Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
  • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
  • C09K15/20—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen
• • 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
  • C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
  • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S585/00—Chemistry of hydrocarbon compounds
  • Y10S585/949—Miscellaneous considerations
  • Y10S585/95—Prevention or removal of corrosion or solid deposits

Definitions

• the present invention is directed to the inhibition of polymerization
• Polymerization can also result in equipment fouling, especially in the case of
• mode of action for polymerization inhibitors is for the inhibiting species to combine
• portion of chain ends are active (propagating) and these are in equilibria with inactive
• organometallic species and catalyzed atom transfer radical polymerization.
• "living" polymer is capable of increasing in molecular weight (growing) through its reaction with additional monomer units of the same or different types of
• reaction (3) depicts growth of the polymer chain.
• reaction (4) depicts re-
• stream typically contains inhibitor, small amounts of monomer, impurities in the
• the polymer will remain within the system indefinitely (potentially for two or more
• shut-down of the plant in order to clean out the undissolved polymer in the equipment.
• Such a shut-down results in loss of monomer production and additional expense to
• radicals are highly efficient polymerization inhibitors under normal use, providing
• compositions that can be used in a purification train, preferably in
• Nitroxyl radicals are known to facilitate polymerization via a "living" free
• the process comprised heating a mixture of monomer(s),
• free-radical initiator and a stable free radical, e.g., 2,2,6,6-tetramethyl-l-
• nitroxyl compounds are known to be very active inhibitors of free radical
• one X represents a halogen and the other X represents a member of the group
• R, R 2 , and R 3 are each an alkyl radical having 1 to 15 carbon atoms.
• N-O* denotes a stable free radical wherein the asterisk is
• N,N.O-trisubstituted hydroxylamines can be used to make
• reaction medium virtually any hydroxylamine that is susceptible to cleavage of the O-
• C bond e.g., tri-t-butylhydroxylamine.
• R is selected from the group consisting of tertiary alkyl, aryl. alkaryl,
• inhibitors or antioxidants are constituted by nitrogenous bicyclic compounds in
• U.S. Patent Number 3,873,564 discloses compounds and a method for
• the compounds found useful are normally stable nitroxide radicals with
• tetravalent radicals are powerful light-stabilizers for organic polymers. They are
• substituents in the 4-position are alkyl, alkylene. alkenyl. aralkyl, and esteralkyl
• peroxide or percarboxylic acids are also said to be good light stabilizers.
• process comprises subjecting a vinyl aromatic compound to elevated temperatures in a
• the process comprises subjecting a vinyl aromatic compound to
• improvement comprises employing 3.5-dinitrosalicylic acid or a derivative or isomer
• the process inhibitor is present in a concentration of
• the compound includes effective amounts of
• composition includes effective amounts of compounds, such as styrene, during heating.
• the composition includes effective amounts of compounds, such as styrene, during heating.
• U.S. Patent Number 4,480,1 16 discloses an improvement in methods for
• improvement comprises employing phenyl-para-benzoquinone. 2.5-di-phenyl-para-
• ppm ppm, and most preferably about 500 ppm.
• polymerization inhibitor such as a nitrated phenol to the vaporous crude vinyltoluene
• inhibitor concentration totals about 500 parts per million by weight relative to the
• ethylenically unsaturated monomers for example, unsaturated carboxylic acids and derivatives thereof.
• producing acrylonitrile comprising adding to the acrylonitrile an effective amount for
• R and R are the same or different and are hydrogen, alkyl, aryl, alkaryl or
• the phenylenediamine is a para-phenylenediamine having
• R 1 , R 2 , R 3 and R 4 are the same or different and are hydrogen, alkyl, aryl,
• R and R' are the same or different and are hydrogen, alkyl, aryl, alkaryl or
• the phenylenediamine is a para-phenylenediamine having
• R 1 , R 2 , R 3 and R 4 are the same or different and are hydrogen, alkyl, aryl, alkaryl, or aralkyl groups with the proviso that at least one of R 1 , R 2 , R 3 or R 4 is
• Mannich reaction product which is prepared from a substituted phenol, an aldehyde
• compositions comprise a combination of (a) a phenylenediamine compound having at least one of (a) a phenylenediamine compound having at least one of (a) a phenylenediamine compound having at least one of (a) a phenylenediamine compound having at least one of (a) a phenylenediamine compound having at least one of (a) a phenylenediamine compound having at
• the methods comprise
• U.S. Patent Number 5,128,022 discloses methods and compositions for
• compositions comprise a combination of
• N-Phenyl-N'-(l ,3-dimethylbutyl)-p-phenylenediamine (PDA) and an organic acid are examples of organic compounds.
