Emulsion polymers including one or more 1,1-disubstituted alkene compounds, emulsion methods, and polymer compositions

Patent metadata

Field	Value
Publication number	US-9637564-B2
Application number	US-201514966409-A
Country	US
Kind code	B2
Filing date	Dec 11, 2015
Priority date	Sep 8, 2014
Publication date	May 2, 2017
Grant date	May 2, 2017

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 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 a number average molecular weight of about 700 g/mole or more;
wherein the activator includes an ionic metal amide, an hydroxide, a cyanide, a phosphine, an alkoxide, an amine, an organometallic compound, or a metal benzoate; and
the carrier liquid includes water and the water is present at a concentration of about 40 weight percent or more, based on the total weight of the carrier liquid and the one or more monomers,
wherein the resulting polymer has a polydispersity index of about 1.7 or less.

2. The process of claim 1 , wherein the reacting step is characterized by a pH of about 5 to about 6.6.

3. The process of claim 2 , wherein the resulting polymer has a weight average molecular weight of about 20,000 g/mole to about 1,000,000 g/mole.

4. The process of claim 1 , wherein the process includes a step of adding the activator to the mixture having the micelles.

5. The process of claim 3 , wherein the molar ratio of the one or more monomers to the activator is from about 50:1 to about 20,000:1.

6. The process of claim 1 , wherein the concentration of the one or more 1,1-disubstituted alkenes is about 50 weight percent or more, based on the total weight of the one or more monomers.

7. The process of claim 6 , wherein the 1,1-disubstituted alkenes includes a compound having a hydrocarbyl group bonded to each of the two carbonyl groups through a direct bond or through an oxygen atom.

8. The process of claim 1 , wherein
the emulsion includes an acid containing compound;
the surfactant includes a nonionic surfactant; and
the process includes a polymerization temperature of about 40° C. or less.

9. 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;
iii) anionically polymerizing the one or more monomers to a number average molecular weight of about 700 q/mole or more; and
iv) adding one or more second monomers to the emulsion following the step of anionically polymerizing the one or more monomers, wherein the one or more second monomers differ from the one or more monomers in composition or includes a different monomer; and a step of anionically polymerizing the one or more second monomers
wherein the activator includes an ionic metal amide, an hydroxide, a cyanide, a phosphine, an alkoxide, an amine, an organometallic compound, or a metal benzoate; and

the carrier liquid includes water and the water is present at a concentration of about 40 weight percent or more, based on the total weight of the carrier liquid and the one or more monomers.

10. The process of claim 9 , wherein the resulting polymer has a polydispersity index of about 1.7 or less.

11. The process of claim 9 , wherein the process step of anionically polymerizing the one or more second monomers includes a step of forming a block copolymer;
wherein the resulting polymer is a block copolymer including a first block having a first glass transition temperature and a second block having a second glass transition temperature, wherein the first and second glass transition temperatures differ by about 20° C. or more.

12. The process of claim 1 , wherein the one or more monomers includes two 1,1-disubstituted alkenes, including a first 1,1-disubstituted alkene and a second 1,1-disubstituted alkene.

13. The process of claim 1 , wherein the resulting polymer includes a random copolymer of a first 1,1-disubstituted alkene and a second monomer.

14. The process of claim 1 , wherein the resulting polymer is a homopolymer.

15. The process of claim 7 , wherein the hydrocarbyl group of the monomer includes a C 1-15 straight or branched chain alkyl, a C 1-15 straight or branched chain alkenyl, a C 5-18 cycloalkyl, a C 6-24 alkyl substituted cycloalkyl, a C 4-18 aryl, a C 4-20 aralkyl, or a C 4-20 aralkyl.

16. The process of claim 15 , wherein the monomer 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.

17. 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 a number average molecular weight of about 700 g/mole or more;
wherein the carrier liquid includes water and the water is present at a concentration of about 40 weight percent or more, based on the total weight of the carrier liquid and the one or more monomers; and

the reacting step is characterized by a pH of about 5 to about 6.6;
wherein the resulting polymer has a polydispersity index of about 1.7 or less.

18. The process of claim 16 , wherein;
the resulting polymer has a weight average molecular weight of about 20,000 g/mole to about 1,000,000 g/mole.

19. 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 a number average molecular weight of about 700 g/mole or more;
wherein the carrier liquid includes water and the water is present at a concentration of about 40 weight percent or more, based on the total weight of the carrier liquid and the one or more monomers; and
the monomer includes methyl propyl methylene malonate, dihexyl methylene malonate, di-isopropyl methyle

Assignees

• Sirrus Inc

Inventors

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

Classifications

• C08F22/10

  Esters · CPC title

• C07C69/38

  Malonic acid esters · CPC title

• C09D135/02

  Homopolymers or copolymers of esters (C09D135/06, C09D135/08 take precedence) · CPC title

• C09J11/06

  organic · CPC title

• C09J11/08

  Macromolecular additives · CPC title