WO2000042079A1 - Sterically-hindered alkyl hydroxylamines for scavenging of free radicals - Google Patents
Sterically-hindered alkyl hydroxylamines for scavenging of free radicals Download PDFInfo
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- WO2000042079A1 WO2000042079A1 PCT/US2000/001291 US0001291W WO0042079A1 WO 2000042079 A1 WO2000042079 A1 WO 2000042079A1 US 0001291 W US0001291 W US 0001291W WO 0042079 A1 WO0042079 A1 WO 0042079A1
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- free radical
- sterically
- hydroxylamine
- radical scavenger
- hindered
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- NQDPYLXOECUYRE-UHFFFAOYSA-N CC(C)(CN(C)C)NO Chemical compound CC(C)(CN(C)C)NO NQDPYLXOECUYRE-UHFFFAOYSA-N 0.000 description 1
- QKVSMSABRNCNRS-UHFFFAOYSA-N CC(C)CN1CCOCC1 Chemical compound CC(C)CN1CCOCC1 QKVSMSABRNCNRS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/42—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using short-stopping agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
- C07C239/08—Hydroxylamino compounds or their ethers or esters
- C07C239/16—Hydroxylamino compounds or their ethers or esters having nitrogen atoms of hydroxylamino groups further bound to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/20—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
- C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—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 an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
Definitions
- Free radical scavengers are required in many industrial processes. Examples include free radical polymerizations, such as styrene-butadiene co-polymerizations, where a radical scavenger is added to stop the reaction prior to complete monomer conversion, and production of unsaturated monomers where radical scavengers are added to prevent unwanted polymerization.
- DEHA also contains diethylamine, which can form nitrosamines, which are undesirable because they have been found to be carcinogenic in laboratory animal studies and are regulated in some countries.
- DEHA can be combined with a non- volatile free radical scavenger like sodium dimethyldithiocarbamate (SDD) or sodium tetrasulfide (ST), however, these can create other problems.
- SDD can form nitrosamines
- ST can generate toxic, corrosive hydrogen sulfide.
- Newer technologies, such as stable free radicals (SFRs) are available which are effective and avoid many of the above shortcomings.
- a good example of an SFR is 4-hydroxy-2,2,6,6- tetramethylpiperidinyloxy, commonly known as 4-hydroxy TEMPO. Although effective, this product is expensive.
- DNP dinitrophenol
- Phenylenediamine (PD) derivatives are also widely used as stabilizers in styrene and other monomers, however, they require the presence of oxygen for optimum performance. Addition of oxygen to monomer purification equipment can be hazardous and must be closely controlled. Newer chemistries, such as SFRs and N-nitroso-N-phenyl hydroxylamine, ammonium salt (Cupferron), are effective, but are expensive and, in the case of Cupferron, there are safety concerns (toxicity, suspected carcinogen). Accordingly, there is a need for a high boiling, effective monomer stabilizer, which is compatible with a variety of monomers and relatively safe to handle and use.
- the invention relates to sterically-hindered alkyl hydroxylamines as free radical scavengers for shortstopping radical polymerizations and as inhibitors for preventing unwanted polymerization of unsaturated monomers during their production.
- Preferred sterically-hindered alkyl hydroxylamines are defined by the formulas below.
- a particularly preferred compound is t-butyl hydroxylamine.
- related stable nitroxides may be used.
- the invention is an improved process for carrying out free radical polymerization reactions in which a sterically-hindered alkyl hydroxylamine is added as a shortstopping agent.
- the invention also includes stabilization of monomers, especially styrene, to limit unwanted polymer formation during production or storage and transportation of such monomers.
- the invention includes using sterically-hindered alkyl hydroxylamines as free radical scavengers for shortstopping radical polymerizations and for stabilizing monomers during their production and purification.
- sterically-hindered alkyl hydroxylamines of the invention are described by the following Formulas.
- Rj, R 2) R 3 , and R 4 are independently hydrogen, C1-C 10 alkyl, hydroxyalkyl, or amino alkyl, optionally substituted with a heterocycMc radical, providing that not more than one of Ri, R 2 and R 3 maybe hydrogen; and R 4 is hydrogen or Ci-Cio alkyl
- hydroxylamines according to Formula I examples include t-butyl hydroxylamine, -hydroxylamine-2-methylbutane, and 2-hydroxylamine-3-methylbutane.
- substituted hydroxylamines include the following.
