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

• US 10,081,685 B2
• Filed: 03/23/2017
• Issued: 09/25/2018
• Est. Priority Date: 09/08/2014
• Status: Active Grant

• Current Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Original Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Inventors: Stevenson, Peter Rulon, Holzer, Alexander R., Palsule, Aniruddha Sudhir, Sullivan, Jeffrey M.
• Primary Examiner(s): NGUYEN, VU ANH
• Application Number:
  US15/467,330
• Publication Number:
  US 20170190807A1
• Time in Patent Office: 551 Days
• Field of Search: None
• CPC Class Codes: B01J 19/10 employing sonic or ultrasonic vibrations
• CPC Class Codes: B01J 19/18 Stationary reactors having moving elements inside B01J19/08, B01J19/26 take precedence
• CPC Class Codes: C07C 69/38 Malonic acid esters
• CPC Class Codes: C08F 122/14 Esters having no free carboxylic acid groups
• CPC Class Codes: C08F 2/22 Emulsion polymerisation
• CPC Class Codes: C08F 2/26 anionic
• CPC Class Codes: C08F 2/30 non-ionic
• CPC Class Codes: C08F 22/10 Esters
• CPC Class Codes: C08F 222/10 Esters
• CPC Class Codes: C08F 222/14 Esters having no free carboxylic acid groups , e.g. dialkyl maleates or fumarates
• CPC Class Codes: C08F 267/06 on to polymers of esters
• CPC Class Codes: C08F 293/00 Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule on to polymers modified by introduction of unsaturated end groups C08F290/02
• CPC Class Codes: C08J 3/07 from polymer solutions
• CPC Class Codes: C08K 5/103 with polyalcohols
• CPC Class Codes: C08K 5/1535 Five-membered rings
• CPC Class Codes: C08K 5/42 Sulfonic acids; Derivatives thereof
• CPC Class Codes: C08L 33/04 Homopolymers or copolymers of esters C08L43/04 takes precedence
• CPC Class Codes: C09D 135/02 Homopolymers or copolymers of esters C09D135/06, C09D135/08 take precedence
• CPC Class Codes: C09D 7/45 Anti-settling agents
• CPC Class Codes: C09D 7/65 macromolecular C09D7/41-C09D7/48 take precedence
• CPC Class Codes: C09J 11/06 : organic
• CPC Class Codes: C09J 11/08 : Macromolecular additives
• CPC Class Codes: C09J 135/02 : Homopolymers or copolymers of esters C09J135/06, C09J135/08 take precedence

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.

Claims

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 fenchyl methylene malonate, 2-phenylpropyl ethyl methylene malonate 3-phenylpropyl ethyl methylene malonate, or dimethoxy ethyl methylene malonate.

17. The method of claim 11, wherein the polymer is a random copolymer including the 1,1-disubstituted alkene and a second monomer.

18. The method of claim 11, wherein the method includes evaporating water following the step of polymerizing the one or more monomers.