• the methods comprise adding from 1 to 2500 ppm PDA and 1 to 3500 ppm organic
• aromatic compound such as styrene
• These methods comprise adding from 1 to about 10,000 parts per million parts
• a phenylenediamine compound Preferably, 2-sec-butyl-4,6-dinitrophenol or 4.6-
• dinitro-o-cresol are used in combination with bis-(hydroxypropyl)hydroxylamine and
• European Patent Application 0 178 168 A2 discloses a method for inhibiting
• polymerization inhibition composition comprising (a) a phenothiazine compound
• compositions for inhibiting the polymerization of vinyl aromatic monomers under
• compositions comprise a combination of a
• European Patent Application 0 765 856 Al discloses a stabilized acrylic acid
• compositions comprise three components: (a) acrylic acid,
• At least one transferable hydrogen e.g., a quinone derivative such as the monomethyl
• components (b) and (c) are present in a polymerization-inhibiting amount.
• oxygen (d) is preferably added with components (b)
• compounds include di-t-butylnitroxide; di-t-amylnitroxide; 2,2,6,6-tetramethyl-
• piperidinyloxy 4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy; 4-oxo-2,2,6,6-
• WO 97/46504 concerns substance mixtures containing: (A) monomers
• WO 98/02403 relates to inhibiting the polymerization of vinyl aromatic
• WO 98/14416 discloses that the polymerization of vinyl aromatic monomers
• N-oxyl compound of a secondary amine which does not carry any hydrogen atoms on the -carbon atoms; and (ii) at least one iron compound; (C) optionally nitro
• R,, R 2 , R 3 , and R 4 are alkyl groups and no hydrogen is bound to the remaining
• R 4 or nitrogen can also form part of a ring (e.g., 2.2,6,6
• CS-260755 B l is directed to the preparation of 4-substituted-2,2,6.6-
• SU-334845 Al is directed to the inhibition of the radical polymerization of
• SU-478838 is directed to the inhibition of the radical polymerization of
• polymerization inhibitor comprising quinone
• FR 2,761 ,060 relates to the prevention of premature polymerization of styrene
• the present invention is directed to a method for inhibiting
• monomers comprising adding to said monomers an effective amount of at least one inhibitor that is a hydrogen donor or an electron acceptor.
• transition metal ion is copper, especially Cu(I)naphthenate.
• the present invention is directed to a method for
• unsaturated monomers comprising adding to said monomers A) an effective amount
• the present invention is directed to a composition
• R, and R 4 are independently selected from the group consisting of
• R 2 and R 3 are independently hydrogen, alkyl, and heteroatom-substituted alkyl and R 2 and R 3 are independently
• X 2 (1) are independently selected from the group consisting of halogen, cyano,
• the nitrogen preferably of five, six, or seven members.
• the present invention is directed to inhibiting systems in
• the hydrogen donor compounds can. for example, be hydroxylamines, oximes.
• Such compounds can include a metal species which facilitates the reduction/oxidation reactions that can accompany growth inhibition through deactivation of the growing
• the hydrogen donor compounds are preferably
• R 101 are independently selected from the group consisting of hydrogen, alkyl.
• heterocyclic and substituted alkyl or aryl where the substituents are C, O. N. S.