- R5, Re, R7, Rs, R9, Rio, ⁇ and Rj 2 are hydrogen or C1-C10 alkyl and two or all of C a , C ⁇ and C c are included in an aliphatic or a heterocyclic ring
- hydroxylamines according to Formula II include cycloaliphatic hydroxylamines, such as methylcyclohexyl hydroxylamine where the methyl and hydroxylamine substituents appear on the same carbon atom, and heterocycUc hydroxylamines such as the following:
- the sterically-hindered hydroxylamines may form or be formed into stable nitroxides, for example, the nitroxide of t-butyl hydroxylamine hydroxylamine nitroxide
- nitroxides will be effective as free radical scavengers and, thus, will serve as shortstopping agents and polymerization inhibitors.
- the sterically-hindered alkyl hydroxylamine is preferably added as a solution in an appropriate solvent.
- an appropriate solvent for example, many free radical polymerizations are carried out in an emulsion process, where it is desirable to introduce the shortstop as a relatively dilute aqueous solution.
- the solvent choice for diluting the radical scavenger will vary with the monomer.
- ethylbenzene is a good choice for styrene
- water or another polar diluent may be preferred for acryhc acid or acrylate esters.
- the diluted scavenger must be easily introduced into the monomer purification system using existing feed equipment, and must readily dissolve in the monomer.
- polymerization systems where the present invention is applicable include, but are not hmited to, free radical polymerizations of 1,3 -butadiene, 2-chlorobutadiene-l,3 (chloroprene), vinyl chloride, tetrafluoroethylene, and vinylidene fluoride, as well as co-polymerizations of styrene-butadiene and acrylonitrile-butadiene.
- the present invention is particularly useful in shortstopping the copolymerizations of styrene-butadiene and acrylonitrile-butadiene.
- Examples of unsaturated monomer systems where the present invention is applicable include, but are not Hmited to, production and purification of styrene, 1,3-butadiene, acrylonitrile, acrylic acid, methyl methacrylate, vinyl chloride, vinyl acetate, n-butyl acrylate, methyl acrylate, tetrafluoroethylene, etc.
- the present invention is especially useful in preventing polymerization of styrene during its production and purification.
- sterically-hindered hydroxylamines as free radical scavengers, it is believed that such hydroxylamines will also be useful as oxygen scavengers in boiler feed water treatment applications and the like.
- combinations of the sterically-hindered hydroxylamines disclosed herein and known compounds such as TEMPO and dinitrophenols, specifically dinitro-o-sec- butylphenol are useful free-radical scavengers.
- TBHA sterically-hindered hydroxylamine t-butyl hydroxylamine
- the vials were placed into a 120°C oven for three hours, removed and cooled at room temperature for thirty minutes.
- the ohgomer/polymer solids in each sample were measured by placing about one gram of sample into methanol and then evaporating the methanol and remaining styrene monomer in a vacuum oven at 70°C (about 16 hours). The following results were obtained.
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Abstract
Free radical scavengers are formed from sterically-hindered alkylhydroxylamines. The free radical scavengers are believed useful to interrupt polymerization reactions or to facilitate storage and transportation of reactive monomers. Free radical scavengers preferably have formula (I).
Description
STERICALLY-HINDERED ALKYL HYDROXYLAMINES FOR SCAVENGING OF FREE RADICALS
Free radical scavengers are required in many industrial processes. Examples include free radical polymerizations, such as styrene-butadiene co-polymerizations, where a radical scavenger is added to stop the reaction prior to complete monomer conversion, and production of unsaturated monomers where radical scavengers are added to prevent unwanted polymerization.
In free radical polymerizations, it is often desired to stop the reaction before complete monomer-to-polymer conversion. Such "shortstopped" polymers often exhibit superior performance properties when compared with fully converted polymers. In order to shortstop the reaction, it is necessary to add a material that will react with the free radicals and prevent them from reforming. Free radical scavengers serve this purpose. There are many free radical scavengers used commercially as shortstops. These products suffer from one or more shortcomings. For example, N,N-diethyl- hydroxylamine (DEHA) is effective, however, it is relatively volatile and during steam stripping of unreacted monomers from emulsion polymers, not enough DEHA remains in the emulsion to completely stop the reaction. DEHA also contains diethylamine, which can form nitrosamines, which are undesirable because they have been found to be carcinogenic in laboratory animal studies and are regulated in some countries. DEHA can be combined with a non- volatile free radical scavenger like sodium dimethyldithiocarbamate (SDD) or sodium tetrasulfide (ST), however, these can create other problems. SDD can form nitrosamines, while ST can generate toxic, corrosive hydrogen sulfide. Newer technologies, such as stable free radicals (SFRs), are available which are effective and avoid many of the above shortcomings. A good example of an SFR is 4-hydroxy-2,2,6,6- tetramethylpiperidinyloxy, commonly known as 4-hydroxy TEMPO. Although effective, this product is expensive. A need exists, therefore, for a relatively non- volatile, cost effective, non-nitrosamine- forming free-radical scavenger (shortshop) for radical polymerizations.
