DE9212966U1 - Water-soluble or dispersible antithermo-oxidants - Google Patents

Description

Lawyer’s file: P 26 687

Date: 25 September 1992
10

Dr. Th. Böhme KG Chem. Fabrik GmbH & Co.

Isardamm 79
D-8192 Geretsried 1

Water-soluble or dispersible antithermo-oxidants

For a wide variety of technical processes at high temperatures, it is often necessary to effectively protect the necessary auxiliary materials, such as mineral oil, rubber, plastics, surfactants, natural oils and fats, as well as glycolic cleaning baths, against oxidative and thermal influences in order to ensure their performance properties.

&igr; 25 A number of bodies of different classes of substances are known to be resistant to thermo-oxidative

\ f\ &igr; dative damage of, for example, spinning fibre preparations (e.g. agents for regulating static and sliding friction, antistatic agents) can be used more or less effectively:

From the group of phenols, the following are mentioned:
2,6-Di-tert.butyl-4-methylphenol,

6,6'-bis-(1-hydroxy-5-chloro-phenyl)-methane,
2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A).

From the group of phosphorus compounds, the following are mentioned:
Zinc dialkyldithiophosphate (Oloa 267 ^R ), '

Di-n-octyl phosphite and triphenyl phosphite.

These substances are used in quantities of 0.1 percent by weight or more, depending on the area of application and the application temperature, to inhibit the oxidative change of, for example, spinning fiber preparations.

The high-temperature stabilizers mentioned are all insoluble in water, which rules out their use in technical areas where rinsing and cleaning steps in an aqueous medium are required. Another disadvantage is their highly toxic potential. In addition, they are poorly or not at all biodegradable or even inhibit the biological degradation process in sewage treatment plants.

Surprisingly, it was found that water-soluble or dispersible antithermooxidants of the general formulas

O Il P - OH [alkanephosphonic acid half ester]

_OR2

O It

P - O" 1/rM ^r+ [Alkanephosphonic acid salts]

Ω" 1/rM ^r+

O

K R-) - P - O" 1/rM ^r+ [Alkanephosphonic acid half ester salts]

OR ₂ and

O

Il R-] - P - OR ₄ [alkanephosphonic acid diester]

_OR3

where

M ^r+ = Li ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ , Mg ²⁺ , Ca ²⁺ , Al ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ ,

H ₃ NC ₂ H ₄ OH ⁺ , H ₂ N(C ₂ H ₄ OH) ₂ ⁺ , HN(C ₂ H ₄ OH) ₃ ⁺ ,

H ₃ N-CH ₂ -CH(OH)CH ₃ ⁺ , H ₂ N(CH ₂ -CH(OH)CH ₃ ) ₂ ⁺ ,
HN(CH ₂ -CH(OH)CH ₃ ) ₃ ⁺ , morpholinium cation, piperidinium cation,

RI = Alkyl saturated with C-chain lengths from C5 to C ₂ Q or unsaturated
with C-chain lengths from C ₃ to C ₆ or

substituted or unsubstituted cycloalkyl with 5 to 12 ring carbon atoms,

R ₂ = (CH - CH ₂ - O-) _m R _6
R5

with R ₅ = H or CH ₃ or C ₂ H ₅ and

m = O, if R ₆ = straight-chain or branched, saturated or unsaturated alkyl with C chain lengths from Cj to C ₂₄ or substituted or unsubstituted cycloalkyl with 5-12 ring C atoms, or

m = 1 - 25, if R ₆ = H, phenyl or substituted phenyl, straight-chain or branched, saturated or unsaturated alkyl with C chain lengths from C-) to C ₂ g or saturated or unsaturated acyl with C chain lengths from C-) to C ₂ Q
20

or

R ₂ = an aminoalkylate of the general formula

(CH - CH ₂ - 0-) _m _i CH - CH ₂ N - R _{7
R5 R5 R7}

with R ₇ = alkyl (C-chain lengths C ₁ -C ₁₈ ) or (CH - CH ₂ -0-) _m H

R5
with m = 1 - 25

or

R ₂ = the residue of a polyhydric alcohol such as pentaerythritol, hexitol or glycerin,
35

R ₃ = (CH - CH ₂ -0-) _m H with m = 1 - 25

and

R ₄ = (CH - CH ₂ - 0-) _n H with η = 1 - 25

and R3 and R ₄ can be identical,
do not have the above disadvantages.

