HRP980338A2 - Stabilized or polymerization-inhibiting mixtures containing diorgano-hydroxylamine - Google Patents

Description

The proposed invention relates to a mixture containing (A) a compound of formula (I)

R1R2N-A-NR3-R4 (I),

where

A represents alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene arylene, o-, m- or p-xylylene, a five- or six-membered saturated or unsaturated heterocycle containing one nitrogen, wherein said radicals can have 1, 2 or 3 substituents that are mutually independently selected from alkyl, alkoxy or hydroxyl, or A represents

-X[-NR-B-]-n

where

B and X represent -CH2CH2- or -CH2CH2CH2-,

n is 10 - 50,0000,

R is H, alkyl, OH-, NH2-, NHCOR5- or COOH- substituted ethylene or propylene radical, CSSH, CH2CN or CH2PO3H2 or a bridge to the nitrogen of another polyethyleneimine or polypropyleneimine chain, wherein the bridge is formed by -[-NR-B -]-o or CH2 CHOH CH2-[-O CH2 CH2]-p CH2 CHOH, CH2-, where o and p independently represent 1 - 15.

R5 is H, C1-C18-alkyl or CHR6COR6, where R6 represents a C12-C18-alkyl radical,

R1, R2, R3 and R4 independently represent H, CH2COOH, CH2PO3H2, alkyl, acyl, CH2CH2OH, CH2CH2NH2 or

[image]

where

R7 is OH, SH, NH2, CN, COOH, alkyl or alkoxy, or its salts,

(B) hydroxylamine derivative of formula (II)

[image]

in which R8 and R9 represent C1-C18-alkyl, C1-C20hydroxylalkyl, C6-C15aryl,. alkylaryl or aralkyl, each having from 1 to 10 carbon atoms in alkyl and from 6 to 20 carbon atoms in aryl,

(C) with or without other components.

The proposed invention further relates to the use of compounds of formula (I) as stabilizers against the decomposition of compounds of formula (I) as stabilizers against decomposition or inhibitors against the polymerization of the mixture defined in the introduction.

Hydroxylamine and its organic derivatives are sensitive to decomposition. The tendency to decomposition generally increases with increasing temperature and increasing the concentration of catalytically active impurities. Derivatives of diogranohydroxylamine can be used as substances that inhibit the polymerization of styrene, for example, that is, they can be used as polymerization inhibitors, as described in US 5,426,257.

The stability of hydroxylamine derivatives towards decomposition, nor the stability of monomers, described for example in US 5,426,257, towards polymerization is not satisfactory, especially at temperatures above 25°C during a relatively long storage period.

The aim of the proposed invention is therefore to provide compounds that significantly inhibit the decomposition of organic derivatives of hydroxylamine, especially at temperatures above 25°C or during a relatively long period of storage, i.e. which stabilize organic derivatives of hydroxylamine. Furthermore, the aim of the proposed invention is to find compounds that inhibit the polymerization of monomers containing C=C double bonds, generally under the same stated conditions.

We have found that this goal is achieved with the mixtures defined in the introduction, and by using the compounds (I) defined in the introduction as stabilizers against decomposition or inhibitors against the polymerization of the mixtures defined in the introduction.

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

R1R2N-A-NR3-R4 (I),

in which A represents alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene arylene, o-, m- or p-xylylene, a five- or six-membered saturated or unsaturated heterocycle containing one nitrogen, wherein said radicals may have 1, 2 or 3 substituents which are mutually independently selected from alkyl, alkoxy or hydroxyl, or A represents

-X[-NR-B-]-n

where

B and X represent -CH2CH2- or -CH2CH2CH2-,

n is 10 - 50,0000,

R is H, alkyl, OH-, NH2-, NHCOR5- or COOH- substituted ethylene or propylene radical, CSSH, CH2CN or CH2PO3H2 or a bridge to the nitrogen of another polyethyleneimine or polypropyleneimine chain, wherein the bridge is formed by -[-NR-B -]-o or CH2 CHOH CH2-[-O CH2 CH2]-p CH2 CHOH, CH2-, where o and p independently represent 1 - 15.

R5 is H, C1-C18-alkyl or CHR6COR6, where R6 represents a C12-C18-alkyl radical,

R1, R2, R3 and R4 independently represent H, CH2COOH, CH2PO3H2, alkyl, acyl, CH2CH2OH, CH2CH2NH2 or

[image]

where

R7 is OG, SH, NH2, CN, COOH, alkyl or alkoxy, or salts thereof.

In the description of the substituents of the compound of formula I, alkyl is a linear or branched radical having preferably from 1 to 18 carbon atoms, especially from 1 to 6 carbon atoms, and especially from 1 to 4 carbon atoms. This also applies accordingly to the alkyl group in alkoxy.

Alkylene is a linear or branched divalent radical having preferably from 2 to 6 carbon atoms, especially from 2 to 4 carbon atoms.

Alkenylene and alkynylene are linear or branched divalent radicals that have preferably from 3 to 6 carbon atoms, usually from 3 to 4 carbon atoms.

Cycloalkylene is preferably cyclopentylene or cyclohexylene, and cycloalkenylene is preferably cyclopentenylene or cyclohexenylene.

Arylene is primarily an aromatic C6-C10 hydrocarbon radical and phenylene.

The saturated or unsaturated heterocycle is preferably a pyrrolidinylene, piperidinylene, pyrrolylene or pyridinylene radical. The heterocycle is connected via carbon to two nitrogens of the compound of formula I.

Acyl is a linear or branched radical, which preferably has from 1 to 19 carbon atoms.

A is preferably alkylene, cycloalkylene, arylene or

-X[-NR-B-]-n, and especially alkylene, cycloalkylene or

-X[-NR-B-]-n.

The radicals R1 to R4 are, then, independently of each other, preferably CH2COOH, CH2CH2OH or

[image]

and especially CH2COOH or

[image]

R 7 is preferably in the o position, and is in particular 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 salts. If acidic functional groups are present, alkali metal salts, such as sodium salts or potassium salts or ammonium salts, are particularly suitable, and acid addition salts with inorganic acids, such as HCl, HBr, H2SO4, H3PO4, etc., if basic are present functional groups.

A further preferred embodiment is the mixture according to the invention containing the compound of formula I, in which A represents alkylene or cycloalkylene, and R1 to R4 independently of each other represent CH2COOH, CH2CH2OH or

[image]

where R 7 has the above meaning and is in particular OH, SH or NH 2 .

If A represents -X[-NR-B-]-n, compounds I are polyethyleneimine polymers or polypropyleneimine polymers, which generally have a low degree of cross-linking. Repeating units in the mentioned formula can be equal or different. This is especially the case if units are present which are substituted on nitrogen, i.e. R is different from hydrogen at least in some units. The degree of substitution can be chosen over a wide range and is generally from 5 to 98%. The low degree of crosslinking due to the preparation of polyethyleneimine and polypropyleneimine can be increased by polyether bridges between the polymers. The polyether bridge is formed by alkylation of some nitrogen atoms with epichlorohydrin and then ethoxylation.

In the case of polyethyleneimine polymers or polyethyleneimine polymers, the radicals R1 to R4 are preferably H or alkyl.

The average molecular weight of the polymer can be chosen over a wide range; it is generally from 800 to 2,000,000, especially from 1,000 to 1,500,000, and in the case of stronger crosslinked polymers from 50,000 to 2,000,000.

According to a further preferred embodiment, the mixture according to the invention contains at least one compound of formula I in which A represents -X[-NR-B-]-n, B and X represent -CH2CH2-, R is CH2COOH, CH2CH2COOH, CH2CH2NH2, NHCOR5 or CSSH, or a bridge as defined above, R 5 has the above meaning and R 1 to R 4 represent H or alkyl.

This applies in particular to:

polyethyleneimine having a low degree of cross-linking and an average molecular weight of 1,000 to 2,000,000;

carboxylated polyethyleneimines having a degree of substitution of 25% to 98% and an average molecular weight of 1,500 to 1,500,000;

carboxylated polyethyleneimines having a degree of substitution of 5% to 50% and an average molecular weight of 1,000 to 1,500,000;

especially amidated polyethyleneimines (one or two radicals R1 to R4 are C1-C19-acyl) having a degree of substitution of 5 to 50% and an average molecular weight of 1,000 to 1,500,000;

polyethyleneimines which are cross-linked with polyether and have an average molecular weight of 50,000 to 1,500,000;

hydrophobically modified polyethyleneimines

(R = - CH2CH2NHCOR5, where R5 represents CHR6COR6 and R6 is C12-C18-alkyl, especially hexadecyl) having a degree of substitution of 1 to 7% and an average molecular weight of 1,500 to 1,500,000. These polymers can be obtained by reacting the corresponding ethylenimines (R = CH2CH2NH2) with the corresponding alkyldihetenes;

hydroxyethyl substituted polyethyleneimines having a degree of substitution of 80 to 100% and an average molecular weight of 1 to 2,000,000;

polyethyleneimine dithiocarbamates (R = CSSH) having a degree of substitution of 30 to 60% and an average molecular weight of 2,000 to 1,000,000 and their sodium salts.

Some of the polyethyleneimines mentioned above are commercially available; they are sold, for example, by BASF AG under the name LUPASOL®.

According to a further preferred embodiment, the mixtures according to the invention contain a compound of formula (I), in which A represents cyclohexylene or -CH2CH2-, R1 to R4 represent CH2COOH or

[image]

where R7 represents OH, SH, NH2 or COOH.

Particular preference is given to trans-1,2-diaminocyclohexane N,N,N',N'-tetraacetic acid and/or N,N'-di(2-hydroxybenzyl)ethyl diamine-N,N'-diacetic acid and its salts.

Compounds of formula (I) are known and commercially available or can be produced by methods similar to known procedures.

Obviously, mixtures of different compounds (I) can also be selected, the mixing ratio being generally not critical.

The compounds of formula (I) can be used without a solvent or in solution, usually in water or organic solvents.

Derivatives of hydroxylamine (B) are compounds of formula (II)

[image]

in which R8m R9 in formula (II) are the same or different and represent C1-C18-alkyl, C1-C20-hydroxyalkyl, where in each case from 1 to 10 hydroxyl groups can be connected to an alkyl radical, C6-C15-aryl, alkylaryl or aralkyl, each having from 1 to 10 carbon atoms in alkyl and from 6 to 20 carbon atoms in aryl. Preferred C1-C20-hydroxyalkyls are those which can be obtained by hydroxyalkylation of hydroxylamine with two equivalents of C2-C20-epoxide, preferably ethylene oxide, propylene oxide, 1-butylene oxide. Very particular preference is given to bi-(hydroxypropyl)hydroxylamine (B) [CH3CH(OH)CH2]2NOH.

Hydroxylamine derivatives (B) can be used without a solvent or in solution, usually in water or in organic solvents.

Suitable polymerizable monomers containing a C=C double bond are generally all representatives of this class of substances. Very suitable compounds are cyclic or linear C2-C10 mono- or polyalkenes, such as ethylene, propene, 1-butene, 1,3-butadiene, cyclopentadiene, norbornene, norbornadiene, alkyl acid, methacrylic acid or esters, preferably methyl or ethyl esters of those acids. Monomers containing a C=C double bond, which can be specially mentioned, are vinylaromatic compounds, primarily those of the formula (III)

[image]

where the substituents have the following meanings:

R10 is hydrogen or C1-C4-alkyl,

R11 to R15 independently represent hydrogen, C1-C12-alkyl, C6-C18-aryl, halogen, or where two adjacent radicals together form cyclic groups having from 4 to 15 carbon atoms.

Preferably, vinylaromatic compounds of formula (II) are used where

R10 is hydrogen, and

R11 to R15 represent hydrogen, C1-C4-alkyl, chlorine or phenyl, or where two adjacent radicals together form cyclic groups having from 4 to 12 carbon atoms, so that compounds of formula IV are obtained, for example naphthalene derivatives or anthracene derivatives.

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 vinylaromatic compounds can also be used, but preferably only one vinylaromatic compound is used.

Particularly preferred vinylaromatic compounds are ethylene and p-methylstyrene.

The preparation of vinylaromatic compounds of formula (IV) is known per se and is described for example in Beilstein 5, 367, 474, 485.

Compounds of formula (IV) and/or (V) can also be added as further components to the mixture containing monomer (C).

[image]

R16 and R17 in formula (IV) are the same or different and represent hydrogen, C1-C18-alkyl, C6-C15-aryl, alkylaryl or aralkyl each of which has from 1 to 10 carbon atoms in the alkyl and from 6 to 20 carbon atoms in the aril. Preferred compounds of formula IV are salicylic aldoxime, 5-dodecylsalicylic aldoxime, alkylacetophenone oxime.

R18, R19, R20 and R21 in formula (V) are the same or different and represent C1-C18-alkyl, C6-C15-aryl, alkylaryl or aralkyl each of which has from 1 to 10 carbon atoms in the alkyl and from 6 to 20 of carbon atoms in the aryl. Preferred compounds of formula (V) are N,N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N'-(1,4-dimethylpentyl)-p-phenylene-diamine.

The concentration of compound (A) in a mixture of compounds (A) and (B) depends on the chemical structure of compound (A) and/or (B) and/or the temperature at which the mixture is processed and cannot be generally quantified, but it can be determined with only a few stabilization attempts. The same applies to mixtures of compounds (A), (B) and (C) or to mixtures of compounds (A), B) and (C) with or without other ingredients such as compounds (IV) and/or (V).

In the mixtures (A), (B) and (C), the amount of (A) and (B) proved suitable, from 1 to 10,000 parts by weight, calculated according to the sum of components (A) + (B) per million parts by weight ( C), preferably vinylaromatic compound (III), especially styrene as component (C).

The content of compound (A) in mixtures (A) + (B) according to the invention is generally from 10 to 100,000 ppm by weight, preferably from 100 to 100,000 ppm by weight, calculated according to the mixture of compound (A) and compound (B).

The mixtures according to the invention can be produced by any mixing method.

Preferably, the mixtures according to the invention are used for the distillation of monomers containing a C=C double bond, especially vinylaromatic monomers (III), such as styrene, at temperatures from 0 to 250°C, preferably from 50 to 150°C.

Examples

Stabilization of N,N-diallylhydroxylamine solutions

50 g of an 82% aqueous solution of bis(hydroxypropyl).hydroxylamine (BHH) is weighed into each of three 50 ml round bottom flasks. Oxygen is removed from each solution by passing nitrogen for 5 minutes. In flask 1, 15 mg of trans-1,2-diaminocyclohexanetetraacetic acid (CDTA) was added for stabilization. In flask 1, for comparison, nothing is added. 1.5 mg of ferrous sulfate is added to flask 3 as a decomposition accelerator. The flasks are closed, protected from air entry by means of a partition and heated in an oil bath to 100°C. Over time, the solutions turn dark due to the decomposition of bis-(hydroxypropyl)hydroxylamine. Table 1 shows the time after which the solutions turned completely black.

