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

Patent metadata

Field	Value
Publication number	US-9790295-B2
Application number	US-201615088340-A
Country	US
Kind code	B2
Filing date	Apr 1, 2016
Priority date	Sep 8, 2014
Publication date	Oct 17, 2017
Grant date	Oct 17, 2017

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 one or more multifunctional 1,1-disubstituted alkene compounds 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, or a polyalkylene 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 1 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-disubstituted 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 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; and where the composition is utilized to prepare 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.

2. A composition according to claim 1 wherein R 3 is C 4-20 aralkylene or C 4-20 alkarylene groups.

3. A composition according to claim 1 wherein R 3 is the residue of 4,4′-(propane-2,2-diyl) diphenyl or 2,2′-methylenediphenyl.

4. 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 composition further comprises one or more multifunctional 1,1-disubstituted alkene compounds 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, or a polyalkylene 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-disubstituted 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 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; and where when the composition is utilized to prepare polymers, 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 by Gel Permeation Chromatography.

5. A composition according to claim 4 wherein b is 1 or more.

6. A composition according to claim 4 which comprises about 1 percent by weight or greater of one or more multifunctional 1,1-disubstituted alkene compounds.

7. A composition according to claim 4 which comprises about 1 percent by weight to about 30 percent by weight of one or more multifunctional 1,1-disubstituted alkene compounds.

8. A composition according to claim 4 which comprises about 5 percent by weight to about 15 percent by weight of the one or more multifunctional 1,1-disubstituted alkene compounds.

9. 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; or 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, 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 composition further comprises one or more multifunctional 1,1-disubstituted alkene compounds 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

Assignees

• Sirrus Inc

Inventors

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

Classifications

• C08F22/10 Primary

  Esters · CPC title

• C07C69/593

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

• C09J135/02

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

• C08F2/06

  Organic solvent · CPC title

• C08F222/14

  Esters having no free carboxylic acid groups {, e.g. dialkyl maleates or fumarates} · CPC title