COMPOSITIONS CONTAINING 1,1-DI-SUBSTITUTED ALKENE COMPOUNDS FOR PREPARING POLYMERS HAVING ENHANCED GLASS TRANSITION TEMPERATURES

• US 20180037681A1
• Filed: 10/13/2017
• Published: 02/08/2018
• Est. Priority Date: 09/08/2014
• Status: Active Grant

• Current Assignee: Nippon Shokubai Company Limited
• Original Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Inventors: Sullivan, Jeffrey M., Palsule, Aniruddha, Holzer, Alexander R., Parab, Kshitij K., Doshi, Ami
• Granted Patent: US 9,890,227 B1
• Time in Patent Office: Days
• CPC Class Codes: C07C 69/593 Dicarboxylic acid esters having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 2/06 Organic solvent
• CPC Class Codes: C08F 22/10 Esters
• CPC Class Codes: C08F 222/145 the ester chains containing seven or more carbon atoms
• CPC Class Codes: C09J 135/02 Homopolymers or copolymers of esters C09J135/06, C09J135/08 take precedence

Abstract

The disclosure relates to compositions containing 1,1-disubstituted alkene compounds capable of preparing polymers having glass transition temperatures above room temperature. The present teaching also relates to polymers prepared 1,1-disubstituted 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-disubstituted alkene compounds.

Claims

1. A composition comprising one or more 1,1-dicarbonylsubstituted 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-disubstituted alkenes exhibit glass transition temperatures of less than 60°

C. and one or more; and

one or more multifunctional 1,1-dicarbonylsubstituted alkene compounds which comprise a core unit of two or more 1,1-dicarbonylsubstituted alkenes which correspond to the formula;

2. A composition according to claim 1 wherein the 1,1-dicarbonylsubstituted 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 second 1,1-disubstituted alkenes correspond to formula 3

4. A composition according to claim 3 wherein R² 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 1,1-dicarbonylsubstituted alkene compounds exhibit a purity of 95 mole percent or greater, have one mole percent or less of the analogous 1,1-disubstituted 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-dicarbonylsubstituted alkene compound.

6. A composition according to claim 1 wherein the one or more multifunctional 1,1-dicarbonylsubstituted alkene compounds are present in an amount of about 1 weight percent or greater to less than 100 weight percent.

7. A composition according to claim 1 wherein the one or more multifunctional 1,1-dicarbonylsubstituted alkene compounds are present in an amount of about 5 weight percent or greater about 30 weight percent or less.

8. A composition according to claim 1 wherein the Tg of the polymers prepared therefrom is 60°

C. or greater.

9. A composition according to claim 1 wherein the Tg of the copolymers prepared therefrom is 80°

C. or greater.

10. A composition comprising a copolymer prepared from a composition of claim 1.

11. A composition comprising a copolymer prepared from a composition of claim 1 having a glass transition temperature of 60°

C. or greater.

12. A composition according to claim 11 wherein the 1,1-dicarbonylsubstituted 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.

13. A composition according to claim 11 wherein the one or more second 1,1-disubstituted alkenes correspond to formula 3

14. A composition according to claim 13 wherein R² 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.

15. A composition according to claim 11 wherein the one or more 1,1-dicarbonylsubstituted alkene compounds exhibit a purity of 95 mole percent or greater, have one mole percent or less of the analogous 1,1-disubstituted 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-dicarbonylsubstituted alkene compound.

16. A composition according to claim 11 wherein the one or more multifunctional 1,1-dicarbonylsubstituted alkene compounds are present in an amount of about 1 weight percent or greater to less than 100 weight percent.

17. A composition according to claim 11 wherein the one or more multifunctional 1,1-dicarbonylsubstituted alkene compounds are present in an amount of about 5 weight percent or greater about 30 weight percent or less.

18. A composition according to claim 11 wherein the polymers 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.

19. A method comprising contacting one or more of the 1,1-dicarbonylsubstituted alkene compounds with one or more of the multifunctional 1,1-dicarbonylsubstituted 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-disubstituted alkene compounds.

20. A method according to claim 19 wherein the one or more multifunctional 1,1-dicarbonylsubstituted alkene compounds are present in an amount of about 1 weight percent or greater to less than 100 weight percent.