In the production of unsaturated monomers, such as styrene, acrylic acid, butadiene, etc., there is a tendency for the monomers to polymerize. This results in undesirable fouling of equipment and yield losses. Free radical scavengers are added to such monomer streams during their purification to prevent such unwanted polymerization. Several scavengers are used commercially, but all suffer from one or more drawbacks. For example, dinitrophenol (DNP) derivatives are widely used as styrene stabilizers, however, they are very toxic and can be an explosion hazard under certain conditions.
Phenylenediamine (PD) derivatives are also widely used as stabilizers in styrene and other monomers, however, they require the presence of oxygen for optimum performance. Addition of oxygen to monomer purification equipment can be hazardous and must be closely controlled. Newer chemistries, such as SFRs and N-nitroso-N-phenyl hydroxylamine, ammonium salt (Cupferron), are effective, but are expensive and, in the case of Cupferron, there are safety concerns (toxicity, suspected carcinogen). Accordingly, there is a need for a high boiling, effective monomer stabilizer, which is compatible with a variety of monomers and relatively safe to handle and use.
In one aspect, the invention relates to sterically-hindered alkyl hydroxylamines as free radical scavengers for shortstopping radical polymerizations and as inhibitors for preventing unwanted polymerization of unsaturated monomers during their production. Preferred sterically-hindered alkyl hydroxylamines are defined by the formulas below. A particularly preferred compound is t-butyl hydroxylamine. Alternatively, related stable nitroxides may be used.
In another aspect, the invention is an improved process for carrying out free radical polymerization reactions in which a sterically-hindered alkyl hydroxylamine is added as a shortstopping agent. The invention also includes stabilization of monomers, especially styrene, to limit unwanted polymer formation during production or storage and transportation of such monomers.
Shortstops And Inhibitors
The invention includes using sterically-hindered alkyl hydroxylamines as free radical scavengers for shortstopping radical polymerizations and for stabilizing monomers during their production and purification. The preferred sterically-hindered alkyl hydroxylamines of the invention are described by the following Formulas. Formula I
Examples of hydroxylamines according to Formula I include t-butyl hydroxylamine, -hydroxylamine-2-methylbutane, and 2-hydroxylamine-3-methylbutane.
Examples of substituted hydroxylamines include the following.
NHOH
4-(2-hydroxylaminobutyl)-morp oline
CH2CH3
CH3 NHOH yCH3 \ N— CH2 c CH2 N 4-hydroxylamino-2,4,6-trimethyl-2,6-diazaheptane
/
CH3 H3
Formula II
where: R5, Re, R7, Rs, R9, Rio, π and Rj2 are hydrogen or C1-C10 alkyl and two or all of Ca, C^ and Cc are included in an aliphatic or a heterocyclic ring
Examples of hydroxylamines according to Formula II include cycloaliphatic hydroxylamines, such as methylcyclohexyl hydroxylamine where the methyl and hydroxylamine substituents appear on the same carbon atom, and heterocycUc hydroxylamines such as the following:
dioxane
The sterically-hindered hydroxylamines may form or be formed into stable nitroxides, for example, the nitroxide of t-butyl hydroxylamine
hydroxylamine nitroxide
It is believed that the nitroxides will be effective as free radical scavengers and, thus, will serve as shortstopping agents and polymerization inhibitors.
Use of the Shortstops and Inhibitors
The sterically-hindered alkyl hydroxylamine is preferably added as a solution in an appropriate solvent. For example, many free radical polymerizations are carried out in an emulsion process, where it is desirable to introduce the shortstop as a relatively dilute aqueous solution. For stabilization of monomers, the solvent choice for diluting the radical scavenger will vary with the monomer. For example, ethylbenzene is a good choice for styrene, while water or another polar diluent may be preferred for acryhc acid or acrylate esters. In general, the diluted scavenger must be easily introduced into the monomer purification system using existing feed equipment, and must readily dissolve in the monomer.
Examples of polymerization systems where the present invention is applicable include, but are not hmited to, free radical polymerizations of 1,3 -butadiene, 2-chlorobutadiene-l,3 (chloroprene), vinyl chloride, tetrafluoroethylene, and vinylidene fluoride, as well as co-polymerizations of styrene-butadiene and acrylonitrile-butadiene. The present invention is particularly useful in shortstopping the copolymerizations of styrene-butadiene and acrylonitrile-butadiene.
