Emulson polymers including one or more 1,1-disubstituted alkene compounds, emulson methods, and polymer compositions

Patent metadata

Field	Value
Publication number	US-10081685-B2
Application number	US-201715467330-A
Country	US
Kind code	B2
Filing date	Mar 23, 2017
Priority date	Sep 8, 2014
Publication date	Sep 25, 2018
Grant date	Sep 25, 2018

Abstract

The present teachings show that it is possible to polymerize 1,1-disubstituted alkene compounds in an emulsion (for example using a water based carrier liquid), despite the possible reactions between the monomer and water. Polymerization of 1,1-disubstituted alkene compounds in an emulsion provides opportunities to better control the polymerization compared with bulk polymerization. The emulsion polymerization techniques can be employed for preparing homopolymers, copolymers (e.g., random copolymers), and block copolymers.

First claim

What is claimed is:

1. A process comprising the steps of:
i) agitating a mixture comprising: about 30 weight percent or more of a carrier liquid, a surfactant, and 10 weight percent or more of one or more monomers to form micelles of the one or more monomers in the carrier liquid, wherein the one or more monomers includes one or more 1,1-disubstituted alkenes;
ii) adding an activator to the carrier liquid after forming the micelles,
iii) reacting the activator with at least one of the monomers in the micelle for initiating the anionic polymerization of the one or more monomers; and
iv) anionically polymerizing the one or more monomers to form a polymer;

wherein the carrier liquid includes water and the mixture includes about 30 weight percent or more of the water.

2. The process of claim 1 , wherein the carrier liquid consists essentially of water.

3. The process of claim 1 , wherein the carrier liquid consists entirely of water and the activator includes an ionic metal amide, an hydroxide, a cyanide, a phosphine, an alkoxide, an amine, an organometallic compound, or a metal benzoate.

4. The process of claim 1 , wherein the molar ratio of the one or more monomers to the activator is greater than about 50:1.

5. The process of claim 3 , wherein the molar ratio of the one or monomers to the activator is from about 100:1 to about 20,000:1.

6. A process comprising the steps of:
i) agitating a mixture comprising: about 25 weight percent or more of a carrier liquid, a surfactant, and one or more monomers to form micelles of the one or more monomers in the carrier liquid, wherein the one or more monomers includes one or more 1,1-disubstituted alkenes;
ii) reacting an activator with at least one of the monomers in the micelle for initiating the anionic polymerization of the one or more monomers; and
iii) anionically polymerizing the one or more monomers to form a polymer;
wherein the wherein the molar ratio of the one or monomers to the activator is from about 50:1 to about 20,000:1, and wherein the polymer has a number average molecular weight of about 700 g/mole or more, and the carrier liquid consists essentially of water.

7. The method of claim 6 , wherein the one or more 1,1-disubstituted alkenes includes methyl propyl methylene malonate, dihexyl methylene malonate, di-isopropyl methylene malonate, butyl methyl methylene malonate, ethoxyethyl ethyl methylene malonate, methoxyethyl methyl methylene malonate, hexyl methyl methylene malonate, dipentyl methylene malonate, ethyl pentyl methylene malonate, methyl pentyl methylene malonate, ethyl ethylmethoxy methylene malonate, ethoxyethyl methyl methylene malonate, butyl ethyl methylene malonate, dibutyl methylene malonate, diethyl methylene malonate (DEMM), diethoxy ethyl methylene malonate, dimethyl methylene malonate, di-n-propyl methylene malonate, ethyl hexyl methylene malonate, methyl fenchyl methylene malonate, ethyl fenchyl methylene malonate, 2-phenylpropyl ethyl methylene malonate, 3-phenylpropyl ethyl methylene malonate, or dimethoxy ethyl methylene malonate.

8. The method of claim 7 , wherein the polymer includes a first 1,1-disubstituted alkene and a second 1,1-disubstituted alkene.

9. The method of claim 8 , wherein the resulting polymer includes a first polymer block including about 10 weight percent or more of a first 1,1-disubstituted alkene; and a second polymer block including less than 10 weight percent of the first 1,1-disubstituted alkene.

10. The method of claim 7 , wherein the polymer is a random copolymer including the 1,1-disubstituted alkene and a second monomer.

11. A method comprising the steps of:
i) emulsion polymerizing one or more monomers including one or more 1,1-disubstituted alkenes; and
ii) quenching the polymerization by adding an acid polymerization terminator to the emulsion;
wherein the polymerization is an anionic polymerization; the emulsion includes 30 weight percent or more of a carrier liquid, a surfactant, and 10 weight percent or more of the one or more monomers, and an activator;
wherein the carrier liquid includes water and the mixture includes about 30 weight percent or more of the water; and the molar ratio of the one or monomers to the activator is greater than about 50:1; and
wherein the conversion of the one or monomers to a polymer is about 80 weight percent or more.

12. The method of claim 11 , wherein the polymerization is at a temperature of about 40° C. or less; and the activator includes an ionic metal amide, an hydroxide, a cyanide, a phosphine, an alkoxide, an amine, an organometallic compound, or a metal benzoate.

13. The method of claim 11 , the polymer has a number average molecular weight of about 700 g/mole or more, and the carrier liquid consists essentially of water.

14. The method of claim 13 , wherein the one or more monomers includes
i) a first 1,1-disubstituted alkenes including methyl propyl methylene malonate, dihexyl methylene malonate, di-isopropyl methylene malonate, butyl methyl methylene malonate, ethoxyethyl ethyl methylene malonate, methoxyethyl methyl methylene malonate, hexyl methyl methylene malonate, dipentyl methylene malonate, ethyl pentyl methylene malonate, methyl pentyl methylene malonate, ethyl ethylmethoxy methylene malonate, ethoxyethyl methyl methylene malonate, butyl ethyl methylene malonate, dibutyl methylene malonate, diethyl methylene malonate (DEMM), diethoxy ethyl methylene malonate, dimethyl methylene malonate, di-n-propyl methylene malonate, ethyl hexyl methylene malonate, methyl fenchyl methylene malonate, ethyl fenchyl methylene malonate 2-phenylpropyl ethyl methylene malonate, 3-phenylpropyl ethyl methylene malonate, or dimethoxy ethyl methylene malonate; and
ii) a second 1,1-disubstituted alkene including methyl propyl methylene malonate, dihexyl methylene malonate, di-isopropyl methylene malonate, butyl methyl methylene malonate, ethoxyethyl ethyl methylene malonate, methoxyethyl methyl methylene malonate, hexyl methyl methylene malonate, dipentyl methylene malonate, ethyl pentyl methylene malonate, methyl pentyl methylene malonate, ethyl ethylmethoxy methylene malonate, ethoxyethyl methyl methylene malonate, butyl ethyl methylene malonate, dibutyl methylene malonate, diethyl methylene malonate (DEMM), diethoxy ethyl methylene malonate, dimethyl methylene malonate, di-n-propyl methylene malonate, ethyl hexyl methylene malonate, methyl fenchyl methylene malonate, ethyl fenchyl methylene malonate, 2-phenylpropyl ethyl methylene malonate, 3-phenylpropyl ethyl methylene malonate, or dimethoxy ethyl methylene malonate.

15. The method of claim 11 , wherein the resulting polymer includes a first polymer block including about 10 weight percent or more of a first 1,1-disubstituted alkene; and a second polymer block including less than 10 weight percent of the first 1,1-disubstituted alkene.

16. The method of claim 15 , wherein the one or more 1,1-disubstituted alkenes includes methyl propyl methylene malonate, dihexyl methylene malonate, di-isopropyl methylene malonate, butyl methyl methylene malonate, ethoxyethyl ethyl methylene malonate, methoxyethyl methyl methylene malonate, hexyl methyl methylene malonate, dipentyl methylene malonate, ethyl pentyl methylene malonate, methyl pentyl methylene malonate, ethyl ethylmethoxy methylene malonate, ethoxyethyl methyl methylene malonate, butyl ethyl methylene malonate, dibutyl methylene malonate, diethyl methylene malonate (DEMM), diethoxy ethyl methylene malonate, dimethyl methylene malonate, di-n-propyl methylene malonate, ethyl hexyl methylene malonate, methyl fenchyl methylene malonate, ethyl fench

Assignees

• Sirrus Inc

Inventors

• Stevenson Peter Rulon
• Holzer Alexander R
• Palsule Aniruddha Sudhir
• Sullivan Jeffrey M

Classifications

• C08F222/14

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

• C08F2/30

  non-ionic · CPC title

• C08F2/22

  Emulsion polymerisation · CPC title

• C09J135/02

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

• C08K5/42

  Sulfonic acids; Derivatives thereof · CPC title