Emulsion including polymers containing a 1,1-disubstituted alkene compound, adhesives, coatings, and methods thereof

• US 10,184,073 B2
• Filed: 03/23/2017
• Issued: 01/22/2019
• Est. Priority Date: 09/08/2014
• Status: Active Grant

• Current Assignee: 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 A
• Application Number:
  US15/467,597
• Publication Number:
  US 20170198181A1
• Time in Patent Office: 670 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. An emulsion comprising:

i) 30 weight percent or more of a continuous phase including a carrier fluid including water;

ii) a dispersed phase including a polymer and having a surfactant layer in contact with the polymer and with the carrier fluid;

wherein the polymer is present in an amount of about 10 weight percent or more, includes one or more monomers including one or more 1,1-disubstituted alkene compounds, and has a number average molecular weight of about 700 g/mole or more, and wherein the polymer has a polydispersity index of about 1.7 or less.

2. The emulsion of claim 1, wherein the polymer has a number average molecular weight of about 2,000 g/mole to about 1,000,000 g/mole.

3. The emulsion of claim 1, wherein the dispersed phase includes micelles having a number average radius of about 0.10 μ

m to about 300 μ

m.

4. The emulsion of claim 3, wherein the concentration of the polymer is about 20 weight percent or more.

5. The emulsion of claim 4, wherein the carrier liquid consists essentially of water, and

i) the concentration of the carrier liquid is sufficiently high so that the emulsion is capable of flowing;

or

ii) the ratio of the zero shear viscosity of the emulsion to the zero shear viscosity of the polymer at 25°

C. is about 0.2 or less.

6. The emulsion of claim 5, wherein the carrier liquid is present in an amount of about 65 weight percent or less, based on the total weight of the emulsion.

7. The emulsion of claim 6, wherein the polymer is formed by a polymerization activated by one or more monomer activators including an ionic metal amide, an hydroxide, a cyanide, a phosphine, an alkoxide, an amine, an organometallic compound, or a metal benzoate;

wherein the molar ratio of the one or more monomers to the monomer activators is greater than about 50;

1.

8. The emulsion 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.

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

11. The emulsion of claim 9, wherein the polymer is a random copolymer including the 1,1-disubstituted alkene and a second monomer.

12. The emulsion of claim 6, wherein the one or more monomers includes:

i) a first 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; and

ii) a different 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 emulsion of claim 1, wherein the 1,1-disubstituted alkene is a compound having a hydrocarbyl group bonded to each of the two carbonyl groups through a direct bond or through an oxygen atom, wherein the 1,1-disubstituted alkene compound has the general formula:

16. The emulsion of claim 15, wherein the polymer is a random copolymer including the 1,1-disubstituted alkene and a second monomer.

17. The process of claim 15, wherein the 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.

18. An adhesive including the emulsion of claim 1, wherein the adhesive is a water-based adhesive and the carrier liquid consists essentially of water.

19. The adhesive of claim 18, wherein the adhesive is a pressure sensitive adhesive.

20. A coating including the emulsion of claim 1, wherein the coating is a water-based coating and the carrier liquid consists essentially of water.

10. An emulsion comprising:

i) 30 weight percent or more of a continuous phase including a carrier fluid including water, wherein the carrier liquid is present in an amount of about 65 weight percent or less, based on the total weight of the emulsion; and

ii) a dispersed phase including a polymer and having a surfactant layer in contact with the polymer and with the carrier fluid, wherein the dispersed phase includes micelles having a number average radius of about 0.10 μ

m to about 300 μ

m and wherein the concentration of the polymer is about 20 weight percent or more;

wherein the polymer is present in an amount of about 10 weight percent or more, includes one or more monomers including one or more 1,1-disubstituted alkene compounds, and has a number average molecular weight of about 700 g/mole or more;

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 wherein the 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.

13. An emulsion comprising:

i) 30 weight percent or more of a continuous phase including a carrier fluid including water;

ii) a dispersed phase including a polymer and having a surfactant layer in contact with the polymer and with the carrier fluid;

wherein the polymer is present in an amount of about 10 weight percent or more, includes one or more monomers including one or more 1,1-disubstituted alkene compounds, and has a number average molecular weight of about 700 g/mole or more and, wherein the 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.

14. An emulsion comprising:

i) 30 weight percent or more of a continuous phase including a carrier fluid including water;

ii) a dispersed phase including a polymer and having a surfactant layer in contact with the polymer and with the carrier fluid;

wherein the polymer is present in an amount of about 10 weight percent or more, includes one or more monomers including one or more 1,1-disubstituted alkene compounds, and has a number average molecular weight of about 700 g/mole or more, and wherein the polymer is a block copolymer including a first block having a glass transition temperature of 15°

C. or more, and a second polymer block having a glass transition temperature of less than 15°

C.