Particularly preferred antithermooxidants are those selected from alkanephosphonic acid monoester salts with R ₁ = C 6 -C ₂ Q -alkyl, R ₂ = C ₁ -C ₁ g-alkyl or a polyalkylene glycol radical and M ^r+ = an alkali or alkaline earth cation or an N-containing cation.

In concentrations of 0.5 to 30 percent by weight, depending on the application, these compounds inhibit the degradation of thermo-oxidatively labile compounds and thus make them stable at temperatures of more than 150 ^° C.

By selecting R ₁ , R ₂ and M, the product properties required for the respective application, such as water solubility, dispersibility, viscosity, acid character and others, can be optimized.

Thermo-oxidatively labile compounds that can be protected by the anti-thermo-oxidation agents according to the invention include thermo-labile hydrocarbons, fatty acids, fatty acid oxalkylates, fatty alcohols, fatty alcohol oxalkylates, fatty alcohol oxalkylate ethers, fatty amines, fatty amine oxalkylates, polyethylene glycols, polypropylene glycols, polyethylene-polypropylene copolymers (block or random polymers) and mixtures thereof. They are required as spinning fiber preparations, winding oils, lubricants, e.g. cutting oils, cooling lubricants, drawing agents, engine oils, gear oils, grinding and lapping oils, hardening oils and continuous casting lubricants, and heat transfer oils and are exposed to high temperatures during their use.

A typical example of the possible use of the compounds according to the invention is the testing of the stability of thermo-oxidatively labile compounds, which are widely used in the form of aids in the production and processing of synthetic fibers.

Examples of such compounds are PEG, PPG, PEG/PPG copolymers, fatty alcohol oxalkylates, fatty acid oxalkylates, fatty alcohol oxalkylate ethers and others. The thermostable properties of these compounds are tested by gravimetric measurement of the weight loss after a 30-minute heat treatment at 200 ^° C in a drying cabinet at normal pressure.

0.5 g of the anhydrous sample is weighed into glass dishes with a diameter of 45 mm. The weight of the residue, expressed as a percentage of the initial weight, and the appearance of the sample serve as a measure of the thermal stability.

The thermostabilizing properties of the compounds according to the invention are tested by gravimetric measurement of the weight loss of a known thermolabile compound after heat treatment at 200 ^° C in a drying cabinet at normal pressure with and without the addition of these thermostabilizing compounds, if necessary by varying their concentration. 0.5 g of the anhydrous thermolabile sample is weighed into glass dishes with a diameter of 45 mm. The weight of the residue, expressed as a percentage of the initial weight, and the appearance of the sample serve as a measure of thermostability.

' Example 1:

y PEG 1000

% Additive Thermostability in % Appearance

without

5 Octanephosphonic acid monoethyl ester K salt
5 Octanephosphonic acid-Ci2'i8' ^a ' ^k y' ^te t ^ra 9glycol-

half-ester K-salt

5 Octanephosphonic acid-PEG 300-half ester-K-salt 97
5 Octanephosphonic acid-PEG 600-half ester-Na-salt 92
5 Octanephosphonic acid-PEG 600 half ester
35

32 dark brown 99 light yellow 94 light yellow 97 light yellow 92 light yellow 94 light yellow

Example 2:

