Multifunctional monomers, methods for making multifunctional monomers, polymerizable compostions and products formed thereform

• US 9,512,058 B2
• Filed: 10/18/2012
• Issued: 12/06/2016
• 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, Hines, Larry, Ellison, Matthew M.
• Primary Examiner(s): Zucker, Paul A
• Application Number:
  US14/352,356
• Publication Number:
  US 20140329980A1
• Time in Patent Office: 1,510 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 multifunctional monomers, including, but not limited to include multifunctional methylene malonate and methylene beta-ketoester monomers; methods for producing the same; and compositions and products formed therefrom. The multifunctional monomers of the invention may be produced by transesterification or by direct synthesis from monofunctional methylene malonate monomers or methylene beta-ketoester monomers. 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 method of making a multifunctional methylene malonate monomer comprising:

(a) reacting at least one methylene malonate monomer with a diol, a polyol or a polymeric resin having at least two hydroxyl groups in the presence of an enzymatic catalyst to form a reaction complex wherein the at least one methylene malonate monomer is provided in an excess amount with respect to the diol, polyol or polymeric resin having at least two hydroxyl groups; and

(b) recovering multifunctional methylene malonate monomer comprising more than one methylene malonate core formula linked by the diol, polyol or polymeric resin having at least two hydroxyl groups from the reaction complex;

(c) adding a stabilizer to the reaction complex formed in step (a);

wherein in step (a) the at least one methylene malonate monomer is provided in an excess amount with respect to the diol, polyol or polymeric resin having at least two hydroxyl groups,

recovering multifunctional methylene malonate monomer in step (b) includes separating the multifunctional methylene malonate monomer from the excess methylene malonate monomer and the diol, polyol or polymeric resin having at least two hydroxyl groups; and

the diol, polyol or polymeric resin having at least two hydroxyl groups correspond to the formula (HO)-[A]-(OH)_m wherein;

[A] is independently selected from —

(CR^AR^B)_n—

, —

(CR^AR^B)_n—

O(C═

O)—

(CH₂)_1-15—

(C═

O)O—

(CR^AR^B)_n—

, —

(CH₂)_n—

[CY]—

(CH₂)_n, a polybutadienyl linking group, a polyethylene glycol linking group, a polyether linking group, a polyurethane linking group, an epoxy linking group, a polyacrylic linking group, or a polycarbonate linking group;

each instance of R^A or R^B is independently selected from H, C₁-C₁₅ alkyl, a moiety corresponding to the formula;

2. The method according to claim 1, wherein the reaction conditions in step (a) comprise room temperature and atmospheric pressure;

elevated temperature and atmospheric pressure;

room temperature and under vacuum;

elevated temperature and under vacuum;

or any combination thereof.

3. The method according to claim 2, wherein step (a) is performed at an elevated temperature between about 40°

C. and 85°

C.

4. The method according to claim 1, wherein step (a) comprises removing alcohol that is formed.

5. The method according to claim 1, wherein the methylene malonate is reacted with the diol or polyol of C₁-C₁₂ alkyl diol, any isomer of cyclohexane dimethanol, polybutyl THF, or trimethylolpropane.

6. The method according to claim 1, wherein step (a) is performed under vacuum conditions.

7. The method according to claim 1, wherein the multifunctional monomers correspond to the formula:

8. The method according to claim 7, wherein [A] is a linking group derived from C₁-C₁₂ alkyl diol, any isomer of cyclohexane dimethanol, polybutyl THF, or trimethylolpropane.

9. The method according to claim 7, wherein [A] is C₁-C₁₅ alkyl, or C₃-C₆ cycloalkyl.

10. The method according to claim 1 wherein an excess of at least one methylene malonate monomer is reacted with a diol, a polyol or a polymeric resin having at least two hydroxyl groups in the absence of a solvent.

11. The method according to claim 1 wherein an acidic stabilizer having a pKa of from −

15 to 5 is added at a concentration of about 0.1 to about 100 ppm and a phenolic free radical stabilizer is added at a concentration of about 0.1 to about 10,000.

12. The method according to claim 1 wherein the stabilizer is one or more acidic stabilizers, volatile acid stabilizers, or free radical stabilizers.

19. The method according to claim 12, wherein the acidic stabilizer is trifluoromethane sulfonic acid, maleic acid, methane sulfonic acid, difluoro acetic acid, trichloroacetic acid, phosphoric acid, dichloroacetic acid, chlorodifluoro acid, hydroquinone, methylhydroquinone, butylated hydroxytoluene, or butylated hydroxyanisole.

20. The method according to claim 12, wherein in step (c), the acidic stabilizer is added to the reaction complex in concentrations of about 0.1 ppm to about 100 ppm of the reaction complex.

13. A method of making a multifunctional methylene malonate monomer comprising:

(a) reacting at least one methylene malonate monomer having disubstituted vinyl functionality with a diol, a polyol or a polymeric resin having at least two hydroxyl groups and which does not have functional groups that react with the disubstituted vinyl functionality on the methylene malonate monomer, in the presence of an enzymatic catalyst to form a reaction complex;

wherein the at least one methylene malonate monomer is provided in an excess amount with respect to the diol, polyol or polymeric resin having at least two hydroxyl groups; and

(b) recovering multifunctional methylene malonate monomer comprising more than one methylene malonate core formula linked by the diol, polyol or polymeric resin having at least two hydroxyl groups from the reaction complex,

(c) adding a stabilizer to the reaction complex formed in step (a);

recovering multifunctional methylene malonate monomer in step (b) includes separating the multifunctional methylene malonate monomer from the excess methylene malonate monomer and the diol, polyol or polymeric resin having at least two hydroxyl groups.

14. The method according to claim 13 wherein the diol, the polyol or the polymeric resin having at least two hydroxyl groups is independently an oligomeric alcohol or polymeric alcohol.

15. The method according to claim 13 wherein the at least one methylene malonate monomer is contacted with the polymeric resin having at least two hydroxyl groups.

16. The method according to claim 15 wherein the at least one methylene malonate monomer is contacted with the polymeric resin having at least two hydroxyl groups which is independently a polybutadienyl, polyethylene glycol, polyether, a polyurethane, epoxy, polyacrylic, or polycarbonate polymeric resin having at least two hydroxyl groups.

17. The method according to claim 13 wherein the at least one methylene malonate monomer is contacted with the polyol comprising a triol.

18. The method according to claim 17 wherein the triol is 1,2,3-propane triol, 1,2,3 butane triol or 1,2,4 butane triol.