METHYLENE BETA-KETOESTER MONOMERS, METHODS FOR MAKING METHYLENE BETA-KETOESTER MONOMERS, POLYMERIZABLE COMPOSITIONS AND PRODUCTS FORMED THEREFROM

• US 20140288230A1
• Filed: 10/18/2012
• Published: 09/25/2014
• Est. Priority Date: 10/19/2011
• Status: Active Grant

• Current Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Original Assignee: Bioformix Inc.
• Inventors: Malofsky, Bernard M., Malofsky, Adam G., Dey, Tanmoy
• Granted Patent: US 9,527,795 B2
• Time in Patent Office: Days
• US Class Current: 524/544
• 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

1-58. -58. (canceled)

59. A methylene beta-ketoester monomer comprising at least one core formula represented by —

C(O)—

C(CH2)-C(O)—

O—

.

60. The methylene beta-ketoester monomer according to claim 59 represented by the following structural formula:

61. The methylene beta-ketoester monomer according to claim 60 having a structural formula selected from the group consisting of:

62. The methylene beta-ketoester monomer according to claim 60 having a structural formula selected from the group consisting of:

63. A polymerizable composition including at least one methylene beta-ketoester monomer according to claim 60.

64. The polymerizable composition according to claim 63 further comprising a stabilizing amount of at least one stabilizer selected from the group consisting of:

an acidic stabilizer, a vapor phase stabilizer, and a free radical stabilizer.

65. The polymerizable composition according to claim 64 wherein the at least one stabilizer includes the acidic stabilizer selected from trifluoromethane sulfonic acid, maleic acid, methane sulfonic acid, difluoro acetic acid, trichloroacetic acid, phosphoric acid, dichloroacetic acid, and chlorodifluoro acid.

66. The polymerizable composition according to claim 63 wherein the at least one stabilizer includes the vapor phase stabilizer selected from hydroquinone, methyl hydroquinone, butylated hydroxytoluene, butylated hydroxyanisole.

67. The methylene beta-ketoester monomer according to claim 60 being formed as a reaction product of a beta-ketoester represented by R₁—

C(O)—

C—

C(O)—

O—

R₂, and a source of formaldehyde.

68. A method of making a methylene beta-ketoester monomer comprising:

a) reacting a beta-ketoester reactant having the structural formula;

69. The method according to claim 68 wherein in step (b), isolating the methylene beta-ketoester monomer comprises:

i. contacting the reaction complex, or a portion thereof, with an energy transfer means to produce a vapor phase including the methylene beta-ketoester monomer; and

ii. collecting the methylene beta-ketoester monomer from the vapor phase.

70. The method according to claim 68, wherein in step (b), isolating the methylene beta-ketoester monomer comprises:

i. heating the reaction complex, or a portion thereof, to a temperature between about 130°

C. and about 300°

C. to produce a vapor phase including the methylene beta-ketoester monomer; and

ii. collecting the methylene beta-ketoester monomer from the vapor phase.

71. The method according to claim 68 wherein the reaction conditions include:

a) an initiating temperature of between about 60°

C. and about 130°

C.; and

b) atmospheric pressure.

72. The method according to claim 68 wherein the source of formaldehyde includes paraformaldehyde, formalin, tiroxane or gaseous formaldehyde, or any combination thereof.

73. The method according to claim 68 wherein isolating the methylene beta-ketoester monomer includes condensing the vapor phase to a condensate and thereafter subjecting the condensate to a separation process selected from simple distillation, fractional distillation, flash distillation, steam distillation, vacuum distillation, short path distillation, thin-film distillation, reactive distillation, pervaporation, extractive distillation, flash evaporation, rotary evaporation, liquid/liquid extraction, centrifuging, or any combination thereof

74. The method according to claim 68, wherein the reaction complex comprises one or more oligomeric complexes capable of forming the methylene beta-ketoester monomer upon cracking.

75. A polymer having repeat units of the formula:

76. A polymer product comprising the polymer according to claim 75.

77. The polymer product according to claim 76 selected from the group consisting of a coating, a paint, a fiber, a composite, a textile fiber, a water-treatment polymer, an ink carrier, a paint carrier, a packaging film, a molding, a medical polymer, a polymer film, and a polymer sheet.

78. An oligomeric complex prepared by reacting a beta-ketoester reactant with a source of formaldehyde;

optionally in the presence of a heat transfer agent;

optionally in the presence of an acidic or basic catalyst; and

optionally in the presence of an acidic or non-acidic solvent.

79. The oligomeric complex according to claim 78, having between 2 and 12 repeat units having the structural formula: