WO1998058891A1 - Melange a base de diorganohydroxylamine stabilise ou inhibiteur de polymerisation - Google Patents

Melange a base de diorganohydroxylamine stabilise ou inhibiteur de polymerisation Download PDF

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Publication number
WO1998058891A1
WO1998058891A1 PCT/EP1998/003520 EP9803520W WO9858891A1 WO 1998058891 A1 WO1998058891 A1 WO 1998058891A1 EP 9803520 W EP9803520 W EP 9803520W WO 9858891 A1 WO9858891 A1 WO 9858891A1
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WIPO (PCT)
Prior art keywords
alkyl
cooh
general formula
independently
another
Prior art date
Application number
PCT/EP1998/003520
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German (de)
English (en)
Inventor
Hans-Michael Schneider
Bernd Leutner
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU85370/98A priority Critical patent/AU8537098A/en
Publication of WO1998058891A1 publication Critical patent/WO1998058891A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C07B63/04—Use of additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • 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

Definitions

  • the present invention relates to a mixture of
  • A represents alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene, arylene, o-, m- or p-xylylene, a 5- or 6-membered saturated or unsaturated heterocycle with a nitrogen tom, the radicals mentioned 1, 2 or 3 substituents aufwei- can sen, which are selected independently from among alkyl, alkoxy or hydroxy, or
  • B and X represent -CH 2 CH 2 - or -CH 2 CH 2 CH 2 -,
  • n 10 - 50,000
  • R represents H, alkyl, an ethylene or propylene radical substituted by OH, NH 2 , NHCOR 5 or COOH, CSSH, CH 2 CN or CH 2 P0 3 H or represents a bridge to a nitrogen atom of another polyethyleneimine or polypropyleneimine chain, where the bridge is formed by — ⁇ -NR-B-3— o or CH 2 CHOH CH 2 - ⁇ - 0 CH 2 CH 2 ⁇ - p CH 2 CHOH CH -, where o and p independently of one another represent 1-15,
  • R 5 represents H, Ci-Ci ⁇ -alkyl or CHR ⁇ COR 5 , where R 6 represents a C 2 -C 8 alkyl radical,
  • R 1 , R 2 , R 3 and R 4 independently of one another are H, CH 2 COOH, CH 2 P0 3 H 2 , alkyl, acyl, CH 2 CH 2 OH, CH 2 CH 2 NH 2 or
  • R7 represents OH, SH, H 2 , CN, COOH, alkyl or alkoxy, or the salts thereof,
  • R 8 , R 9 Ci to -C 8 alkyl, Ci to C 2 o -hydroxyalkyl, C 5 - bis
  • the present invention further relates to the use of compounds of the general formula (I) as a stabilizer against decomposition or inhibitor against polymerization of mixtures defined at the outset.
  • Diorganohydroxylamine derivatives can be used as substances which inhibit the polymerization of, for example, styrene, that is to say as polymerization inhibitors, as described in US Pat. No. 5,426,257.
  • Component (A) of the mixtures according to the invention is a compound of the formula I:
  • A represents alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene, arylene, o-, m- or p-xylylene, a 5- or 6-membered saturated or unsaturated heterocycle with a nitrogen atom
  • the radicals mentioned 1, 2 or 3 may have substituents which are independently selected from alkyl, alkoxy or hydroxy, or for
  • B and X represent -CH 2 CH 2 - or -CH 2 CH 2 CH 2 -,
  • n 10 - 50,000
  • R represents H, alkyl, an ethylene or propylene radical substituted by OH, NH 2 , NHCOR 5 or COOH, CSSH, CH 2 CN or
  • CHP0H stands or is a bridge to a nitrogen atom of another polyethyleneimine or polypropyleneimine chain, the bridge being through - [- RB — 3-0 or CH 2 CHOH CH 2 - (- 0 CH 2 CH 2 -4— p CH 2 CHOH CH 2 - is formed, where o and p independently of one another represent 1-15,
  • R 5 represents H, -CC 8 -alkyl or CHR 6 COR 6 , where R 6 is a c i 2 ⁇ Ci 8 -alkyl radical,
  • R 1 , R 2 , R 3 and R 4 independently of one another are H, CH 2 COOH, CH 2 P0 3 H 2 , alkyl, acyl, CH 2 CH 2 OH, CH 2 CH 2 NH 2 or
  • R 7 represents OH, SH, NH 2 , CN, COOH, alkyl or alkoxy, or the salts thereof.
  • alkyl represents a straight-chain or branched radical which preferably has 1 to 18 carbon atoms, in particular 1 to 6 carbon atoms and in particular 1 to 4 carbon atoms. The same applies to the alkyl group in alkoxy.
  • Alkylene stands for a straight-chain or branched divalent radical which preferably has 2 to 6 and in particular 2 to 4 carbon atoms.
