DE19726671A1 - Stabilized or polymerization-inhibited mixtures containing diorganohydroxylamine - Google Patents

Abstract

The invention relates to mixtures consisting of: (a) a compound having general formula (I) R<1>R<2>N-A-NR<3>R<4>, in which R<1>-R<4> and A have the meanings given in the description; (b) a compound having general formula (II) R<8>-N(OH)-R<9>, in which R<8> and R<9> have the meanings given in the description; (c) optionally other components, like for example styrene or its derivatives. These mixtures are characterized by enhanced stability in relation to decomposition, as well as being effective polymerization inhibitors.

Description

The present invention relates to a mixture of

• (A) a compound of the general formula (I)
  R ¹ R ² NA-NR ³ R ⁴ (I)
  wherein
  A represents alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene, arylene, o-, m- or p-xylylene, a 5- or 6-membered saturated or unsaturated heterocycle having a nitrogen atom, the radicals mentioned 1, 2 or 3 May have substituents which are independently selected from alkyl, alkoxy or hydroxy, or for
  stands in what
  B and X represent -CH ₂ CH ₂ - or -CH ₂ CH ₂ CH ₂ -,
  n stands for 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 PO ₃ H ₂ or represents a bridge to a nitrogen atom of another polyethyleneimine or polypropyleneimine chain, being the bridge through
  is formed, where o and p independently of one another represent 1-15,
  R ^{5 represents} H, C ₁ -C ₁₈ alkyl or CHR ⁶ COR ⁶ , where R ^{6 represents} a C ₁₂ -C ₁₈ alkyl radical,
  R ¹ , R ² , R ³ and R ⁴ independently of one another are H, CH ₂ COOH, CH ₂ PO ₃ H ₂ , alkyl, acyl, CH ₂ CH ₂ OH, CH ₂ CH ₂ NH ₂ or
  stand where
  R ^{7 represents} OH, SH, NH ₂ , CN, COOH, alkyl or alkoxy, or the salts thereof,
• (B) a hydroxylamine derivative of the general formula (II)
  in which
  R ⁸ , R ⁹ C ₁ to C ₁₈ alkyl, C ₁ to C ₂₀ hydroxyalkyl, C ₆ to C ₁₅ aryl, alkylaryl or aralkyl each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C -Atoms in the aryl rest,
• (C) optionally further components.

Furthermore, the present invention relates to the use of Compounds of general formula (I) as a stabilizer against Decomposition or inhibitor against polymerization of defi mixed mixtures.

Hydroxylamine and its organic derivatives are sensitive against decomposition. The tendency to decompose generally increases with increasing temperature and increasing concentration effective contaminants. Diorganohydroxylamine derivatives can be used as substances that, for example, the polymerization Inhibit styrene, that is, used as polymerization inhibitors as described in US 5,426,257.

Neither the stability of the hydroxylamine derivatives against decomposition nor the stability of those described, for example, in US Pat. No. 5,426,257 is monomers against polymerization, especially in Tempe temperatures above 25 ° C or longer storage, satisfactory. The present invention is therefore based on the object Find compounds that decompose organic Hydroxylamine derivatives, especially at temperatures above 25 ° C practically inhibit or prolonged storage, d. H. the organic  Stabilize hydroxylamine derivatives. The present invention is still the task of finding compounds that the polymerization of monomers with C = C double bonds, in generally inhibit under the same conditions mentioned.

Accordingly, the mixtures defined at the outset, such as the Use of the compounds (I) defined at the outset as stabilizers sator against decomposition or inhibitor against polymerization of the mixtures defined at the beginning were found.

Component (A) of the mixtures according to the invention is a compound of the formula I:

R ¹ R ² NA-NR ³ R ⁴ (I),

wherein
A represents alkylene, alkenylene, alkynylene, cycloalkylene, cycloal kenylene, arylene, o-, m- or p-xylylene, a 5- or 6-membered saturated or unsaturated heterocycle having a nitrogen atom, the said radicals 1, 2 or 3 May have substituents which are independently selected from alkyl, alkoxy or hydroxy, or for

stands in what
B and X represent -CH ₂ CH ₂ - or -CH ₂ CH ₂ CH ₂ -,
n stands for 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 PO ₃ H ₂ or represents a bridge to a nitrogen atom of another polyethyleneimine or polypropyleneimine chain , the bridge through

is formed, where o and p independently of one another represent 1-15,
R ^{5 represents} H, C ₁ -C ₁₈ alkyl or CHR ⁶ COR ⁶ , where R ^{6 represents} a C ₁₂ -C ₁₈ alkyl radical,
R ¹ , R ² , R ³ and R ⁴ independently of one another are H, CH ₂ COOH, CH ₂ PO ₃ H ₂ , alkyl, acyl, CH ₂ CH ₂ OH, CH ₂ CH ₂ NH ₂ or

stand where
R ^{7 represents} OH, SH, NH ₂ , CN, COOH, alkyl or alkoxy, or the salts thereof.

As part of the description of the substituents of the general For mel I alkyl is a straight-chain or branched radical, of preferably 1 to 18 carbon atoms, in particular 1 to 6 Carbon atoms and in particular 1 to 4 carbon atoms is. The same applies to the alkyl group in alkoxy.

Alkylene stands for a straight-chain or branched divalent Balance, preferably 2 to 6 and in particular 2 to 4 coals has atoms of matter.

Alkenylene and alkynylene stand for straight-chain or branched, divalent radicals, preferably 3 to 6 carbon atoms and in particular have 3 or 4 carbon atoms.

Cycloalkylene and cycloalkenylene are preferably cyclo pentylene or cyclohexylene or for cyclopentenylene or cyclo hexenylene.

Arylene is preferably an aromatic C ₆ -C ₁₀ hydrocarbon residue and phenylene.

The saturated or unsaturated heterocycle is is preferably a pyrrolidinylene, piperidinylene, pyr rolylene or pyridinylene. The heterocycle is about coals atoms attached to the two nitrogen atoms of formula I.

Acyl stands for a straight-chain or branched radical which preferably has 1 to 19 carbon atoms.

A is preferably alkylene, cycloalkylene, arylene or

and especially for alkylene, cycloalkylene or

The radicals R ¹ to R ⁴ are then independent of one another, preferably CH ₂ COOH, CH ₂ CH ₂ OH, CH ₂ CH ₂ NH ₂ or

and especially for

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, HCl, HBr, H ₂ SO ₄ , 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 is alkylene or cycloalkylene and R ¹ to R ⁴ independently of one another are CH ₂ COOH, CH ₂ CH ₂ OH or

stand, wherein R ^{7 has} the meanings given above and in particular stands for OH, SH or NH ₂ .

If A for

stands, it is the Compounds of formula I around polyethyleneimine or polypropylene imine polymers that are generally weakly cross-linked. Which Repeating units of the formula mentioned can be the same or be different. This is especially true when units are present which are substituted on the nitrogen atom, d. H. R is ver in at least some of the units of hydrogen divorced. The degree of substitution can be in a wide range can be selected and is generally in the range from 5 to 98%. The through the manufacture of polyethylene and polypropy Light crosslinking due to lenimine can be achieved through polyether bridges between the polymers can be increased. The polyether bridge will formed by alkylating some of the nitrogen atoms with Epichlorohydrin and subsequent ethoxylation.

The radicals R ¹ to R ⁴ in the case of polyethylene or polypropylene imine polymers, preferably H or alkyl.

The average molecular weight of the polymers can vary widely Be selected, it is generally in the range of 800 to 2,000,000, especially 1,000 to 1,500,000 and higher cross-linked polymers in the range of 50,000 to 2,000,000.

According to a further preferred embodiment, the mixture according to the invention contains at least one compound of the formula I, in which A is

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.

These are particularly preferably:
weakly cross-linked polyethyleneimine with an average molecular weight in the range from 1000 to 2,000,000;
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 C ₁ to C ₁₉ acyl) with a 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 with an average molecular weight which is in the range from 50,000 to 1,500,000;
Hydrophobically modified polyethyleneimines (R = -CH ₂ CH ₂ NHCOR ⁵ , where R ^{5 stands} for CHR ⁶ COR ⁶ and R ^{6 stands} for C ₁₂ to C ₁₈ alkyl, in particular hexadecyl) with a degree of substitution in the range from 1 to 7% and an average molecular weight which is in the range from 1500 to 1,500.00. These polymers are obtainable by reacting the corresponding ethyleneimines (R = CH ₂ CH ₂ NH ₂ ) with the corresponding alkyldiketenes;
Hydroxyethyl substituted polyethyleneimines with a degree of substitution of 80 to 100% and an average molecular weight that is in the range of 1 to 2,000,000;
Polyethyleneiminedithiocarbamate (R = CSSH) with a degree of substitution of 30 to 60% and an average molecular weight of 2000 to 1,000,000, and the sodium salts thereof.

Some of the above polyethyleneimines are commercially available, they will e.g. B. from BASF AG under the name LUPASOLO® expelled.