Sorbitol 22 moles ethylene oxide

% Additive Thermostability in % Appearance

without 4 dark brown

5 Octanephosphonic acid monoethyl ester K salt 99 light yellow

Example 3 :

co-C ₁ 2"18-Alkyl-iJ-methyl-heptaglykolether

% Additive

Thermostability in % Appearance

without 8 brown

1 Octanephosphonic acid monoethyl ester K salt 45 dark brown

3 Octanephosphonic acid monoethyl ester K salt 56 light yellow

5 Octanephosphonic acid monoethyl ester K salt 61 light yellow

7 Octanephosphonic acid monoethyl ester K salt 76 light yellow

10 Octane phosphonic acid monoethyl ester K salt 84 light yellow

15 Octanephosphonic acid monoethyl ester K salt 84 light yellow

20 Octanephosphonic acid monoethyl ester K salt 86 light yellow

ether-half ester-K-salt 64 light yellow 5 Octanephosphonic acid-methyl octaglycol ether-

half ester-K-salt 70 light yellow 5 Octanephosphonic acid-PEG 300-half ester-

K-Salt 73 light yellow 5 Decanephosphonic acid monoethyl ester-

K-Salt 76 light yellow STetradecanephosphonic acid monoethyl ester-

K-Salt 79 light yellow 5 Octadecanephosphonic acid monoethyl ester-

K-SaIz 64 light yellow

-&bgr;

Example 4:

Methyl octaglycol ether

% Additive

Thermostability in % Appearance

without 13 dark brown 5 Octanephosphonic acid monoethyl ester

K-salt 84 light yellow 5 Decanephosphonic acid-monoethyl-mono-

ethanol ester 63 light yellow 10 Decanephosphonic acid monoethyl mono-

ethanol ester 75 light yellow 5 octanephosphonic acid oleoyl monopropyl glycol

ether-half-ester-K-salt 79 light yellow

Example 5

0.5 g of a mixture consisting of 20% polyethylene glycol 200, 5% polyethylene glycol 600 and 75% polypropylene glycol monobutyl ether (viscosity 80 cst at ^550° C), which is used as a lubricant in rolling mills, paper machines and calenders, is heated for 100 minutes at 200 ^° C in a glass dish in a drying oven. The final weight after this treatment is 0.025 g, which corresponds to a decomposition of 95%. With the addition of 5% octanephosphonic acid monoethyl ester K salt, the final weight increases to 0.475 g, which corresponds to a decomposition of 5%.

Example 6

Staple fibre preparations are used to produce chemical fibres.
They primarily act as lubricants and antistatic agents. Especially texturing processes in polyester continuous threads for the textile sector, such as

The hot stretching of polyester threads for technical applications is also associated with a high thermal load on the fiber preparation. With a preparation layer of 0.45%, based on the fiber weight, the spun fiber preparation consists of

40 parts by weight of FeOaIkOhL-C ₁₂ -18" ⁷ EO-methyl ether

40 parts by weight of EO-PO block polymers (MG 2400)
5 parts by weight isotridecyl stearate
3 parts by weight fatty alcohol CI ₂ .14-4 EO
3 parts by weight of octanephosphonic acid monoethyl ester K salt
9 parts water by weight

After texturing, only 0.43%, corresponding to 95.5% of the original coating, can be extracted from the fiber. In contrast, the proportion of the fiber preparation that can be extracted from the fiber without the use of octanephosphonic acid monoethyl ester K salt drops to less than 0.2%, corresponding to 0.44% of the original coating. The use of the thermal stabilizer thus results in a reduction in the coating of fiber preparation due to the formation of volatile degradation products and thus prevents a loss of the sliding effect and antistatic properties of the prepared fiber, which ultimately results in a reduction in thread breaks and downtime. Last but not least, emissions of organic crack products into the environment are drastically reduced.

Claims (8)

