Methylidene malonate process
View Patent ↗An improvement in the production of methylidene malonates is attained by use of specific reaction phase and/or separation phase polymerization inhibitors and combinations thereof.
1. A process for the separation and isolation of methylidene malonates from a crude methylidene malonate comprising:
a) adding a separation phase polymerization inhibitor to a crude or unpurified methylidene malonate reaction product;
b) adding at least a portion of a separation phase polymerization inhibitor to the collection vessel used in the separation and/or isolation step,
c) conducting the separation and/or isolation step to thereby collect the separated or isolated methylidene malonate in the collection vessel, wherein the separation phase polymerization inhibitor comprises at least one primary anionic polymerization inhibitor, at least one free radical polymerization inhibitor, and, optionally, at least one secondary anionic polymerization inhibitor.
2. The process of claim 1 wherein additional separation phase polymerization inhibitor is added to the materials resulting from the separation or isolation process.
3. The process of claim 1 wherein a series of separation and/or isolation processes are conducted, each repeating the steps of claim 1 until the desired degree of purity is attained.
4. The process of claim 3 wherein additional separation phase polymerization inhibitor is added to the materials resulting from each separation and/or isolation process including the final separation or isolation process.
5. The process of claim 1 wherein the separation phase polymerization inhibitor further comprises at least one secondary anionic polymerization inhibitor.
6. The process of claim 1 wherein the primary anionic polymerization inhibitor is selected from trifluoroacetic acid, sulfuric acid, maleic acid, perchloric acid and chlorosulfonic acid.
7. The process of claim 1 wherein the separation process comprises a sequence of at least two distillations on a crude methylidene malonate product with the first distillation comprising the isolation of the liquid crude methylidene malonate from any non-liquid components in the crude product and the second distillation comprising a re-distillation of the product of the first distillation.
8. The process of claim 1 wherein the separation process comprises a sequence of at least three distillations on a crude methylidene malonate product with the first distillation comprising the isolation of the liquid crude methylidene malonate from any non-liquid components in the crude product, the second distillation comprising a re-distillation of the product of the first distillation and the third or subsequent distillation comprising the distillation of those fractions from the preceding distillation containing at least 50% by weight of methylidene malonate.
9. The process of claim 1 wherein the initial separation of the liquid methylidene malonate is by a method other than distillation and the method further comprises one or more additional purification steps, at least one of which is a distillation step.
10. The process of claim 1 wherein the crude methylidene malonate is produced by an adduct process.
11. The process of claim 1 wherein the crude methylidene malonate is produced by a non-adduct process.
12. The process of claim 1 wherein the separation, isolation and/or purification of the methylidene malonate is performed in multiple steps with the separation phase polymerization inhibitor having been added to the crude or impure methylidene malonate prior to commencement of the first step and the same or a different separation phase polymerization inhibitor is employed in at least one of the other, subsequent steps.
13. The process of claim 12 wherein the at least one other separation or isolation step involves the use of, a secondary anionic polymerization inhibitor, alone or in combination with a free radical polymerization inhibitor and the amount of the secondary anionic polymerization inhibitor is from about 1 to about 10,000 ppm.
14. The process of claim 1 wherein the primary anionic polymerization inhibitor is present in an amount of from about 1 to about 10,000 ppm, the free radical polymerization inhibitor is present in an amount of from about 100 to about 20,000 ppm, and the secondary anionic polymerization inhibitor is present, if present, in an amount of from about 1 to about 500 ppm.