According to a further preferred embodiment, 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

stand, wherein R ^{7 stands} for OH, SH, NH ₂ or COOH.

These are particularly preferably trans-1,2-diaminocytes clohexane-N, N, N ', N'-tetraacetic acid and / or N, N'-di (2-hydroxy benzyl) ethylenediamine-N, N'-diacetic acid and the salts thereof.

The compounds of formula (I) are known and commercially available available or can be prepared analogously by known methods will.

Mixtures of different ones can of course also be used Compounds (I) are selected, the mixing ratio in general is not critical.

The compounds of formula (I) can be used as a substance or in Solution, usually in water or organic solvents, be used.

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 ₁ - to C ₁₈ -alkyl, C ₁ - to C ₂₀ -hydroxyalkyl, where in each case 1 to 10 hydroxyl groups can be bonded to the alkyl radical, C ₆ - bis C ₁₅ aryl, alkylaryl or aralkyl, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical. Preferred C ₁ to C ₂₀ hydroxyalkyl groups are those which are obtainable by the hydroxyalkylation of hydroxylamine with two equivalents of C ₂ to C ₂₀ 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 be set.

All representatives of this class of substance are generally suitable as polymerizable monomers with a C = C double bond. Cyclic or linear C ₂ -C ₁₀ -mono- or poly-alkenes, such as ethylene, propene, 1-butene, 1,3-butadiene, cyclopentadiene, norbornene, norbornadiene, acrylic acid, methacrylic acid or ester, preferably methyl, are particularly suitable. or ethyl esters, these acids. Particularly worth mentioning as monomers with a C =C double bond are vinylaromatic compounds, preferably those of the general formula (III)

in which the substituents have the following meaning:
R ^{10 is} hydrogen or C ₁ to C ₄ alkyl,
R ¹¹ to R ¹⁵ independently of one another are hydrogen, C ₁ to C ₁₂ alkyl, C ₆ to C ₁₈ aryl, halogen or where two adjacent radicals together represent cyclic groups having 4 to 15 C atoms.

Vinylaromatic compounds of the formula (III) in which
R ^{10 is} hydrogen and
R ¹¹ to R ^{15 represent} hydrogen, C ₁ - to C ₄ -alkyl, chlorine or phenyl or where two adjacent radicals together represent cyclic groups containing 4 to 12 C atoms, so that naphthalene derivatives, for example, are compounds of the general formula IV or Anthracenderi vate.

Examples of such preferred compounds are:
Styrene, p-methylstyrene, p-chlorostyrene, 2,4-dimethylstyrene, 1,4-divinylbenzene, 4-vinylbiphenyl, 2-vinylnaphthalene or 9-vinylanthracene.

Mixtures of different vinyl aromatic compounds can also be used be used, but preferably only one vinyl aromatic compound used.

Particularly preferred vinyl aromatic compounds are styrene and p-methylstyrene.

The production of vinyl aromatic compounds of the general my formula (IV) is known per se and for example in Beilstein 5, 367, 474, 485.

The monomer (C) can be used as further components Mixtures or compounds of the general formulas (IV) and / or (V) can be added.

R ¹⁶ , R ¹⁷ in (IV) are identical or different and stand for What serstoff, C ₁ - to C ₁₈ alkyl, C6 to C ₁₅ aryl, alkylaryl or aralkyl each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical. Preferred compounds IV are salicyl 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 ₁ - to C ₁₈ -alkyl, C ₆ - to C ₁₅ -aryl, alkylaryl or aralkyl, each with 1 to 10 C atoms in the alkyl radical and 6 to 20 C 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 of the temperature at which the mixture is processed and can are not generally quantified, but can be determine a few stabilization attempts. The same is true for Mixtures of (A), (B) and (C) or for mixtures of (A), (B), (C) and optionally further components, such as (IV) and / or (V) too.

As a suitable amount of (A) and (B) in mixtures of (A), (B) and (C) have 1 to 10000 parts by weight based on the total the components from (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 of 100 to 100 00 ppm by weight on the mixtures of (A) and (B).

The mixtures according to the invention can be mixed with any method getting produced.

The mixtures according to the invention preferably come from Distillation of monomers with a C = C double bond, in particular of vinyl aromatic monomers (III), such as styrene, in temperature range from 0 to 250 ° C, preferably in the temperature range from 50 up to 150 ° C for use.