Attorney File: 2003/3 Date: 25 September 1992 Claims: 1. Water-soluble or dispersible antithermo-oxidant as a stabilizing agent for substrates exposed to high temperatures, characterized in that it consists of one or more alkanephosphonic acid derivative(s) selected from those of the general formulae listed below: O Il RIP- OH [alkanephosphonic acid half ester] _OR2 R-) - P - O' 1/rM ^r+ [Alkanephosphonic acid salts] O" 1/rM ^r+ O Ri-PO" 1/rM ^r+ [Alkanephosphonic acid half ester salts] OR ₂ and I? Ri-P- OR ₄ [alkanephosphonic acid diester] _OR3 30 where M ^r+ = Li ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ , Mg ²⁺ , Ca ²⁺ , Al ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , H ₃ NC ₂ H ₄ OH ⁺ , H ₂ N(C ₂ H ₄ OH) ₂ ⁺ , HN(C ₂ H ₄ OH) ₃ ⁺ , H ₃ N-CH ₂ -CH(OH)CH ₃ ⁺ , H ₂ N(CH ₂ -CH(OH)CH ₃ ) ₂ ⁺ , HN(CH ₂ -CH(OH)CH ₃ )3 ⁺ , morpholinium cation, piperidinium cation, -2- R ₁ = Alkyl saturated with C-chain lengths from Cg to C20 or unsaturated with C-chain lengths from C3 to Cg or substituted or unsubstituted cycloalkyl with 5 to 12 ring carbon atoms,
5 R ₂ - (CH - CH ₂ - O-) _m R ₆ R5
with R ₅ = H or CH ₃ or C ₂ H ₅ and m = O, if Rg = straight-chain or branched, saturated or unsaturated alkyl with C-chain lengths from C-| to C ₂ 4 or sub substituted or unsubstituted cycloalkyl with 5-12 ring carbon atoms, or m = 1 - 25, if Rg = H, phenyl or substituted phenyl, straight-chain or branched, saturated or unsaturated alkyl with C chain lengths from C ₁ to C ₂ Q or saturated or unsaturated tes acyl with C-chain lengths from C-) to C ₂₀ , or R ₂ = an aminoalkylate of the general formula (CH - CH ₂ - O-) _m .-| CH - CH ₂ N - R _{7
R5 R5 R7} with R ₇ = alkyl (C-chain lengths C-| - C ₁₈ ) or (CH - CH ₂ -O-) _m H R ₅ with m = 1 - 25 or R ₂ = the residue of a polyhydric alcohol such as pentaerythritol, hexitol or glycerin, R ₃ = (CH - CH ₂ -O-) _m H with m = 1 - 25 R5
and -3- R ₄ = (CH - CH ₂ - 0-) _n H with η = 1 - 25 where R3 and _R4 can be identical. 2. Antithermooxidant according to claim 1, characterized in that the alkanephosphonic acid derivative(s) is/are selected from monoester salts with R-) = C(O-C2o-alkyl, R ₂ = C-pC-jg-alkyl or a polyalkylene glycol radical and M ^r+ = an alkali or alkaline earth cation or an N-containing cation. 3. Antithermo-oxidizing agents according to claim 1 or 2, characterized in that they are stabilizers for thermolabile hydrocarbons, fatty acids, fatty acid oxalkylates, fatty alcohols, fatty alcohol oxalkylates, fatty alcohol oxalkylate ethers, fatty amines, fatty amine oxalkylates, polyethylene glycols, polypropylene glycols, polyethylene-polypropylene copolymers (block or random polymers) and mixtures of these substances. 4. Antithermal oxidation agents according to one of claims 1 to 3, characterized in that they are stabilizing agents for spun fiber preparations, winding oils, lubricants such as cutting oils, cooling lubricants, drawing agents, engine oils, gear oils, grinding and lapping oils, hardening oils and continuous casting lubricants, and heat transfer oils. 5. Mixture of an antithermo-oxidant according to one of claims 1 to 4 with a substrate to be protected. 6. Mixture according to claim 5, characterized in that the substrate to be protected is selected from thermolabile hydrocarbons, fatty acids, fatty acid oxalkylates, fatty alcohols, fatty alcohol oxalkylates, fatty alcohol oxalkylate ethers, fatty amines, fatty amine oxalkylates, polyethylene glycols, polypropylene glycols, polyethylene-polypropylene copolymers (block or random polymers) and mixtures thereof. 7. Mixture according to claim 5 or 6, characterized in that the substrate to be protected is selected from among spinning fiber preparations, winding oils, lubricants -4- tels, e.g. cutting oils, cooling lubricants, drawing agents, engine oils, gear oils, grinding and lapping oils, hardening oils and continuous casting lubricants, and heat transfer oils. 8. Mixture according to one of claims 5 to 7, characterized in that the antithermo-oxidizing agent is present in an amount of 0.5 to 30% by weight.