  • Alkenylene and alkynylene represent straight-chain or branched, divalent radicals which preferably have 3 to 6 carbon atoms and in particular 3 or 4 carbon atoms.
  • Cycloalkylene and cycloalkenylene are preferably cyclopentylene or cyclohexylene or cyclopentenylene or cyclohexenylene.
  • Arylene is preferably an aromatic C ß- Cio hydrocarbon residue and phenylene.
  • the saturated or unsaturated heterocycle is preferably a pyrrolidinylene, piperidinylene, pyrrolylene or pyridinylene radical.
  • the heterocycle is bonded to the two nitrogen atoms of formula I via carbon atoms.
  • Acyl stands for a straight-chain or branched radical, which preferably has 1 to 19 carbon atoms.
  • A is preferably alkylene, cycloalkylene, arylene or
  • radicals R 1 to R 4 then stand independently of one another, preferably CH 2 COOH, CH 2 CH 2 OH, CH 2 CH 2 NH 2 or especially for CH 2 COOH or
  • R 7 is preferably in the o-position and in particular means OH, COOH or a branched (bulky) alkyl radical, such as isopropyl, t-butyl, etc.
  • the compounds I according to the invention can also be used as a salt
  • Suitable salts are, in particular, alkali metal salts, such as sodium or potassium salts or ammonium salts, if acidic functions are present, and acid addition salts with inorganic acids, such as HF, HC1, HBr, H 2 SO, H 3 PO 4, etc., if basic functions are present are.
  • a further preferred embodiment is a mixture according to the invention which contains a compound of the formula I in which A represents alkylene or cycloalkylene and R 1 to R 4 independently of one another are CH 2 COOH, CH 2 CH 2 OH or
  • R 7 has the meanings given above and in particular represents OH, SH or NH 2 .
  • Compounds of the formula I are polyethyleneimine or polypropyleneimine polymers which are generally weakly crosslinked.
  • the repeating units of the formula mentioned can be the same or different. This is especially true when there are units that are substituted on the nitrogen tom, i.e. R is different from hydrogen in at least some of the units.
  • the degree of substitution can be chosen in a wide range and is generally in the range from 5 to 98%.
  • the slight crosslinking caused by the production of the polyethylene and polypropylene imines can be increased by means of polyether bridges between the polymers.
  • the polyether bridge is formed by alkylation of some of the nitrogen atoms with epichlorohydrin and subsequent ethoxylation.
  • the radicals R 1 to R 4 are preferably H or alkyl.
  • the average molecular weight of the polymers can be selected in a wide range, it is generally in the range from 800 to 2,000,000, in particular 1000 to 1,500,000 and in the case of more highly crosslinked polymers in the range from 50,000 to 2,000,000.
  • the mixture according to the invention contains at least one compound of the formula
  • A is - X _-NR -B — 3 n
  • B and X are CH 2 CH 2 -
  • R is CH 2 COOH, CH 2 CH 2 COOH, CH 2 CH 2 OH, CH 2 CH 2 NH 2 , NHCOR 5 or CSSH or represents a bridge as defined above
  • R 5 has the meanings given above and R 1 to R 4 are H or alkyl.
  • carboxymethylated polyethyleneimines with a degree of substitution in the range of 25 to 98% and an average molecular weight in the range of 1,500 to 1,500,000;
  • carboxyethylated polyethyleneimines with a degree of substitution in the range of 5 to 50% and an average molecular weight in the range of 1000 to 1,500,000;
  • partially amidated polyethyleneimines one or two of the radicals R 1 to R 4 are Ci to C 19 acyl
  • R 1 to R 4 are Ci to C 19 acyl
  • degree of substitution in the range from 5 to 50% and an average molecular weight which is in the range from 1000 to 1,500,000;
  • polyether crosslinked polyethyleneimines having an average molecular weight ranging from 50,000 to 1,500,000;
  • R 5 stands for CHR 6 COR 6
  • R 6 stands for C ⁇ 2 to C ⁇ 8 alkyl, in particular hexadecyl
  • polyethyleneimines are commercially available, e.g. distributed by BASF AG under the name UPASOL®.
  • the mixtures according to the invention contain a compound of the formula (I) in which A is cyclohexylene or -CH 2 CH 2 -, R 1 to R 4 is CH 2 COOH or
  • R 7 stands for OH, SH, NH 2 or COOH.