Examples

Stabilization of N, N-dialkylhydroxylamine solutions:
50 g of an aqueous 82% bis (hydroxypropyl) hydroxylamine solution (BHH) were weighed into three 50 ml round-bottom flasks. The solutions were freed from oxygen by introducing nitrogen for 5 minutes each time. 15 mg of trans-1,2-diaminocyclohexanetetraacetic acid (CDTA) were added to flask 1 for stabilization. For comparison, piston 2 remained without further addition. 1.5 mg of iron sulfate was added to flask three as a decomposition accelerator. The flasks were protected from air ingress by sealing with a septum and heated to 100 ° C. in an oil bath. The solutions turned dark over time due to decomposition of the bis (hydroxypropyl) hydroxylamine. Table 1 shows the times after which a complete blackening had occurred.

Table 1

Claims (5)

1. Mix of

• (A) a compound of the general formula (I)
  R ¹ R ² NA-NR ³ R ⁴ (I),
  wherein
  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
  stands in what
  B and X represent -CH ₂ CH ₂ - or -CH ₂ CH ₂ CH ₂ -,
  n stands for 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 PO ₃ H ₂ or represents a bridge to a nitrogen atom of another polyethylenimine or polypropyleneimine chain , the bridge through
  is formed, where o and p independently of one another represent 1-15,
  R ^{5 represents} H, C ₁ -C ₁₈ alkyl or CHR ⁶ COR ⁶ , where R ^{6 represents} a C ₁₂ -C ₁₈ alkyl radical,
  R ¹ , R ² , R ³ and R ⁴ independently of one another are H, CH ₂ COOH, CH ₂ PO ₃ H ₂ , alkyl, acyl, CH ₂ CH ₂ OH, CH ₂ CH ₂ NH ₂ or
  stand where
  R ^{7 represents} OH, SH, NH ₂ , CN, COOH, alkyl or alkoxy, or the salts thereof,
• (B) a hydroxylamine derivative of the general formula (II)
  in which
  R ⁸ , R ⁹ C ₁ to C ₁₈ alkyl, C ₁ to C ₂₀ hydroxyalkyl, C ₆ to C ₁₅ aryl, alkylaryl or aralkyl each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C -Atoms in the aryl residue,
• (C) optionally further components.

2. Practically polymerization-inhibited mixture according to claim 1, containing

• (A) a compound of the general formula (I)
  R ¹ R ² NA-NR ³ R ⁴ (I),
  wherein
  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
  stands in what
  B and X represent -CH ₂ CH ₂ - or -CH ₂ CH ₂ CH ₂ -,
  n stands for 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 PO ₃ H ₂ or represents a bridge to a nitrogen atom of another polyethylenimine or polypropyleneimine chain , the bridge through
  is formed, where o and p independently of one another represent 1-15,
  R ^{5 represents} H, C ₁ -C ₁₈ alkyl or CHR ⁶ COR ⁶ , where R ^{6 represents} a C ₁₂ -C ₁₈ alkyl radical,
  R ¹ , R ² , R ³ and R ⁴ independently of one another are H, CH ₂ COOH, CH ₂ PO ₃ H ₂ , alkyl, acyl, CH ₂ CH ₂ OH, CH ₂ CH ₂ NH ₂ or
  stand where
  R ^{7 represents} OH, SH, NH ₂ , CN, COOH, alkyl or alkoxy, or the salts thereof,
• (B) a hydroxylamine derivative of the general formula (II)
  in which
  R ⁸ , R ⁹ C ₁ to C ₁₈ alkyl, C ₁ to C ₂₀ hydroxyalkyl, C ₆ to C ₁₅ aryl, alkylaryl or aralkyl each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C -Atoms in the aryl residue,
• (C) a polymerizable monomer with a C = C double bond.

3. Practically polymerization-inhibited mixture according to claim 2, wherein as component (C) a vinyl aromatic compound of the general formula
in which the substituents have the following meaning:
R ^{10 is} hydrogen or C ₁ to C ₄ alkyl,
R ¹¹ to R ¹⁵ independently of one another are hydrogen, C ₁ to C ₁₂ alkyl, C ₆ to C ₁₈ aryl, halogen or where two adjacent radicals together represent cyclic groups having 4 to 15 C atoms,
is used. 4. Practically polymerization-inhibited mixture, according to claims 1 to 3, containing

• (A) trans-1,2-diaminocyclohexane-N, N, N ', N'-tetraacetic acid,
• (B) bis (hydroxypropyl) hydroxylamine and
• (C) styrene or a styrene derivative.

5. Use of compounds of the general formula (I) according to Claim 1 as a stabilizer against decomposition or inhibitor against polymerization of mixtures according to claims 1 to 4.