Compositions containing 1,1-disubstituted alkene compounds for preparing polymers having enhanced glass transition temperatures

Patent metadata

Field	Value
Publication number	US-9315597-B2
Application number	US-201514859992-A
Country	US
Kind code	B2
Filing date	Sep 21, 2015
Priority date	Sep 8, 2014
Publication date	Apr 19, 2016
Grant date	Apr 19, 2016

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.

First claim

What is claimed is:

1. A composition comprising about 10 weight percent or greater of one or more first 1,1-disubstituted alkene compounds wherein each carbonyl group independently has a hydrocarbyl group bonded to the carbonyl groups by a direct bond, an oxygen atom, a nitrogen atom or a sulfur atom wherein one or more of the hydrocarbyl groups comprise 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; and about 10 weight percent or greater of one or more second 1,1-disubstituted alkene compounds wherein each carbonyl group independently has a hydrocarbyl group bonded to the carbonyl groups by a direct bond or a heteroatom, and the hydrocarbyl groups are selected such that homopolymers prepared from the second 1,1-disubstituted alkenes exhibit glass transition temperatures of less than 60° C., wherein the first 1,1-disubstituted alkene compounds are different from the second 1,1-disubstituted alkene compounds, and wherein a polymer prepared from the composition exhibits a glass transition temperature of greater than 35° C.

2. A composition according to claim 1 wherein the second 1,1-disubstituted 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 or the heteroatom, 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 first 1,1-disubstituted alkenes correspond to one of formulas 1 or 2

and the one or more second 1,1-disubstituted alkenes correspond to formula 3

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 a hydrocarbyl group selected such that homopolymers prepared from the alkenes of formula 3 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 first 1,1-disubstituted alkene compounds have at least one hydrocarbyl group which is 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 and at least one hydrocarbyl group which is alkyl with a primary 1 carbon atom or a secondary 1 carbon atom and a primary 2 carbon atom, alkenyl with a primary 1 carbon atom or a secondary 1 carbon atom and a 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, a polyalkylene ether.

6. A composition according to claim 1 wherein the one or more first 1,1-disubstituted alkene compounds and the one or more second 1,1-disubstituted alkene compounds each 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 or 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-disubstituted alkene compound.

7. A composition according to claim 1 wherein the one or more first 1,1-disubstituted alkene compounds contain one or more hydrocarbyl groups comprising menthyl, fenchyl, isobornyl, furfuryl, cyclohexyl, phenethyl, benzyl, tertiary butyl, 2-phenyl propyl and, or adamantyl.

8. A composition according to claim 1 which further comprises one or more multifunctional 1,1-disubstituted alkene compounds which comprise the core unit of two or more 1,1-disubstituted alkene 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.

9. A composition according to claim 1 wherein copolymers prepared from the composition exhibit a glass transition temperature determined according to the formula:
Tg=Y*W+V± 15°

wherein
Y is the mole percent of the first 1,1-disubstituted alkene compound;
W is the Tg of the first 1,1-disubstituted alkene compound minus the Tg of the second 1,1-disubstituted alkene compound: and
V is the Tg of the second 1,1-disubstituted alkene compound;
wherein Tg is expressed in ° C.

10. A composition comprising a copolymer prepared from about 10 weight percent or greater of one or more first 1,1-disubstituted alkene compounds wherein each carbonyl group independently has a hydrocarbyl group bonded to the carbonyl groups by a direct bond, an oxygen atom, nitrogen atom or a sulfur atom wherein one or more of the hydrocarbyl groups comprising an aryl group, aralkyl gr

Assignees

• Sirrus Inc

Inventors

• Sullivan Jeffrey M
• Palsule Aniruddha
• Holzer Alexander R
• Parab Kshitij K
• Doshi Ami

Classifications

• C07C69/593

  Dicarboxylic acid esters having only one carbon-to-carbon double bond · CPC title

• C08F2/06

  Organic solvent · CPC title

• C08F22/10 Primary

  Esters · CPC title

• C09J135/02

  Homopolymers or copolymers of esters (C09J135/06, C09J135/08 take precedence) · CPC title

• C08F222/145

  the ester chains containing seven or more carbon atoms · CPC title