 1,1-di-carbonyl-substituted alkenes exhibit glass transition temperatures of less than 60° C., and
one or more multifunctional 1,1-dicarbonyl-substituted alkene compounds which comprise a core unit of two or more 1,1-dicarbonyl-substituted alkenes which correspond to the formula:
wherein:
R 1 is separately in each occurrence a hydrocarbyl group comprising an aryl group, aralkyl group, alkaryl group with the aryl group bonded to the 1 or 2 carbon atom, a cycloalkyl group, an alkyl group with a cycloalkyl group on the 1 or 2 carbon atom, or a branched alkyl group wherein the 1 carbon atom is a tertiary or the 1 and 2 carbon atoms are secondary;
R 2 is, separately in each occurrence, alkyl with a primary 1 carbon atom or a secondary 1 carbon atom and a primary second carbon atom, alkenyl with a primary 1 carbon atom or a secondary 1 carbon atom and a primary second carbon atom, alkaryl wherein the aryl group is bonded to a carbon atom which is 3 or more carbon atoms from X, alkyl group with a cycloalkyl group bonded to a carbon atom which is 3 or more carbon atoms from the X, a polyalkylene or ether;
R 3 is separately in each occurrence a polyvalent hydrocarbon group;
R′ is separately in each occurrence hydrocarbyl or hydrogen;
X is a heteroatom or a direct bond;
a is separately in each occurrence an integer of 1 or more;
b is separately in each occurrence an integer of 0 or more wherein the sum of a and b is 2 or greater and the number of valences of R 3 is equal to the sum of a and b;
wherein the one or more 1,1-dicarbonyl-substituted alkene compounds exhibit a purity of 95 mole percent or greater, have one mole percent or less of the analogous 1,1-di-substituted alkane, 1 mole percent or less of an impurity containing a dioxane group, about 1 mole percent of less of any impurity having the alkene group replaced by an analogous hydroxyalkyl group wherein mole percent is based on the total moles in the 1,1-dicarbonyl-substituted alkene compound; and the one or more multifunctional 1,1-dicarbonyl-substituted alkene compounds are present in an amount of about 1 weight percent to less than 100 weight percent.
2. A composition according to claim 1 wherein the 1,1-dicarbonyl-substituted alkenes have hydrocarbyl groups of alkyl with a primary 1 carbon atom or a secondary 1 carbon atom and primary 2 carbon atom, alkenyl with a primary 1 carbon atom or a secondary 1 carbon atom and primary 2 carbon atom, alkaryl wherein the aryl group is bonded to a carbon atom which is 3 or more carbon atoms from the direct bond, oxygen atom, nitrogen atom or sulfur atom, alkyl group with a cycloalkyl group bonded to a carbon atom which is 3 or more carbon atoms from the direct bond, oxygen atom, nitrogen atom or sulfur atom, or a polyalkylene ether.
3. A composition according to claim 1 wherein the one or more 1,1-di-carbonyl-substituted alkenes correspond to formula 3
wherein: R 2 is, separately in each occurrence a hydrocarbyl group selected such that homopolymers prepared having the selected hydrocarbyl groups exhibit glass transition temperatures of less than 60° C.; R′ is separately in each occurrence hydrocarbyl or hydrogen and X is a heteroatom or a direct bond.
4. A composition according to claim 3 wherein R 2 is separately in each occurrence alkyl with a primary 1 carbon atom or a secondary 1 carbon atom and primary 2 carbon atom, alkenyl with a primary 1 carbon atom or a secondary 1 carbon atom and primary 2 carbon atom, alkaryl wherein the aryl group is bonded to a carbon atom which is 3 or more carbon atoms from X, alkyl group with a cycloalkyl group bonded to a carbon atom which is 3 or more carbon atoms from the X, or a polyalkylene ether.
5. A composition according to claim 1 wherein the one or more multifunctional 1,1-dicarbonyl-substituted alkene compounds are present in an amount of about 5 weight percent to about 30 weight percent.