  • Mixtures of different compounds (I) can of course also be chosen, the mixing ratio generally not being critical.
  • the compounds of formula (I) can be used as a substance or in solution, usually in water or organic solvents.
  • the hydroxylamine derivatives (B) are compounds of the general formula (II)
  • R 8 , R 9 in (II) are the same or different and stand for C ⁇ ⁇ to C ⁇ 8 alkyl, Ci- to C 2 o-hydroxyalkyl, where 1 to 10 hydroxyl groups can be bonded to the alkyl radical, C 6 - bis Cis-aryl, alkylaryl or aralkyl, each with 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical.
  • Preferred Ci to C 2 o ⁇ hydroxyalkyl groups are those which can be obtained by the hydroxyalkylation of hydroxylamine with two equivalents of C 2 to C 0 epoxides, preferably ethylene oxide, propylene oxide, 1-butylene oxide.
  • Bis (hydroxypropyl) hydroxylamine [CH 3 CH (OH) CH 2 ] 2 NOH is very particularly preferred.
  • the hydroxylamine derivatives (B) can be used as a substance or in solution, usually in water or organic solvents.
  • R 10 is hydrogen or -C ⁇ to C -alkyl
  • R 11 to R 15 independently of one another hydrogen, C] _ to C ⁇ alkyl, ⁇ - to cis aryl, halogen or two adjacent
  • radicals together represent cyclic groups having 4 to 15 carbon atoms.
  • R 10 means hydrogen
  • R 11 to R 15 represent hydrogen, Ci to C alkyl, chlorine or phenyl or where two adjacent radicals together represent cyclic groups containing 4 to 12 carbon atoms, so that compounds of the general formula IV 5, for example, naphthalene derivatives or Anthracender derivatives.
  • Mixtures of different vinyl aromatic compounds can also be used, but preferably only one vinyl aromatic compound is used.
  • Particularly preferred vinyl aromatic compounds are styrene and p-methylstyrene. 20th
  • R 16 , R 17 in (IV) are the same or different and stand for hydrogen, C ⁇ ⁇ to cis-alkyl, C 6 - to cis-aryl, alkylaryl or aralkyl, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical.
  • Preferred compounds IV are salicyl-40 aldoxime, 5-dodecylslicylaldoxime, alkylacetophenone oxime.
  • R 18 , R 19 , R 20 , R 21 in (V) are the same or different and stand for hydrogen, C ⁇ ⁇ to Cis-alkyl, C ⁇ - to cis-aryl, alkylaryl or aralkyl, each with 1 to 10 carbon atoms in the Alkyl radical and 6 to 45 20 carbon atoms in the aryl radical.
  • Preferred compounds (V) are N, N'- di-sec-butyl-p-phenylenediamine, N-phenyl-N '- (1,4-dimethylpentyl) -p-phenylenediamine.
  • the concentration of (A) in a mixture of (A) and (B) depends on the chemical structure of (A) and / or (B) and / or on the temperature at which the mixture is processed and cannot in general quantified, but can be determined by a few stabilization attempts. The same applies to mixtures of (A), (B) and (C) or for mixtures of (A), (B), (C) and optionally further components, such as (IV) and / or (V).
  • a suitable amount of (A) and (B) in mixtures of (A), (B) and (C) has 1 to 10000 parts by weight, based on the sum of the components of (A) + (B) per 1 million Parts by weight (C), preferably vinyl aromatic compound (III), in particular styrene, as component (C).
  • the content of (A) in the mixtures (A) + (B) according to the invention is generally in the range from 10 to 100,000 ppm by weight, preferably in the range from 100 to 100,000 ppm by weight, based on the mixtures of (A) and (B).
  • the mixtures according to the invention can be produced using any mixing method.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne des mélanges comprenant (a) un composé de formule générale (I) R?1R2N-A-NR3R4¿, dans laquelle R1-R4 et A ont les significations données dans la description, (b) un composé de formule générale (II) R8-N(OH)-R9, dans laquelle R8 et R9 ont les significations données dans la description, (c) éventuellement d'autres composants tels que le styrol ou ses dérivés. Ces mélanges sont remarquables en ce qu'ils sont d'une stabilité à la décomposition plus élevée et en ce qu'ils sont fortement inhibiteurs de la polymérisation.
PCT/EP1998/003520 1997-06-23 1998-06-10 Melange a base de diorganohydroxylamine stabilise ou inhibiteur de polymerisation WO1998058891A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU85370/98A AU8537098A (en) 1997-06-23 1998-06-10 Stabilized or polymerization-inhibiting mixtures containing diorgano-hydroxylamine

