Polymerization inhibitor composition and method of inhibiting polymerization of distillable monomers

Patent metadata

Field	Value
Publication number	US-9447201-B2
Application number	US-201013147733-A
Country	US
Kind code	B2
Filing date	Feb 18, 2010
Priority date	Feb 18, 2009
Publication date	Sep 20, 2016
Grant date	Sep 20, 2016

Abstract

The present invention relates to a polymerization inhibitor composition and a method of inhibiting polymerization of distillable monomers in liquid and evaporated/condensed phases with the polymerization inhibitor composition. The polymerization inhibitor composition is useful for inhibiting polymerization of the distillable monomers during manufacture, purification (e.g., distillation), handling, and storage thereof.

First claim

What is claimed is:

1. A distillable-monomer polymerization inhibitor composition comprising a liquid mixture comprising a distillable monomer, a captive polymerization inhibitor and a fugitive polymerization inhibitor, wherein:
the distillable monomer is an acrylic acid-type monomer of formula (M):

wherein R 11 is hydrogen or (C 1 -C 18 )alkyl and each of R 12 to R 14 independently is hydrogen or (C 1 -C 8 )alkyl;
the captive polymerization inhibitor comprises a mixture of molecular oxygen and phenothiazine, or an acid addition salt thereof, and is present in an amount of from 5 parts per million to 500 parts per million of the liquid mixture;
the captive polymerization inhibitor and the fugitive polymerization inhibitor are different and not interconvertible between one another;
each of the fugitive polymerization inhibitor and the captive polymerization inhibitor independently is characterizable as being an inhibitor of polymerization of the distillable monomer; and
the fugitive polymerization inhibitor is characterizable as being capable of evaporating with the distillable monomer from a first location and condensing with the distillable monomer at a second location that is different than the first location during distillation of the distillable monomer, wherein the fugitive polymerization inhibitor comprises nitrosobenzene and is present in an amount of from greater than 25 parts per million to 2000 parts per million of the liquid mixture; and
wherein the acrylic acid-type monomer of formula (M) and the fugitive polymerization inhibitor are characterized by either (i) respective first and second liquid vapor pressures of substantially pure forms thereof or (ii) relative volatility of a test mixture consisting essentially of the acrylic acid-type monomer of formula (M), the fugitive polymerization inhibitor, and the captive polymerization inhibitor, wherein the first and second liquid vapor pressures are independently determined at a same elevated temperature, the elevated temperature being 50 degrees Celsius or higher, and the first liquid vapor pressure and the second liquid vapor pressure independently are at least 5 kiloPascals and are within 40 kiloPascals of each other; and the relative volatility of the test mixture is from 0.5 to 10.

2. The composition as in claim 1 , wherein the acrylic acid-type monomer of formula (M) and the fugitive polymerization inhibitor are characterized by (i) respective first and second liquid vapor pressures of substantially pure forms thereof, wherein the first and second liquid vapor pressures are independently determined at a same elevated temperature, the elevated temperature being 50 degrees Celsius or higher, and the first liquid vapor pressure and the second liquid vapor pressure independently are at least 5 kiloPascals and are within 40 kiloPascals of each other.

3. The composition as in claim 1 , wherein the nitrosobenzene is present in an amount of from greater than 50 parts per million to 200 parts per million of the liquid mixture.

4. The composition of claim 1 , wherein the captive polymerization inhibitor further comprises a manganese salt that is Mn(HCO 2 − ) 2 , Mn((C 1 -C 8 )alkylCO 2 − ) 2 , or potassium permanganate.

5. The composition of claim 4 , wherein the manganese salt is manganese(II) acetate.

6. The composition of claim 1 , wherein the captive polymerization inhibitor further comprises a mixture of an N-oxyl compound and a manganese salt that is Mn(HCO 2 − ) 2 , Mn((C 1 -C 8 )alkylCO 2 − ) 2 , or potassium permanganate, optionally wherein the N-oxyl compound is 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl.

7. The composition of claim 1 , wherein the phenothiazine is present in an amount of from 10 parts per million to 250 parts per million of the liquid mixture.

