Methylene beta-ketoester monomers, methods for making methylene beta-ketoester monomers, polymerizable compositions and products formed therefrom

• US 9,527,795 B2
• Filed: 10/18/2012
• Issued: 12/27/2016
• Est. Priority Date: 10/19/2011
• 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:
  US14/352,406
• Publication Number:
  US 20140288230A1
• Time in Patent Office: 1,531 Days
• US Class Current: 1/1
• 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 69/593 Dicarboxylic acid esters having only one carbon-to-carbon double bond
• CPC Class Codes: C07C 69/604 Polycarboxylic acid esters, the acid moiety containing more than two carboxyl groups
• 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 222/14 : Esters having no free carboxylic acid groups , e.g. dialkyl maleates or fumarates
• 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: 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: Y02P 20/10 : Process efficiency

Abstract

The present invention provides methylene beta-ketoester monomers, methods for producing the same, and compositions and products formed therefrom. In the method for producing the methylene beta-ketoesters of the invention, a beta-ketoester is reacted with a source of formaldehyde in a modified Knoevenagel reaction optionally in the presence of an acidic or basic catalyst, and optionally in the presence of an acidic or non-acidic solvent, to form reaction complex. The reaction complex may be an oligomeric complex. The reaction complex is subjected to further processing, which may be vaporization by contact with an energy transfer means in order to isolate the beta-ketoester monomer. The present invention further compositions and products formed from methylene beta-ketoester monomers of the invention, including 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 methylene beta-ketoester monomer having the structural formula:

2. The monomer of claim 1, wherein the monomer includes a chlorine atom.

3. The monomer of claim 1, wherein the monomer includes a bromine atom.

4. A polymerizable composition including:

i) at least one methylene beta-ketoester monomer according to claim 1; and

ii) at least one additive selected from the group consisting of an acidic stabilizer, a free radical stabilizer, a sequestering agent, a cure accelerator, a rheology modifier, a plasticizing agent, a thixotropic agent, a natural rubber, a synthetic rubber, a filler agent and a reinforcing agent.

5. The polymerizable composition according to claim 4, wherein the polymerizable composition includes an acid stabilizer or a free radical stabilizer.

6. A methylene beta-ketoester monomer having the structural formula:

7. A polymerizable composition including:

i) at least one methylene beta-ketoester monomer according to claim 6; and

ii) at least one additive selected from the group consisting of an acidic stabilizer, a free radical stabilizer, a sequestering agent, a cure accelerator, a rheology modifier, a plasticizing agent, a thixotropic agent, a natural rubber, a synthetic rubber, a filler agent and a reinforcing agent.