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

• US 9,279,022 B1
• Filed: 07/28/2015
• Issued: 03/08/2016
• 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: Holzer, Alexander R., Sullivan, Jeffrey M., Palsule, Aniruddha, Stevenson, Peter Rulon, Parab, Kshitij Kishen
• Primary Examiner(s): Nguyen, Vu A
• Application Number:
  US14/810,741
• Publication Number:
  US 20160068616A1
• Time in Patent Office: 224 Days
• Field of Search: 428/402, 428/402.2, 428/402.21, 428/402.22, 428/402.24, 428/407
• US Class Current: 1/1
• 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 for polymerizing a block copolymer comprising:

anionically polymerizing at least one monomer including a 1,1-disubstituted alkene compound in solution;

wherein the at least one monomer includes a first monomer; and

the process comprises the steps of;

i) mixing at least the first monomer and a solvent to form a solution including the first monomer and the solvent;

ii) adding an initiator;

iii) anionically polymerizing the first monomer in the presence of the solvent to form a first polymer block including the first monomer and having a weight average molecular weight of about 1000 daltons or more, wherein the first polymer block has a reactive chain end;

iv) after polymerizing the first polymer block, adding at least a second monomer to the solvent to form a solution including the second monomer and the solvent, wherein the second monomer is different from the first;

v) reacting the second monomer to the reactive chain end of the first polymer block; and

vi) anionically polymerizing the second monomer to form a second polymer block including the second monomer and having a weight average molecular weight of about 1000 daltons or more, wherein the second polymer block has a reactive chain end, and the composition of second polymer block is different from the composition of the first polymer block;

wherein the first monomer or the second monomer is a first 1,1-disubstituted alkene compound, the concentration of the first 1,1-disubstituted alkene is greater than 50 weight percent based on the total weight of the entire block copolymer, and the first polymer block or the second polymer block has a glass transition temperature of 50°

C. or more.

6. The process of claim 1, wherein the first polymer block or the second polymer block has a concentration of the first 1,1-disubstituted alkene compound of 70 weight percent or more, based on the total weight of said polymer block.

11. The process of claim 1, 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.

17. The process of claim 1, 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.

18. The process of claim 1, wherein

i) an acid compound is added to the solvent so that the initial pH of the solution is from about 5 to about 7;

ii) the activator includes a salt including a benzoate, an acetate, a silicate, or a carbonate;

iii) the block copolymer has a polydispersity index of 1.5 or less; and

iv) the block copolymer has a weight average molecular weight of about 20,000 daltons or more,

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.

19. The process of claim 1, 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.

20. The method of claim 1, wherein the method includes applying the block copolymer to a substrate as a pressure sensitive adhesive.

2. A process comprising:

anionically polymerizing at least one monomer including a 1,1-disubstituted alkene compound in solution;

wherein the at least one monomer includes a first monomer; and

the process comprises the steps of;

i) mixing at least the first monomer and a solvent to form a solution including the first monomer and the solvent;

wherein the first monomer is a first 1,1-disubstituted alkene compound;

ii) adding an initiator;

iii) anionically polymerizing the first monomer in the presence of the solvent to form a first polymer block including the first 1,1-disubstituted alkene compound and having a weight average molecular weight of about 1000 daltons or more, wherein the first polymer block has a reactive chain end;

iv) after polymerizing the first polymer block, adding at least a second monomer to the solvent to form a solution including the second monomer and the solvent, wherein the second monomer is different from the first monomer;

v) reacting the second monomer to the reactive chain end of the first polymer block; and

vi) anionically polymerizing the second monomer to form a second polymer block including the second monomer and having a weight average molecular weight of about 1000 daltons or more, wherein the second polymer block has a reactive chain end, and the composition of second polymer block is different from the composition of the first polymer block.

3. The process of claim 2 wherein the second polymer block has a different glass transition temperature than the glass transition temperature of the first polymer block.

4. The process of claim 2, wherein the second polymer block and the first polymer block have different concentration of monomers.

5. The process of claim 2, wherein the polymer is a linear polymer.

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

8. The process of claim 7, wherein the process includes a step of separating the polymer from the solvent.

9. The process of claim 8, wherein the process includes a step of drying the polymer.

10. The process of claim 9, wherein the process includes a polymerization temperature of about 40°

C. or less.

12. 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.

13. The process of claim 12, 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;

a polydispersity index from about 1 to about 11;

or both.

14. The process of claim 2, wherein the resulting polymer is a block copolymer including a first block having a first glass transition temperature and a second polymer block having a second glass transition temperature, wherein the first glass transition temperature differ by about 20°

C. or more.

15. The process of claim 14, wherein the first glass transition temperature is about 40°

C. or more, and the second glass transition temperature is less than the first glass transition temperature.

16. The process of claim 15, wherein

the resulting polymer has a polydispersity index of about 3.5 or less;

and

the molar ratio of the first monomer to the activator is from about 10;

1 to about 50,000;

1.

21. The method of claim 2, wherein the first polymer block includes 70 weight percent or more of the first 1,1-disubstituted alkene compound.

22. The method of claim 21, wherein the block copolymer has a weight average molecular weight of 20,000 g/mole or more, and a polydispersity index of 1.5 or more.

23. The method of claim 22, wherein the first polymer block has a glass transition temperature of 50°

C. or more.

24. The method of claim 23, wherein the activator includes a salt including a benzoate, an acetate, a silicate, or a carbonate.