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

• US 9,249,265 B1
• Filed: 07/01/2015
• Issued: 02/02/2016
• 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: Stevenson, Peter Rulon, Holzer, Alexander R., Palsule, Aniruddha Sudhir
• Primary Examiner(s): NGUYEN, VU ANH
• Application Number:
  US14/789,178
• Time in Patent Office: 216 Days
• US Class Current: 1/1
• 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 first monomers to form micelles of the one or more first monomers in the carrier liquid, wherein the one or more first monomers includes one or more 1,1-disubstituted alkenes;

ii) reacting an activator with at least one of the one or more first monomers in the micelle for initiating the anionic polymerization of the one or more first monomers;

iii) anionically polymerizing the one or more first monomers to a number average molecular weight of about 700 g/mole or more;

iv adding one or more second monomers to the emulsion following the step of anionically polymerizing the one or more first monomers, wherein the one or more second monomers differ from the one or more first monomers in composition or includes a different monomer; and

v. anionically polymerizing the one or more second monomers.

2. The process of claim 1, wherein the concentration of the one or more 1,1-disubstituted alkenes is about 30 weight percent or more, based on the total weight of the one or more first monomers.

3. The process of claim 1, wherein the emulsion includes an acid containing compound.

4. The process of claim 1, wherein the surfactant includes a nonionic surfactant.

5. The process of claim 1, wherein the process step of anionically polymerizing the one or more second monomers includes a step of forming a block copolymer.

6. The process of claim 1, wherein the one or more 1,1-disubstituted alkenes include a compound having a first hydrocarbyl group bonded to one of the carbonyl groups through a direct bond or through an oxygen atom and a second hydrocarbyl group bonded to the other carbonyl group through a direct bond or through an oxygen atom.

7. The process of claim 1, wherein the polymerization temperature is about 40°

C. or less.

8. The process of claim 1, 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 first monomers.

9. The process of claim 1, wherein the one or more first monomers includes two 1,1-disubstituted alkenes, including a first 1,1-disubstituted alkene and a second 1,1-disubstituted alkene.

10. The process of claim 1, wherein the resulting polymer includes a polymer block that is a random copolymer of a first 1,1-disubstituted alkene and a different monomer.

12. The process of claim 1, wherein the resulting polymer is characterized by a weight average molecular weight from about 700 to about 3,000,000 daltons;

a polydispersity index from about 1 to about 8;

or both.

14. The process of claim 1, wherein

i) the resulting polymer has a polydispersity index of about 1.5 or less;

and/or

ii) the molar ratio of the one or more monomers to the activator is from about 50;

1 to about 20,000;

1.

15. The process of claim 1, wherein the monomer includes a hydrocarbyl group selected from the group consisting of 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, and a C_4-20 aralkyl.

16. The process of claim 1, the conversion of the one or more first monomers to the polymer is about 98 mole percent or more, based on a total number of moles of the one or more first monomers added during the process.

17. The process of claim 16, wherein the resulting polymer includes 30 weight percent or more of the one or more 1,1-disubstituted alkene compounds.

18. The process of claim 17, wherein the 1,1-disubstituted alkene compound is provided as a high purity monomer, wherein the high purity monomer includes the 1,1-disubstituted alkene compound having an alkene group and wherein the total concentration of any analogous impurity compound having the alkene group replaced by hydroxyalkyl group is about 3 mole percent or less, based on the total moles of the 1,1-disubstituted alkene compound.

19. The process of claim 18, wherein the high purity monomer has a concentration of impurities having a dioxane group of 1 mole percent or less.

20. The process of claim 12, wherein the block copolymer is a diblock copolymer or a triblock copolymer.

11. 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 resulting 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. 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 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.