• R 100 and R 10 can be taken together to form a ring structure of five to seven
• R ]02 and R 103 are independently selected from the group consisting of hydrogen, alkyl,
• substituents are C. O, N, S, or P, or R ]02 and R 103 can be taken together to form
• R 104 , R 10ache R I06 , R 107 , R ]08 . and R 109 are independently selected from the group consisting
• halogen includes fluorine, chlorine, bromine, and iodine), and/or any two
• adjacent groups can be taken together to form ring structure(s) of five to seven
• R, 04 , R 105 , R 106 , R l07 . R 108 , and R ]09 is OH
• R ⁇ o and R, , are independently selected from the group consisting of hydrogen, alkyl,
• R 1 12 is R, 02 , OR, 02 , or NR 102 R 103
• R I 13 , R 1 14 , and R 1 15 are independently selected from the group consisting of hydrogen,
• alkyl aryl, cycloalkyl, and heterocyclic moieties
• R 121 , R ]22 , and R ]23 are independently selected from the group
• alkyl consisting of hydrogen, alkyl, aryl, cycloalkyl, heterocyclic. substituted alkyl,
• the electron accepting compounds can, for example, be quinones, quinone
• Such compounds can include a metal
• electron accepting compounds are preferably chosen from compounds having the formula
• X and Y are independently selected from the group consisting of oxygen, NR no , and
• , R 122 , and R 123 are independently selected from the group consisting of
• R 120 and R, 2I can be taken together and/or R 122 and R 123 can be taken together to form
• one or two ring structures respectively, either of which can be of five to seven members;
• R, 24 and R I25 are independently selected from the group consisting of hydrogen, alkyl,
• aryl cycloalkyl, heterocyclic, substituted alkyl, substituted aryl. 0R 1 UI .
• R ⁇ o and R n ⁇ are independently selected from the group consisting of hydrogen, alkyl,
• R, 10 and R ⁇ n can be taken together to form
• R, 12 is R, 02 , OR, 02 , or NR 102 R, 03 ;
• R, 02 and R 103 are independently selected from the group consisting of hydrogen, alkyl,
• substituents are C, O, N, S, or P. or R, 02 and R 103 can be taken together to form
• R, 26 and R I27 are independently selected from the group consisting of hydrogen, alkyl,
• R 112 are defined as for formula VI.
• alkyl (or substituted alkyl) groups preferably contain 1 to 15
• carbon atoms e.g., methyl, ethyl, propyl. butyl, pentyl, hexyl, heptyl. octyl. nonyl,
• alkyl (or substituted alkyl) groups be of one to five carbon atoms (e.g., methyl, ethyl, propyl.
• Aryl groups are preferably of from 6 to 10 carbon atoms.
• phenyl or naphthyl which, in addition, may be substituted with non-interfering
• substituents e.g., lower alkyl groups, halogens, and the like.
• Exemplary hydrogen donating compounds include, but are not limited to,
• Exemplary electron accepting compounds include, but are not limited to,
• the present invention is directed to a
• monomers comprising adding to said monomers, in addition to at least one first
• R, and R 4 are independently selected from the group consisting of hydrogen, alkyl, and heteroatom-substituted alkyl and R 2 and R 3 are independently selected from
• -OCOR 7 (wherein R 7 is alkyl or aryl), amido, -S-C 6 H 5 , carbonyl. alkenyl, or alkyl of 1
• the stable hindered nitroxyl compound in a particularly preferred embodiment, the stable hindered nitroxyl compound
• R, and R 4 are independently selected from the group consisting of hydrogen,
• alkyl, and heteroatom-substituted alkyl and R 2 and R 3 are independently selected from the group consisting of alkyl and heteroatom-substituted alkyl, and the
• portion represents the atoms necessary to form a five-, six-, or seven-membered
• Z,, Z 2 . and Z 3 are independently selected from the group consisting of oxygen,
• substituted or unsubstituted carbon atoms such as >CH 2 .
• >CHCH 3 , >C 0, >C(CH 3 ) 2 , >CHBr, >CHC1.
• R 13 R, 4 and R, 5 are independently selected from the group consisting of unshared
• R 16 , R, 7 and R, 8 are independently selected from the group consisting of hydrogen, alkyl, and aryl .
• alkyl are alkyl, it is preferred that they be a lower alkyl (i.e., one having one to five carbon
• atoms e.g., methyl, ethyl, propyl, butyl, pentyl, and isomers thereof).
• R 5 and/or R 6 are aryl, it is preferred that they be aryl of from 6 to 10
• non-interfering substituents e.g., lower alkyl groups, halogens, and the like.
• R 5 and/or R 6 are acyl. it is preferred that they be acyl of the structure
• R 19 is alkyl, aryl, OR 20 , or NR 20 R 21 and where R 20 and R 2 , are alkyl, aryl, or
• R 22 is alkyl or aryl. Where R 19 . R 20 . R 21 , or R 22 are alkyl, they are preferably
• alkyl of from 1 to 15 carbon atoms, more preferably lower alkyl of from 1 to 5 carbon
• R, 9 . R 20 , R 2 ,, or R 22 are aryl, they are preferably aryl
• Z, and Z 2 which may be the same or different, are nitrogen or substituted or
• Z 2 and Z 3 which may be the same or different, are sulfur, oxygen, secondary amines, tertiary amines, phosphorus of various oxidation states, or substituted or
• Z 4 and Z tripod which can be the same or different, can be nitrogen or a substituted
• R 5 and R 6 are as described above.