6. A composition according to claim 1 wherein the Tg of polymers prepared therefrom is 60° C. or greater.
7. A composition according to claim 1 wherein the Tg of copolymers prepared therefrom is 80° C. or greater.
8. A composition comprising a copolymer prepared from a composition comprising one or more 1,1-dicarbonyl-substituted alkene compounds wherein each carbonyl group independently has a hydrocarbyl group bonded to the carbonyl groups by a direct bond, a heteroatom, and the hydrocarbyl groups are selected such that homopolymers prepared from the 1,1-di-carbonyl-substituted alkenes exhibit glass transition temperatures of less than 60° C., and
one or more multifunctional 1,1-dicarbonyl-substituted alkene compounds which comprise a core unit of two or more 1,1-dicarbonyl-substituted alkenes which correspond to the formula:
wherein:
R 1 is separately in each occurrence a hydrocarbyl group comprising an aryl group, aralkyl group, alkaryl group with the aryl group bonded to the 1 or 2 carbon atom, a cycloalkyl group, an alkyl group with a cycloalkyl group on the 1 or 2 carbon atom, or a branched alkyl group wherein the 1 carbon atom is a tertiary or the 1 and 2 carbon atoms are secondary;
R 2 is, separately in each occurrence, alkyl with a primary 1 carbon atom or a secondary 1 carbon atom and a primary second carbon atom, alkenyl with a primary 1 carbon atom or a secondary 1 carbon atom and a primary second carbon atom, alkaryl wherein the aryl group is bonded to a carbon atom which is 3 or more carbon atoms from X, alkyl group with a cycloalkyl group bonded to a carbon atom which is 3 or more carbon atoms from the X, a polyalkylene or ether;
R 3 is separately in each occurrence a polyvalent hydrocarbon group;
R′ is separately in each occurrence hydrocarbyl or hydrogen;
X is a heteroatom or a direct bond;
a is separately in each occurrence an integer of 1 or more;
b is separately in each occurrence an integer of 0 or more wherein the sum or a and b is 2 or greater and the number of valences of R 3 is equal to the sum of a and b;
wherein the one or more multifunctional 1,1-dicarbonyl-substituted alkene compounds are present in sufficient amount to increase the glass transition temperatures of polymers prepared from the composition.
9. A composition according to claim 8 having a glass transition temperature of 60° C. or greater.
10. A composition according to claim 9 wherein the 1,1-dicarbonyl-substituted alkenes have hydrocarbyl groups of alkyl with a primary 1 carbon atom or a secondary 1 carbon atom and primary 2 carbon atom, alkenyl with a primary 1 carbon atom or a secondary 1 carbon atom and primary 2 carbon atom, alkaryl wherein the aryl group is bonded to a carbon atom which is 3 or more carbon atoms from the direct bond, oxygen atom, nitrogen atom or sulfur atom, alkyl group with a cycloalkyl group bonded to a carbon atom which is 3 or more carbon atoms from the direct bond, oxygen atom, nitrogen atom or sulfur atom, or a polyalkylene ether.
11. A composition according to claim 9 wherein the one or more 1,1-di-carbonyl-substituted alkenes correspond to formula 3
wherein: R 2 is, separately in each occurrence a hydrocarbyl group selected such that homopolymers prepared having the selected hydrocarbyl groups exhibit glass transition temperatures of less than 60° C.; R′ is separately in each occurrence hydrocarbyl or hydrogen and X is a heteroatom or a direct bond.
12. A composition according to claim 11 wherein R 2 is separately in each occurrence alkyl with a primary 1 carbon atom or a secondary 1 carbon atom and primary 2 carbon atom, alkenyl with a primary 1 carbon atom or a secondary 1 carbon atom and primary 2 carbon atom, alkaryl wherein the aryl group is bonded to a carbon atom which is 3 or more carbon atoms from X, alkyl group with a cycloalkyl group bonded to a carbon atom which is 3 or more carbon atoms from the X, or a polyalkylene ether.
13. A composition according to claim 9 wherein the one or more 1,1-dicarbonyl-substituted alkene compounds exhibit a purity of 95 mole percent or greater, have one mole percent or less of the analogous 1,1-di-substituted alkane, 1 mole percent or less of an impurity containing a dioxane group, about 1 mole percent of less of any impurity having the alkene group replaced by an analogous hydroxyalkyl group wherein mole percent is based on the total moles in the 1,1-dicarbonyl- substituted alkene compound.
14. A composition according to claim 9 wherein the one or more multifunctional 1,1-dicarbonyl-substituted alkene compounds are present in an amount of about 1 weight percent to less than 100 weight percent.
15. A composition according to claim 9 wherein the one or more multifunctional 1,1-dicarbonyl-substituted alkene compounds are present in an amount of about 5 weight percent to about 30 weight percent.
16. A composition according to claim 9 wherein the copolymers exhibit a weight average molecular weight of about 2000 to about 3,000,000 daltons and a polydispersity of about 1.01 to 10 as determined Gel Permeation Chromatography.
17. A method comprising contacting one or more of the 1,1-dicarbonyl-substituted alkene compounds with one or more of the multifunctional 1,1-dicarbonyl-substituted alkene compounds according to claim 1 with a polymerization initiator under conditions to polymerize the composition and the glass transition temperature of the resulting polymer is increased over the glass transition temperature of a homopolymer of the one or more 1,1-di-carbonyl-substituted alkene compounds.
18. A method according to claim 17 wherein the one or more multifunctional 1,1-dicarbonyl-substituted alkene compounds are present in an amount of about 1 weight percent to less than 100 weight percent.