Solution polymers including one or more 1,1-disubstituted alkene compounds, solution polymerization methods, and polymer compositions

• US 9,676,875 B2
• Filed: 12/11/2015
• Issued: 06/13/2017
• Est. Priority Date: 09/08/2014
• Status: Active Grant

• Current Assignee: Nippon Shokubai Company Limited
• Original Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Inventors: Sullivan, Jeffrey M., Palsule, Aniruddha, Holzer, Alexander R., Stevenson, Peter Rulon, Parab, Kshitij Kishen
• Primary Examiner(s): NGUYEN, VU ANH
• Application Number:
  US14/966,247
• Publication Number:
  US 20160096906A1
• Time in Patent Office: 550 Days
• CPC Class Codes: B05D 3/007 After-treatment
• CPC Class Codes: C08F 2/06 Organic solvent
• CPC Class Codes: C08F 2/26 anionic
• CPC Class Codes: C08F 222/14 Esters having no free carboxylic acid groups , e.g. dialkyl maleates or fumarates
• CPC Class Codes: C08F 297/02 using a catalyst of the anionic type
• CPC Class Codes: C09D 135/02 Homopolymers or copolymers of esters C09D135/06, C09D135/08 take precedence
• CPC Class Codes: C09D 153/00 Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
• CPC Class Codes: C09J 135/02 Homopolymers or copolymers of esters C09J135/06, C09J135/08 take precedence
• CPC Class Codes: C09J 153/00 Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers

Abstract

The present teachings show that it is possible to polymerize 1,1-disubstituted alkene compounds in a solution (for example using one or more solvents). Polymerization of 1,1-disubstituted alkene compounds in an solution provides opportunities to better control the polymerization compared with bulk polymerization. The solution 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) mixing two or more monomers with a solvent;

ii) adding an initiator to the solvent or a mixture of the solvent and the two or more monomers, wherein the molar ratio of the two or more monomers to the initiator is about 50;

1 or more;

iii) anionically polymerizing the two or more monomers to form a polymer having a weight average molecular weight of about 3000 daltons or more, wherein the two or more monomers includes a first monomer which is a 1,1-disubstituted alkene compound and a second monomer different from the first monomer;

in solution,

the step of anionically polymerizing includes initiating the polymerization of the first monomer with the initiator,

the polymer includes both the first monomer and the second monomer; and

the step of anionically polymerizing is in a polymerization solution including a base or a compound capable of forming a base or a nucleophile that can initiate the anionic polymerization of the first monomer.

22. The process of claim 1, wherein

the initiator includes a salt including a benzoate, an acetate, a silicate, or a carbonate, the solvent includes 0 to 10 weight percent protic solvent, the polymerization is in a solution having a liquid phase, wherein 90 volume percent or more of the liquid phase is the solvent, the at least one monomers, and any of the polymer in the liquid phase,

and the method includes a step of separating the polymer from the solvent.

2. A process comprising the steps of:

i) mixing at least one monomer with a solvent;

ii) adding an initiator to the solvent or the mixture of the solvent and the at least one monomer; and

iii) anionically polymerizing, in solution, the at least one monomer to form a polymer having a weight average molecular weight of about 3000 daltons or more,

wherein the at least one monomer includes two or more monomers,

wherein the two or more monomers includes a first monomer which is a 1,1-disubstituted alkene compound and a second monomer different from the first monomer;

the polymer includes both the first monomer and the second monomer; and

the polymer has a glass transition temperature of 50°

C. or more.

3. The process of claim 2, wherein the polymer is a random copolymer.

4. The process of claim 2, wherein the concentration of the first 1,1-disubstituted alkene compound is about 30 weight percent or more, based on the total weight of the polymer.

5. The process of claim 4, wherein the process includes a step of terminating the polymerization reaction.

6. The process of claim 5, wherein the process includes a step of separating the polymer from the solvent and a step of drying the polymer.

7. The process of claim 6 wherein the process includes a polymerization temperature of about 40°

C. or less.

8. The process of claim 2, wherein the polymerization solution includes a base or a compound capable of forming a base or a nucleophile that can initiate polymerization of the monomer.

9. The process of claim 2, wherein the ratio of the first monomer to the second monomer is from about 5:

95 to about 95;

5; and

wherein the resulting polymer is characterized by a weight average molecular weight or a number average molecular weight from about 3,000 to about 3,000,000 daltons; and

a polydispersity index from about 1 to about 11.

10. The process of claim 3, wherein the one or more monomers includes one or more monomers selected from the group consisting of 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 methoxyethyl methylene malonate, ethoxyethyl methyl methylene malonate, butyl ethyl methylene malonate, dibutyl methylene malonate, diethyl methylene malonate (DEMM), diethoxyethyl methylene malonate, dimethyl methylene malonate, di-N-propyl methylene malonate, ethyl hexyl methylene malonate, fenchyl methyl methylene malonate, menthyl methyl methylene malonate, 2-phenylpropyl ethyl methylene malonate, and dimethoxyethyl methylene malonate.

11. The process of claim 3, wherein

the first monomer is provided as a high purity monomer having a purity of about 95 weight percent or more, based on the total weight of the high purity monomer.

12. The process of claim 3, wherein the process includes

a step of depositing a solution onto a substrate, the solution including a polymer resulting from the polymerization step;

and

a step of evaporating some or all of the solvent so that the substrate is partially or entirely coated with a layer of the polymer.

13. The process of claim 3, wherein the random copolymer has a single glass transition temperature.

14. The process of claim 13, wherein the single glass transition temperature is greater than 80°

C.

15. The process of claim 14, wherein the random copolymer has a weight average molecular weight greater than 20,000 g/mole.

20. The process of claim 3, wherein an acid compound is employed so that a pH of the mixture of the solvent and monomer at a start of the polymerization is from about 5 to about 7.

16. A process comprising the steps of:

anionically polymerizing two or more monomers in solution to form a random copolymer, wherein the two or more monomers includes a first monomer that is a 1,1-disubstituted alkene compound and a second monomer different from the first monomer, wherein the anionically polymerizing process comprises the steps of;

i) mixing at least the first monomer, the second monomer, and the solvent;

ii) adding an initiator;

ii) reacting the initiator with one of the two or more monomers for initiating the anionic polymerization of the two or more monomers; and

iii) anionically polymerizing the two or more monomers to form a polymer having a weight average molecular weight of about 3000 daltons or more, including both the first monomer and the second monomer;

wherein the random copolymer has a polydispersity index of 1.5 or less.

17. The process of claim 16, wherein the first monomer is present at greater than 50 weight percent, based on the total weight of the random copolymer.

18. The process of claim 17, wherein the initiator includes a salt including a benzoate, an acetate, a silicate, or a carbonate.

19. The process of claim 18, wherein the random copolymer consists of more than one 1,1-disubstituted alkene compounds.

21. A process comprising the steps of:

anionically polymerizing two or more monomers in solution to form a random copolymer, wherein the two or more monomers includes a first monomer that is a 1,1-disubstituted alkene compound and a second monomer different from the first monomer, wherein the anionically polymerizing process comprises the steps of;

i) mixing at least the first monomer, the second monomer, and the solvent;

ii) adding an initiator;

ii) reacting the initiator with one of the two or more monomers for initiating the anionic polymerization of the two or more monomers; and

iii) anionically polymerizing the two or more monomers to form a polymer having a weight average molecular weight of about 3000 daltons or more, including both the first monomer and the second monomer;

wherein the first monomer is present at greater than 70 weight percent, based on the total weight of the random copolymer.