Method to obtain methylene malonate via bis(hydroxymethyl) malonate pathway

• US 9,522,381 B2
• Filed: 08/11/2015
• Issued: 12/20/2016
• Est. Priority Date: 01/11/2013
• Status: Active Grant

• Current Assignee: Nippon Shokubai Company Limited
• Original Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Inventors: Malofsky, Bernard Miles, Malofsky, Adam Gregg, Sullivan, Jeffrey M., Kisanga, Philip B, Anderson, John Joseph, Cockrem, Michael Charles Milner, Carlberg, Philip Jay
• Primary Examiner(s): YOUNG, NATASHA E
• Application Number:
  US14/823,581
• Publication Number:
  US 20150343415A1
• Time in Patent Office: 497 Days
• US Class Current: 1/1
• CPC Class Codes: B01J 19/245 placed in series
• CPC Class Codes: B01J 2208/00168 with heat exchange elements outside the bed of solid particles
• CPC Class Codes: B01J 2208/065 Heating or cooling the reactor
• CPC Class Codes: B01J 2219/00033 Continuous processes
• CPC Class Codes: B01J 2219/0004 Processes in series
• CPC Class Codes: B01J 2219/00087 with heat exchange elements outside the reactor
• CPC Class Codes: B01J 2219/00177 controlling the pH
• CPC Class Codes: B01J 2219/24 Stationary reactors without moving elements inside
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 8/067 Heating or cooling the reactor B01J8/062 takes precedence
• CPC Class Codes: C07C 67/31 by introduction of functional groups containing oxygen only in singly bound form
• CPC Class Codes: C07C 67/327 by elimination of functional groups containing oxygen only in singly bound form
• 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 67/56 by solid-liquid treatment; by chemisorption
• CPC Class Codes: C07C 69/593 Dicarboxylic acid esters having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 222/14 Esters having no free carboxylic acid groups , e.g. dialkyl maleates or fumarates
• 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 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

Abstract

Method to obtain methylene malonate and related monomers following a bis(hydroxymethyl) malonate pathway. A bis(hydroxymethyl) malonate intermediary is subsequently reacted (i.e., subjected to thermolysis) to provide a methylene malonate monomer species. A source of formaldehyde (e.g., formalin) is provided in the presence of a basic catalyst (e.g., calcium hydroxide), to which a malonate (e.g., diethyl malonate) is added under suitable reaction conditions to obtain the desired intermediary (e.g., dialkyl bis(hydroxymethyl) malonate). The intermediary is reacted (i.e., subjected to thermolysis) under suitable conditions in the presence of a suitable catalyst (e.g., a zeolite) to obtain a methylene malonate monomer. In an exemplary embodiment, the thermolysis reaction includes the addition of the bis(hydroxymethyl) malonate intermediary onto a heated catalyst. The reaction product is collected and purified. The disclosed methods may be performed in a continuous operation. Discrete steps may be performed by using modular units within a plant.

Claims

1. A plant for producing a methylene malonate monomer comprising:

at least one diol production unit comprising a diol reactor apparatus capable of reacting a dialkyl malonate ester and a source of formaldehyde in the presence of a catalyst,

at least one diol purification unit comprising an ion-exchange column and a short heat residence time apparatus capable of performing an evaporation step,

at least one monomer production unit comprising a plurality of catalyst columns and at least one heating apparatus for maintaining the temperature of the plurality of catalyst columns, and

at least one monomer purification unit comprises a condensation apparatus, a fractional distillation apparatus, or both;

wherein the at least one diol production unit is in communication with the at least one diol purification unit, the at least one diol purification unit is in communication with the at least one monomer production unit, and the at least one monomer production unit is in communication with the at least one monomer purification unit.

2. The plant according to claim 1 wherein the at least one monomer production unit comprises at least a single reactant feed line to feed the plurality of catalyst columns.

3. The plant according to claim 1 wherein the short heat residence apparatus comprises a wiped-film evaporator, a rotary evaporator, a horizontal thin-film evaporator or a vertical thin-film evaporator.

4. The plant according to claim 1 wherein the short heat residence apparatus comprises a wiped-film evaporator.

5. The plant according to claim 1 wherein the at least one diol production unit is a continuous flow reactor.

6. The plant according to claim 5 wherein the at least one diol production unit comprises a shell having a plurality of static mixers and reactant inlets.

7. The plant according to claim 5 wherein the at least one diol production unit comprises an inlet to add a pH lowering agent.

8. The plant according to claim 5 wherein the at least one diol production unit is maintained in a medium to control reaction temperature.

9. The plant according to claim 8 wherein the medium to control reaction temperature is a water bath.

10. The plant according to claim 1 wherein the at least one monomer production unit which comprises a plurality of catalyst columns packed with ZSM catalyst.

11. The plant according to claim 1 wherein the did purification unit communicates with the monomer production unit through feed lines wherein the feed lines are heated.

12. The plant according to claim 1 wherein the at least one heating apparatus is a heat transfer system.

13. The plant according to claim 1 wherein the at least one heat transfer system uses hot oil to heat the plurality of catalyst columns.

14. The plant according to claim 1 wherein the at least one monomer production unit comprises an output line for heavies, an output line for volatile species.

15. The plant according to claim 1 wherein the at least one monomer production unit comprises a plurality of catalyst columns having a diameter of about 0.5 to about 4.0 inches and a length of about 12 to about 72 inches.

16. The plant according to claim 1 wherein:

the at least one diol purification unit is capable of purifying bis(hydroxymethyl) malonate,

the at least one monomer production unit is capable or reacting bis(hydroxymethyl) malonate with a catalyst to form a methylene malonate monomer, and

the at least one monomer purification unit is capable of isolating methylene malonate monomer.