Polymers including one or more 1,1-disubstituted alkene compounds and polymer compositions thereof

• US 10,308,802 B2
• Filed: 09/08/2015
• Issued: 06/04/2019
• Est. Priority Date: 09/08/2014
• Status: Active Grant

• Current Assignee: Nippon Shokubai Company Limited
• Original Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Inventors: Sullivan, Jeffrey M., Palsule, Aniruddha Sudhir, Holzer, Alexander R., Stevenson, Peter R., Parab, Kshitij K.
• Primary Examiner(s): Nguyen, Vu A
• Application Number:
  US15/509,403
• Publication Number:
  US 20170275446A1
• Time in Patent Office: 1,365 Days
• 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 disclosure relates to polymers including one or more 1,1-disubstituted alkene monomers. By employing a plurality of monomers and/or tailored chain structure, polymers having improved combinations of properties are achieved. The polymer may be a copolymer, preferably including two or more 1,1-disubstituted alkene monomers. The polymer may be a homopolymer having a tailored chain structure.

Claims

1. A copolymer comprising:

i) from about 2 weight percent to about 98 weight percent of a first monomer; and

ii) from about 2 weight percent to about 98 weight percent of a second monomer;

wherein the first monomer is one or more 1,1-disubstituted alkene monomers, wherein the 1,1-disubstituted alkene monomer includes a central carbon atom doubly bonded to another carbon atom and further bonded to two carbonyl groups;

wherein the first monomer has a structure such that homopolymers of the first monomer have a Tg of about 50°

C. or more;

the second monomer has a structure such that homopolymers of the second monomer have a Tg of about 15°

C. or less; and

wherein the copolymer has a single glass transition temperature of about −

100°

C. to about 15°

C.; and

wherein the first monomer corresponds to Formula IIA;

2. The copolymer of claim 1, wherein the first monomer is present at a concentration of about 20 weight percent or more, based on the total weight of the copolymer and the second monomer is present at a concentration of about 20 weight percent or more, based on the total weight of the copolymer.

4. The copolymer of claim 2, wherein the copolymer includes one or more additional monomers different from the first monomer and the second monomer.

5. The copolymer of claim 1, wherein the first monomer is selected from the group consisting of dimethyl methylene malonate, phenylpropyl methyl methylene malonate, fenchyl methyl methylene malonate, fenchyl ethyl methylene malonate, menthyl ethyl methylene malonate, phenylpropyl ethyl methylene malonate, dicyclohexyl methylene malonate, cyclohexyl ethyl methylene malonate, isobornyl ethyl methylene malonate, benzyl ethyl methylene malonate, benzyl methyl methylene malonate, dibenzyl methylene malonate, and any combination thereof.

6. The copolymer of claim 5, wherein the second monomer is selected from the group consisting of methylmethoxy ethyl methylene malonate, ethylethoxy ethyl methylene malonate, hexyl methyl methylene malonate, dibutyl methylene malonate, dihexyl methylene malonate, hexyl ethyl methylene malonate, and any combination thereof.

7. The copolymer of claim 1, wherein the copolymer is a block copolymer including a first polymer block attached to a second polymer block, wherein the first polymer block includes the first monomer.

9. The copolymer of claim 7, wherein

(i) the first polymer block includes about 50 weight percent or more of one or more monomers selected from the group consisting of diethyl methylene malonate, dimethyl methylene malonate, phenylpropyl methyl methylene malonate, phenylpropyl methyl methylene malonate fenchyl methyl methylene malonate, fenchyl ethyl methylene malonate, menthyl ethyl methylene malonate, phenyl propyl ethyl methylene malonate, dicyclohexyl methylene malonate, cyclohexyl ethyl methylene malonate, isobornyl ethyl methylene malonate, benzyl ethyl methylene malonate, benzyl methyl methylene malonate, dibenzyl methylene malonate, and any combination thereof;

or

(ii) the second polymer block includes from about 50 weight percent or more of one or more monomers selected from the group consisting of methylmethoxy ethyl methylene malonate, ethylethoxy ethyl methylene malonate, hexyl methyl methylene malonate, dibutyl methylene malonate, dihexyl methylene malonate, hexyl ethyl methylene malonate, and any combination thereof.

10. The copolymer of claim 7, wherein

(i) the copolymer includes three or more polymer blocks;

or

(ii) the copolymer is a diblock copolymer or a triblock copolymer having a structure of A-B-A or A-B-C, wherein A, B, and C are different blocks each having different monomers or a monomer at a different concentration.

11. The copolymer of claim 1, wherein the copolymer is a random copolymer having a blockiness index of about 0.6 or more.

12. The copolymer of claim 1, wherein

i) the copolymer has 1 or more long chain branches;

or

the copolymer has 5 or more arms;

or

the copolymer includes one or more multifunctional monomers.

13. The copolymer of claim 1, wherein the second monomer is not a 1,1-disubstituted alkene monomer.

3. A copolymer comprising:

i) from about 2 weight percent to about 98 weight percent of a first monomer; and

ii) from about 2 weight percent to about 98 weight percent of a second monomer;

wherein the first monomer is one or more 1,1-disubstituted alkene monomers, wherein the 1,1-disubstituted alkene monomer includes a central carbon atom doubly bonded to another carbon atom and further bonded to two carbonyl groups;

wherein the first monomer has a structure such that homopolymers of the first monomer have a Tg of about 50°

C. or more; and

the second monomer has a structure such that homopolymers of the second monomer have a Tg of about 15°

C. or less; and

wherein the copolymer has a single glass transition temperature of about −

100°

C. to about 15°

C. and the first monomer is a first 1,1-disubstituted alkene monomer and the second monomer is a second 1,1-disubstituted alkene monomer different from the first monomer; and

the total concentration of the first monomer and the second monomer is about 30 weight percent or more, based on the total weight of the copolymer.

8. A copolymer comprising:

i) from about 2 weight percent to about 98 weight percent of a first monomer; and

ii) from about 2 weight percent to about 98 weight percent of a second monomer;

wherein the first monomer is one or more 1,1-disubstituted alkene monomers, wherein the 1,1-disubstituted alkene monomer includes a central carbon atom doubly bonded to another carbon atom and further bonded to two carbonyl groups,

wherein the copolymer is a block copolymer including a first polymer block attached to a second polymer block, wherein the first polymer block includes the first monomer,

wherein the copolymer has a first glass transition of about 25°

C. to about 250°

C., and the copolymer has a second glass transition temperature from about −

100°

C. to about 15°

C.; and

wherein a difference in a melting point of the first polymer block and the second polymer block is about 10°

C. or more.