Examples of unsaturated monomer systems where the present invention is applicable include, but are not Hmited to, production and purification of styrene, 1,3-butadiene, acrylonitrile, acrylic acid, methyl methacrylate, vinyl chloride, vinyl acetate, n-butyl acrylate, methyl acrylate, tetrafluoroethylene, etc. The present invention is especially useful in preventing polymerization of styrene during its production and purification.
In addition to the use of sterically-hindered hydroxylamines as free radical scavengers, it is believed that such hydroxylamines will also be useful as oxygen scavengers in boiler feed water treatment applications and the like. Further, combinations of the sterically-hindered hydroxylamines disclosed herein and known compounds such as TEMPO and dinitrophenols, specifically dinitro-o-sec- butylphenol, are useful free-radical scavengers.
Example 1
The usefulness of the sterically-hindered hydroxylamine t-butyl hydroxylamine (TBHA) at preventing polymerization of styrene was demonstrated in a laboratory aging test. The t-butyl catechol (TBC) inhibitor was removed from a sample of commercial styrene by passing through a TBC adsorption column. The uninhibited styrene was split into three portions. To one portion was added 500 parts per million (ppm) of active TBHA. TBHA was supplied as a 90.6 percent active solid. To a second portion was added 500 ppm active dinitro-p-cresol (DNPC). The third portion was used as a control (uninhibited). The TBHA and DNPC were dissolved by mixing, and then all of the samples were sparged with nitrogen and sealed under nitrogen in glass vials
The vials were placed into a 120°C oven for three hours, removed and cooled at room temperature for thirty minutes. The ohgomer/polymer solids in each sample were measured by placing about one gram of sample into methanol and then evaporating the methanol and remaining styrene monomer in a vacuum oven at 70°C (about 16 hours). The following results were obtained.
Both TBHA and DNPC are equally effective at preventing styrene polymerization. TBHA, however, is believed to be relatively safe to handle and use, while DNPC presents safety hazards as previously described.
Example 2
The efficacy of TBHA at preventing polymerization of acrylic acid was assessed in the laboratory. Commercial acryhc acid containing monomethylether hydroquinone (MEHQ) as an inhibitor was distilled. The inhibitor-free distilled material was split into two portions. To one portion was added 500 ppm of active TBHA, while the other portion served as a control (uninhibited). The samples were sealed under air and placed into an 80°C oven. The samples were checked frequently and observed for physical changes indicative of polymerization (haziness, precipitate, solidification, etc.). The elapsed time at which polymerization was first noted was recorded for each sample and the results are reported below.
The results show that TBHA is very effective at delaying the onset of polymerization of acryhc acid.
While the present invention has been described with reference to one or more particular embodiments, those skilled in the art will recognize that many changes may be made thereto without departing from the spirit and scope of the present invention. Each of these embodiments and obvious variations thereof is contemplated as falling within the spirit and scope of the claimed invention, which is set forth in the following claims.
Claims
WHAT IS CLAIMED IS:
1. A free radical scavenger comprising a sterically-hindered alkyl hydroxylamine.
2. The free radical scavenger of Claim 1 , wherein said sterically-hindered hydroxylamine has the formula
where Ri, R2, R3 and R4are independently hydrogen, Ci-Cio alkyl, hydroxylalkyl, or amino alkyl, optionally substituted with a heterocyclic radical providing that not more than one of Ri, R2 and R3 may be hydrogen.
3. The free radical scavenger of Claim 2 wherein Ri, R2 and R3 are alkyl groups or hydroxyalkyl groups, and R4 is hydrogen.
4. The free radical scavenger of Claim 2, wherein Ri, R2 and R3 are methyl and R is hydrogen.
5. The free radical scavenger of Claim 2, wherein R4 is hydrogen, Ri and R2 are methyl, and R3is ethyl.
6. The free radical scavenger of Claim 2, wherein Ri and R4 are hydrogen, R2 is methyl, and R3is i-propyl.
7. The free radical scavenger of Claim 2 having the formula
NHOH
O N CH -H 4-(2-hydroxylaminobutyl)-mo holine
CH2CH3
The free radical scavenger of Claim 2 having the formula
9. The free radical scavenger of Claim 2 having the formula
,4,6-trirιιeuιyl-2,6-diazaheptane
10. The free radical scavenger of Claim 1 , wherein said sterically-hindered hydroxylamine has the formula
Formula II
where R5, Re, R7, Re, R9, Rio, R11 and Ri2 are hydrogen or C Cι0 alkyl and two or all of Ca, CD and Cc are included in an aliphatic or heterocyclic ring.