Table 1:

[image]

Claims (5)

1. A mixture, indicated by the fact that it contains compound of formula (I) R1R2N-A-NR3-R4 (I), where A represents alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene arylene, o-, m- or p-xylylene, a five- or six-membered saturated or unsaturated heterocycle containing one nitrogen, wherein said radicals can have 1, 2 or 3 substituents that are mutually independently selected from alkyl, alkoxy or hydroxyl, or A represents -X[-NR-B-]-n where B and X represent -CH2CH2- or -CH2CH2CH2-, n is 10 - 50,0000, R is H, alkyl, OH-, NH2-, NHCOR5- or COOH- substituted ethylene or propylene radical, CSSH, CH2CN or CH2PO3H2 or a bridge to the nitrogen of another polyethyleneimine or polypropyleneimine chain, wherein the bridge is formed by -[-NR-B -]-o or CH2 CHOH CH2-[-O CH2 CH2]-p CH2 CHOH, CH2-, where o and p independently represent 1 - 15. R5 is H, C1-C18-alkyl or CHR6COR6, where R6 represents a C12-C18-alkyl radical, R1, R2, R3 and R4 independently represent H, CH2COOH, CH2PO3H2, alkyl, acyl, CH2CH2OH, CH2CH2NH2 or [image] where R7 is OH, SH, NH2, CN, COOH, alkyl or alkoxy, or its salts, hydroxylamine derivative of formula (II) [image] in which R8 and R9 represent C1-C18-alkyl, C1-C20hydroxylalkyl, C6-C15aryl,. alkylaryl or aralkyl, each having from 1 to 10 carbon atoms in alkyl and from 6 to 20 carbon atoms in aryl, with or without other components. 2. A mixture of substantially inhibited polymerization according to claim 1, characterized in that it contains (A) compound of formula (I): R1R2N-A-NR3-R4 (I), where A represents alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene arylene, o-, m- or p-xylylene, a five- or six-membered saturated or unsaturated heterocycle containing one nitrogen, wherein said radicals may have 1, 2 or 3 substituents which are mutually independently selected from alkyl, alkoxy or hydroxyl, or A represents -X[-NR-B-]-n where B and X represent -CH2CH2- or -CH2CH2CH2-, n is 10 - 50,0000, R is H, alkyl, OH-, NH2-, NHCOR5- or COOH- substituted ethylene or propylene radical, CSSH, CH2CN or CH2PO3H2 or a bridge to the nitrogen of another polyethyleneimine or polypropyleneimine chain, wherein the bridge is formed by -[-NR-B -]-o or CH2 CHOH CH2-[-O CH2 CH2]-p CH2 CHOH, CH2-, where o and p independently represent 1 - 15. R5 is H, C1-C18-alkyl or CHR6COR6, where R6 represents a C12-C18-alkyl radical, R1, R2, R3 and R4 independently represent H, CH2COOH, CH2PO3H2, alkyl, acyl, CH2CH2OH, CH2CH2NH2 or [image] where R7 is OG, SH, NH2, CN, COOH, alkyl or alkoxy, or salts thereof. hydroxylamine derivative of formula (II) [image] in which R8 and R9 represent C1-C18-alkyl, C1-C20-hydroxylalkyl, C6-C15aryl,. alkylaryl or aralkyl, each having from 1 to 10 carbon atoms in alkyl and from 6 to 20 carbon atoms in aryl, a monomer containing a C=C double bond that can polymerize. 3. Bino-inhibited polymerization mixture according to claim 2 characterized in that it contains component (C) in which a vinylaromatic compound of the formula is used [image] in which the substituents have the following meanings: R10 is hydrogen or C1-C4-alkyl, R11 to R15 independently represent hydrogen, C1-C12-alkyl, C6-C18-aryl, halogen, or where two adjacent radicals together form cyclic groups having from 4 to 15 carbon atoms. 4. A substantially inhibited polymerization mixture according to any of claims 1 to 3, characterized in that it contains (A) trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid, (B) bis(hydroxypropyl)hydroxylamine and (C) styrene or a styrene derivative. 5. The use of compounds of formula (I) according to claim 1, characterized in that they are used as stabilizers against decomposition or inhibitors against polymerization of mixtures according to claims 1 to 4.