Solution polymers formed from methylene malonate monomers, polymerization, and solution polymer products

• US 10,167,348 B2
• Filed: 05/08/2017
• Issued: 01/01/2019
• 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: Palsule, Aniruddha, Holzer, Alexander R., Stevenson, Peter Rulon, Parab, Kshitij Kishen, Sullivan, Jeffrey M.
• Primary Examiner(s): Nguyen, Vu A
• Application Number:
  US15/589,274
• Publication Number:
  US 20170240657A1
• Time in Patent Office: 603 Days
• Field of Search: None
• 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 a 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 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, wherein the molar ratio of the one or more monomers to the initiator is about 50;

1 or more;

iii) anionically polymerizing 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 a 1,1-disubstituted alkene compound in solution, wherein the resulting polymer is substantially free of a melting temperature and is substantially free of a glass transition temperature of about 15°

C. or more.

2. The process of claim 1, wherein the polymer is a random copolymer.

3. The process of claim 1, wherein the polymer is a block copolymer having a first polymer block and a second polymer block, wherein the second polymer block and the first polymer block have different concentration of monomers.

4. The process of claim 1, wherein the process includes a step of terminating the polymerization reaction.

5. The process claim 1, wherein

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

and

the molar ratio of the first monomer to the initiator is about 50,000;

1 or less.

8. 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.

9. 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.

10. The process of claim 1, wherein

the 1,1-disubstituted alkene compound 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.

6. 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, wherein the molar ratio of the one or more monomers to the initiator is about 50;

1 or more;

iii) anionically polymerizing 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 a 1,1-disubstituted alkene compound in solution, 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 and the second glass transition temperature differ by about 20°

C. or more.

7. The process of claim 6, wherein the block copolymer includes at least one block having a glass transition temperature or melting temperature of about 15°

C. or more and at least one different block having no melting temperature above 15°

C. and having a glass transition temperature about 0°

C. or less.

15. The process of claim 6, 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. 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, wherein the molar ratio of the one or more monomers to the initiator is about 50;

1 or more;

iii) anionically polymerizing 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 a 1,1-disubstituted alkene compound in solution, wherein the polymer is a homopolymer, and the method includes a step of separating the polymer from the solvent and the homopolymer is substantially free of a melting temperature and is substantially free of a glass transition temperature of about 15°

C. or more.

12. The process of claim 11, wherein the homopolymer has a polydispersity index of 1.5 or less and/or a weight average molecular weight greater than 20,000 g/mole.

17. The process of claim 11, wherein

the homopolymer has a polydispersity index of 1.5 or less;

the homopolymer has a weight average molecular weight greater than 20,000 g/mole;

the initiator includes a salt including a benzoate, an acetate, a silicate, or a carbonate;

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; and

the monomer is 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, or dimethoxyethyl methylene malonate.

13. 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, wherein the molar ratio of the one or more monomers to the initiator is about 50;

1 or more;

iii) anionically polymerizing 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 a 1,1-disubstituted alkene compound in solution;

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;

wherein the initiator includes a salt selected from a benzoate, an acetate, a silicate, or a carbonate;

and wherein the polymer is a random copolymer.

14. The process of claim 13, 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.

16. The process of claim 13, 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.