Polymers including a methylene beta-ketoester and products formed therefrom

• US 10,414,839 B2
• Filed: 07/27/2017
• Issued: 09/17/2019
• Est. Priority Date: 10/20/2010
• Status: Active Grant

• Current Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Original Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Inventors: Malofsky, Bernard M., Malofsky, Adam G., Dey, Tanmoy, Sullivan, Jeffrey M.
• Primary Examiner(s): Buie-Hatcher, Nicole M.
• Application Number:
  US15/661,893
• Publication Number:
  US 20170355789A1
• Time in Patent Office: 782 Days
• Field of Search: None
• CPC Class Codes: C07C 2601/02 with a three-membered ring
• CPC Class Codes: C07C 2601/04 with a four-membered ring
• CPC Class Codes: C07C 2601/08 the ring being saturated
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 45/75 Reactions with formaldehyde
• CPC Class Codes: C07C 49/794 having unsaturation outside an aromatic ring
• CPC Class Codes: C07C 49/796 polycyclic
• CPC Class Codes: C07C 49/798 containing rings other than six-membered aromatic rings
• CPC Class Codes: C07C 49/80 containing halogen
• CPC Class Codes: C07C 67/03 by reacting an ester group with a hydroxy group
• CPC Class Codes: C07C 67/30 by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
• CPC Class Codes: C07C 67/333 by isomerisation; by change of size of the carbon skeleton introduction or elimination of carboxyl groups C07C67/313, C07C67/32
• CPC Class Codes: C07C 67/343 by increase in the number of carbon atoms
• CPC Class Codes: C07C 69/604 Polycarboxylic acid esters, the acid moiety containing more than two carboxyl groups
• CPC Class Codes: C07C 69/716 Esters of keto-carboxylic acids or aldehydo-carboxylic acids
• CPC Class Codes: C07C 69/738 Esters of keto-carboxylic acids or aldehydo-carboxylic acids
• CPC Class Codes: C07D 307/46 Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
• CPC Class Codes: C07D 307/54 Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• CPC Class Codes: C07D 333/22 Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
• CPC Class Codes: C07D 333/24 Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• CPC Class Codes: C08F 116/36 : by a ketonic radical
• CPC Class Codes: C08F 128/06 : by a heterocyclic ring containing sulfur
• CPC Class Codes: C08F 20/14 : Methyl esters , e.g. methyl (meth)acrylate
• CPC Class Codes: C08F 20/28 : containing no aromatic rings in the alcohol moiety
• CPC Class Codes: C08F 20/30 : containing aromatic rings in the alcohol moiety
• CPC Class Codes: C08F 20/38 : Esters containing sulfur
• CPC Class Codes: C08F 20/68 : Esters
• CPC Class Codes: C08F 22/20 : Esters containing oxygen in addition to the carboxy oxygen
• CPC Class Codes: C08F 24/00 : Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen cyclic esters of polyfunctional acids C08F18/00; cyclic anhydrides of unsaturated acids C08F20/00, C08F22/00
• CPC Class Codes: C08F 28/06 : by a heterocyclic ring containing sulfur
• CPC Class Codes: C08K 3/013 : Fillers, pigments or reinforcing additives
• CPC Class Codes: C08K 5/0008 : Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
• CPC Class Codes: C08K 5/005 : Stabilisers against oxidation, heat, light, ozone
• CPC Class Codes: C08K 5/08 : Quinones
• CPC Class Codes: C08K 5/13 : Phenols; Phenolates
• CPC Class Codes: C08L 21/00 : Compositions of unspecified rubbers
• CPC Class Codes: C08L 33/14 : of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C08L 33/16 : Homopolymers or copolymers of esters containing halogen atoms
• CPC Class Codes: C08L 35/02 : Homopolymers or copolymers of esters C08L35/06, C08L35/08 take precedence
• CPC Class Codes: C09D 129/12 : Homopolymers or copolymers of unsaturated ketones
• CPC Class Codes: C09D 133/14 : of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C09D 133/16 : Homopolymers or copolymers of esters containing halogen atoms
• CPC Class Codes: C09D 135/02 : Homopolymers or copolymers of esters C09D135/06, C09D135/08 take precedence
• CPC Class Codes: C09D 141/00 : Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur; Coating compositions based on derivatives of such polymers
• CPC Class Codes: C09D 4/00 : Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• CPC Class Codes: C09J 133/06 : of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
• CPC Class Codes: C09J 133/14 : of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C09J 133/16 : Homopolymers or copolymers of esters containing halogen atoms
• CPC Class Codes: C09J 135/02 : Homopolymers or copolymers of esters C09J135/06, C09J135/08 take precedence
• CPC Class Codes: C09J 4/00 : Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• CPC Class Codes: Y02P 20/10 : Process efficiency

Abstract

The present teachings are directed at 1,1-disubstituted alkene monomers (e.g., methylene beta-ketoester monomers), methods for producing the same, polymerizable compositions including a methylene beta-ketoester monomer, and polymers, compositions and products formed therefrom. The monomer preferably is a high purity monomer. In the method for producing the methylene beta-ketoesters of the invention, a beta-ketoester may be reacted with a source of formaldehyde. The methylene beta-ketoester monomers may be used in monomer-based products (e.g., inks, adhesives, coatings, sealants or reactive molding) and polymer-based products (e.g., fibers, films, sheets, medical polymers, composite polymers and surfactants).

Claims

1. A polymer prepared from a polymerizable composition comprising:

at least one methylene beta-ketoester monomer having the structural formula;

2. The polymer prepared from the polymerizable composition of claim 1, wherein the polymer includes a difunctional monomeric cross-linking agent.

3. The polymer prepared from the polymerizable composition of claim 1,

wherein R₁ and R₂ are independently C₁-C₆ alkyl or aryl.

4. The polymer prepared from the polymerizable composition of claim 1, wherein the methylene beta-ketoester monomer has the structure:

5. The polymer prepared from the polymerizable composition of claim 1, wherein the methylene beta-ketoester monomer has the structure:

6. The polymer prepared from the polymerizable composition of claim 1 further comprising one or more components which include tougheners, plasticizers, thixotropic agents, rubbers or reinforcing agents.

7. The polymer prepared from the polymerizable composition of claim 1, wherein the polymer is a fiber, a film, a sheet, a medical polymer, a composite polymer or a surfactant.