8. The composition of claim 1 , wherein the captive polymerization inhibitor further comprises a mixture of molecular oxygen and a compound of formula (II):

or an acid addition salt thereof,
wherein X is S, O, or N—R 3 ;
R 1 is hydrogen or (C 1 -C 3 )alkyl;
R 2 is phenyl; and
R 3 is (C 1 -C 3 )alkyl.

9. The composition of claim 8 , wherein X is S.

10. The composition of claim 8 , wherein R 1 is hydrogen.

11. The composition of claim 8 , wherein R 1 is (C 1 -C 3 )alkyl.

12. The composition of claim 8 , wherein R 1 is methyl.

13. The composition of claim 1 , wherein the distillable monomer is acrylic acid.

14. The composition of claim 1 , wherein the acrylic acid-type monomer of formula (M) and the fugitive polymerization inhibitor are characterized by (ii) relative volatility of a test mixture consisting essentially of the acrylic acid-type monomer of formula (M), the fugitive polymerization inhibitor, and the captive polymerization inhibitor, wherein the relative volatility of the test mixture is from 0.5 to 10.

15. The composition of claim 1 , wherein the captive polymerization inhibitor further comprises hydroquinone.

16. A method of inhibiting polymerization of a distillable monomer during a distillation thereof, wherein the distillable monomer is an acrylic acid-type monomer of formula (M):

wherein R 11 is hydrogen or (C 1 -C 18 )alkyl and each of R 12 to R 14 independently is hydrogen or (C 1 -C 8 )alkyl, the method comprising steps of:

(a) contacting together a distillable-monomer polymerization inhibitor composition and an amount of the distillable monomer to give a liquid mixture thereof at a first location, wherein the composition comprises a first polymerization inhibiting amount of a fugitive polymerization inhibitor and an inhibiting amount of a captive polymerization inhibitor, wherein the captive polymerization inhibitor and the fugitive polymerization inhibitor are different, not interconvertible between one another, and each of the fugitive polymerization inhibitor and the captive polymerization inhibitor independently is characterized as being an inhibitor of polymerization of the distillable monomer, and wherein the captive polymerization inhibitor comprises a mixture of molecular oxygen and phenothiazine, or an acid addition salt thereof, and is present in an amount of from 5 parts per million to 500 parts per million of the liquid mixture;
(b) evaporating from the first location at least some of the distillable monomer and at least some of the fugitive polymerization inhibitor to respectively give an evaporated distillable monomer and an evaporated fugitive polymerization inhibitor; and
(c) condensing together at least some of the evaporated distillable monomer and at least some of the evaporated fugitive polymerization inhibitor to give a condensate mixture thereof at a second location that is different than and in fluid communication with the first location, wherein the condensate mixture comprises some of the amount of the distillable monomer and a second polymerization inhibiting amount of the fugitive polymerization inhibitor;
wherein polymerization of the distillable monomer at the second location is inhibited by the second polymerization inhibiting amount of the fugitive polymerization inhibitor; in and under conditions of distilling steps (b) and (c), the fugitive polymerization inhibitor has a vapor pr

Assignees

• Kar Kishore K
• Cloeter Michael D
• Fruchey Olan Stanley
• Harner Richard S
• Matyjaszewski Krzysztof
• Nicolay Renaud
• Mosná{Hacek Over (C)}Ek Jaroslav
• Dow Global Technologies Llc

Inventors

• Kar Kishore K
• Cloeter Michael D
• Fruchey Olan Stanley
• Harner Richard S
• Matyjaszewski Krzysztof
• Nicolay Renaud
• Mosná{Hacek Over (C)}Ek Jaroslav

Classifications

• C07C57/04

  Acrylic acid; Methacrylic acid · CPC title

• C08F2/40

  using retarding agents · CPC title

• C07C51/44

  by distillation · CPC title

• C07C51/50

  Use of additives, e.g. for stabilisation · CPC title

• C08F2/42 Primary

  using short-stopping agents · CPC title