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1997126671 DE19726671A1 (de) 1997-06-23 1997-06-23 Stabilisierte oder polymerisationsinhibierte Diorganohydroxylamin-haltige Mischungen
DE19726671.1 1997-06-23

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WO1998058891A1 true WO1998058891A1 (fr) 1998-12-30

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AU (1) AU8537098A (fr)
DE (1) DE19726671A1 (fr)
HR (1) HRP980338A2 (fr)
WO (1) WO1998058891A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000034220A2 (fr) * 1998-12-08 2000-06-15 Basf Aktiengesellschaft Procede pour empecher la polymerisation radicalaire non souhaitee de composes chimiques presentant au moins une liaison ethyleniquement insaturee

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0594341A1 (fr) * 1992-10-21 1994-04-27 Betz Europe, Inc. Compositions et procédés inhibitant la polymérisation de monomères vinyliques aromatiques
US5426257A (en) * 1994-06-30 1995-06-20 Betz Laboratories, Inc. Compositions and methods for inhibiting vinyl aromatic monomer polymerization
US5446220A (en) * 1994-08-24 1995-08-29 Betz Laboratories, Inc. Methods for inhibiting vinyl aromatic monomer polymerization
EP0690117A2 (fr) * 1994-06-30 1996-01-03 Betz Europe, Inc. Compositions et procédés pour inhiber la polymérisation de monomères vinylaromatiques
WO1997035821A1 (fr) * 1996-03-26 1997-10-02 Betzdearborn Inc. Compositions et procedes d'inhibition de la polymerisation de monomeres aromatiques vinyliques

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0594341A1 (fr) * 1992-10-21 1994-04-27 Betz Europe, Inc. Compositions et procédés inhibitant la polymérisation de monomères vinyliques aromatiques
US5426257A (en) * 1994-06-30 1995-06-20 Betz Laboratories, Inc. Compositions and methods for inhibiting vinyl aromatic monomer polymerization
EP0690117A2 (fr) * 1994-06-30 1996-01-03 Betz Europe, Inc. Compositions et procédés pour inhiber la polymérisation de monomères vinylaromatiques
US5446220A (en) * 1994-08-24 1995-08-29 Betz Laboratories, Inc. Methods for inhibiting vinyl aromatic monomer polymerization
WO1997035821A1 (fr) * 1996-03-26 1997-10-02 Betzdearborn Inc. Compositions et procedes d'inhibition de la polymerisation de monomeres aromatiques vinyliques

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000034220A2 (fr) * 1998-12-08 2000-06-15 Basf Aktiengesellschaft Procede pour empecher la polymerisation radicalaire non souhaitee de composes chimiques presentant au moins une liaison ethyleniquement insaturee
WO2000034220A3 (fr) * 1998-12-08 2002-10-31 Basf Ag Procede pour empecher la polymerisation radicalaire non souhaitee de composes chimiques presentant au moins une liaison ethyleniquement insaturee
US6518453B1 (en) 1998-12-08 2003-02-11 Basf Aktiengesellschaft Method for stabilizing chemical compounds containing at least one ethylenically unsaturated bond in order to prevent undesirable radical polymerization

Also Published As

Publication number Publication date
HRP980338A2 (en) 1999-02-28
DE19726671A1 (de) 1998-12-24
AU8537098A (en) 1999-01-04

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