11. The free radical scavenger of Claim 10, wherein said cycloaliphatic ring is methylcyclohexyl.
12. The free radical scavenger of Claim 10, wherein said hydroxylamine has the formula
dioxane
13. In a free radical polymerization reaction, the improvement comprising adding to the reacting mixture a sterically-hindered alkyl hydroxylamine as a shortstopping agent.
14. The free radical polymerization reaction of Claim 13, wherein said shortstopping agent is t-butyl hydroxylamine.
15. As a free radical polymerization inhibitor, a sterically-hindered hydroxylamine.
16. An inhibitor of Claim 15 , wherein said sterically-hindered hydroxylamine is t-butyl hydroxylanime.
17. In a process for making a monomer which polymerizes by a free radical reaction, the improvement comprising adding a sterically-hindered hydroxylamine as a polymerization inhibitor.
18. The process of Claim 17, wherein said monomer is styrene.
19. The process of Claim 17, wherein said sterically-hindered hydroxylamine is t-butyl hydroxylamine
20. A method of inhibiting free radical polymerization of monomers during storage and transportation, comprising adding a sterically-hindered hydroxylamine to said monomer.
21. The method of Claim 20, wherein said monomer is styrene.
22. The method of Claim 20, wherein said monomer is acryhc acid.
23. The free radical scavenger of Claim 2 in the form of a nitroxide.
24. The free radical scavenger of Claim 10 in the form of a nitroxide.
25. In a process of operating a steam boiler, the improvement of adding a sterically- hindred hydroxylamine of any of Claims 1 - 16 as an oxygen scavenger.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU29683/00A AU2968300A (en) | 1999-01-19 | 2000-01-19 | Sterically-hindered alkyl hydroxylamines for scavenging of free radicals |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11639899P | 1999-01-19 | 1999-01-19 | |
| US60/116,398 | 1999-01-19 |
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|---|---|
| WO2000042079A1 true WO2000042079A1 (en) | 2000-07-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2000/001291 WO2000042079A1 (en) | 1999-01-19 | 2000-01-19 | Sterically-hindered alkyl hydroxylamines for scavenging of free radicals |
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| WO (1) | WO2000042079A1 (en) |
Cited By (8)
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|---|---|---|---|---|
| DE3205776A1 (en) | 1982-02-18 | 1983-08-25 | Truetzschler & Co | DEVICE FOR REGULATING THE AMOUNT OF FIBERS TO BE ADDED TO A TEXTILE MACHINE |
| WO2003016268A1 (en) * | 2001-08-13 | 2003-02-27 | Basf Aktiengesellschaft | Stabilisation of ethylenically-unsaturated compounds with amidoximes |
| WO2005021630A1 (en) * | 2003-08-27 | 2005-03-10 | Ciba Specialty Chemicals Holding Inc. | Composition and process for the controlled synthesis of block copolymers |
| WO2009129097A1 (en) * | 2008-04-16 | 2009-10-22 | Angus Chemical Company | Nitrated hydrocarbons, derivatives, and processes for their manufacture |
| US8519199B2 (en) | 2008-04-16 | 2013-08-27 | Angus Chemical Company | Process for the manufacture of nitropropanes |
| JP2015519466A (en) * | 2013-06-13 | 2015-07-09 | アンガス ケミカル カンパニー | Alkylhydroxylamine compounds and their use for terminating free radical polymerization |
| US9234052B2 (en) | 2012-06-14 | 2016-01-12 | Angus Chemical Company | Alkyl hydroxylamine compounds and their use for shortstopping free radical polymerizations |
| US9309331B2 (en) | 2012-09-28 | 2016-04-12 | Angus Chemical Company | Alkyl hydroxylamine compounds and their use for shortstopping free radical polymerizations |
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2000
- 2000-01-19 WO PCT/US2000/001291 patent/WO2000042079A1/en active Application Filing
- 2000-01-19 AU AU29683/00A patent/AU2968300A/en not_active Abandoned
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| JPS5849323A (en) * | 1981-09-17 | 1983-03-23 | Tokai Denka Kogyo Kk | Stabilization of methylchloroform |
| US4929660A (en) * | 1986-03-14 | 1990-05-29 | The Kendall Company | Acrylic adhesive compositions having improved stability |
| EP0243936A2 (en) * | 1986-04-30 | 1987-11-04 | E.I. Du Pont De Nemours And Company | Photopolymer color-proofing films with improved white light stability |
| US5001233A (en) * | 1989-09-14 | 1991-03-19 | The Curators Of The University Of Missouri | Synthesis of hydroxylamines using dioxiranes |
| EP0698580A1 (en) * | 1994-08-22 | 1996-02-28 | Faborga S.A. | Means for preventing deposit formation and oxygen corrosion in industrial process waters |
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