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

• US 9,637,564 B2
• Filed: 12/11/2015
• Issued: 05/02/2017
• 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:
  US14/966,409
• Publication Number:
  US 20160096907A1
• Time in Patent Office: 508 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 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.

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.

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.

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.

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.

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 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;

wherein the resulting polymer has a polydispersity index of about 1.7 or less.

20. The process of claim 19, wherein the process includes a step of 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.