• present invention is of the structure:
• Z 2 and Z 3 which may be the same or different, are sulfur, oxygen, secondary
• amines tertiary amines, or substituted or unsubstituted carbon atoms, such as, >CH 2 ,
• the several R groups are as described above. Further, two or more nitroxyl groups can be present in the same molecule, for
• R 2 and R 3 are independently selected from the group consisting of
• alkyl and heteroatom-substituted alkyl.
• the alkyl or heteroatom-substituted alkyl.
• groups R, through R 4 can be the same or different and preferably contain 1 to 15
• carbon atoms e.g., methyl, ethyl, propyl. butyl, pentyl, hexyl, heptyl. octyl, nonyl,
• R, through R 4 thereof, e.g., t-butyl, 2-ethylhexyl, and the like. It is more preferred that R, through R 4
• five carbon atoms e.g., methyl, ethyl, propyl, butyl, pentyl, and isomers thereof.
• heteroatom substituents can, for example, include halogen.
• R, through R 4 are oxygen, sulfur, nitrogen, and the like. It is most preferred that all of R, through R 4 be
• TEMPO 2,2,6,6-tetramethyl-l-
• 4-amino-TEMPO is 4-amino-2.2.6,6-tetramethyl-l-
• 4-oxo-TEMPO is 4-oxo-2,2,6,6-tetramethyl-l -
• the present invention be 4-amino-TEMPO, 4-oxo-TEMPO, 4-hydroxy-TEMPO, or
• TEMPO TEMPO
• stable nitroxide free radical compounds can be prepared by known
• distillations are generally
• polymer growth of which is an object of the present invention can be any such
• chloroprene isoprene, and the like.
• the ethylenically unsaturated monomers will not necessarily be stabilized
• substituted benzene compounds having at least one transferable hydrogen e.g., a
• quinone derivative such as the mono-methyl-ether of hydroquinone disclosed in
• the polymerization inhibitor(s) can be introduced into the monomer to be reacted.
• the inhibiting composition Since the inhibitors are gradually depleted during the
• Adding inhibitors can be done either on a generally continuous basis or
• the total inhibitor concentration should be from about 1 to about 2000 ppm
• nitroxyls based on the total of both components is from about 1 to 100 wt % A : about
• ert-butylcatechol (TBC) is removed from commercially a ⁇ ailable rene b ⁇
• insoluble polymer can be retained in the Pot by any suitable means.
• the insoluble polymer can be retained in the Pot by any suitable means.
• insoluble polymer is securely wrapped in a piece of filter paper or wire mesh and
• the Pot is placed in a hot oil bath, and the Feed Solution
• Feed and Bottoms Streams causes the quantity in the Pot to remain constant over the
• the filter paper bag of polymer is removed.
• the Pot solution is filtered to recover
• the polymer in the filter paper bag are allowed to dry open to the atmosphere for at
• the polymer can be further dried by placing it in a vacuum oven at 40-
• % growth weight of final insoluble polymer - weight of initial insoluble polymer x 100 weight of initial insoluble polymer
• TBC Tert-butylcatechol
• TBC Tert-butylcatechol
• Feed Solution is begun at a rate that will add the volume of the initial Pot solution to the
• the residence time typically, one hour
• inhibiting system does not effectively prevent polymer growth during recycle.
• Passes is an indication of the ability of the inhibiting system to prevent or allow
• 1 -3 are baseline examples of nitroxyl inhibitors used alone - conditions that are known
• the first example in Table 4 is also a baseline example of a nitroxyl inhibitor
• ⁇ DA N-phenyl-N'-(l,4-dimethylpentyl)-para-phenylenediamine
• DNBP 2,4-dinitro-6-sec-butylphenol
• PDA N-phenyl-N'-(l,4-dimethylpentyl)-para-phenylenediamine
• DNBP 2,4-dinitro-6-sec-butylphenol

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• 2000
  • 2000-11-13 CA CA2392526A patent/CA2392526C/en not_active Expired - Fee Related
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• 2004
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• 2009
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