DE4017687A1 - IMPROVED FUNCTIONAL LIQUIDS - Google Patents

Description

The present invention relates to functional liquids based on water as a thickener Contain polyoxyalkylene polymers.

It is known that certain polyoxyalkylene polymers can use as a thickener for aqueous systems (see e.g. DE-PS 22 20 338, DE-OS 38 36 902, EP-OS 54 953, EP-OS 1 09 515, US-PS 44 52 712, US-PS 44 81 367, CA-PS 8 62 804, WO-OS 84/361, Macromolecules 1987 (20), Pp. 3089 to 3091 and Technical data on Pluronic® Polyols - Customer circular from BASF-Wyandotte Corp.). In particular with those described in DE-OS 38 36 902 Polyoxyalkylene block polymers are made very good thickening effect. It has now been found that such systems tend to foam and the air separation capacity is often too low for them.  

It is also known that silicones are used as defoamers can use, the silicones in the foaming liquid should not be soluble (see Römpps Chemistry Lexicon, 8th edition, volume 5, p. 3705 (1987).

Functional liquids have now been found Water and polyoxyalkylene polymers, and optionally Contain alcohols and optional additives, which are characterized in that they are related on polyoxyalkylene polymers, additionally 0.2 to 5% by weight contain modified polyethers of the formula (I)

R- (CH ₂ ) _p - (Y) _q - (OCHR¹-CHR²) _x - (OCHR³-CHR⁴) _y -OR⁵ (I),

in the
R for

or for

R¹, R², R³ and R⁴ independently of one another are hydrogen or methyl,
R⁵ for a C₁ to C₁₈ alkyl, C₆ to C₁₈ aryl, C₇ to C₁₈ aralkyl or C₇ to C₁₈ alkaryl

-O-CH₂-CHOH-CH₂-

or

p for zero or an integer from 1 to 8,
q for zero or 1 and
x and y each independently represent an integer from 5 to 100,
where in formula (II)
R⁶, R⁷ and R⁸ independently of one another each have a C₁ to C₁₀ alkyl or C₆ to C₁₀ aryl radical which may be substituted by halogen,
R⁹ is hydrogen or a C₁ to C₁₀ alkyl or C₆ to C₁₀ aryl radical which is optionally substituted by halogen,
n is an integer from 1 to 50 and
m zero or an integer from 1 to 50
and in formula (III)
R¹⁰ are each a C₆ to C₂₀ alkylene radical or a C₆ to C₂₀ cycloalkylene or arylene radical which is optionally substituted by C₁ to C₄ alkyl or halogen,
R¹¹ each have a C₂ to C₁₄ alkylene or C₃ to C₁₄ cycloalkylene radical and
R¹² each means - (CH ₂ ) _p - (Y) _q - (OCHR¹-CHR²) _x - (OCHR³-CHR⁴) _y - OR⁵, where R¹ to R⁵ have the meaning given above.

In the water-based functional ones according to the invention Liquids can e.g. B. lubricants, Tools for metalworking or Act hydraulic or heat transfer medium.

Functional liquids according to the invention can e.g. B. 30 to 85 wt .-% water and 0.02 to 20 wt .-% modified Contain polyether of formula (I). Prefers are contents of 35 to 50 wt .-% water and 0.05 to 2% by weight of modified polyethers of the formula (I).

As polyoxyalkylene polymers such. B. the in the beginning indicated references cited in question. Preferred are polyoxyalkylene block copolymers which consist of a hydrophobic bonded to a starter molecule (S) Polyoxyalkylene block (P) and then one consist of hydrophilic polyoxyalkylene oxide block (E), wherein  (S + P) the reaction product of (S) with 20 to 45 mol (per equivalent of active hydrogen in S) propylene oxide or an ethylene oxide containing predominant propylene oxide / Represents propylene oxide mixture and on this, if appropriate after partial or complete amination of the OH groups present on (S + P), 5 to 30 moles (per alkylene oxide unit in P) of ethylene oxide or an ethylene oxide containing predominantly ethylene oxide / Propylene oxide mixture have been polymerized (see DE-OS 38 36 902).

Alcohols, e.g. B. monoethylene glycol, diethylene glycol, Butoxy-ethoxy-ethanol, monopropylene glycol and / or Dipropylene glycol, preferably diethylene glycol, can be used in the functional liquids according to the invention, for. B. be contained in an amount of 0 to 40 wt .-%. This amount is preferably 20 to 40% by weight.

As usual additives such. B. corrosion inhibitors, such as toluene triazole, di- and / or triethanolamine and Boric acid amine ester (e.g. Rewocoros® RA-BE), wear protection agent, such as polyoxyethylene octadecylene ether phosphate (e.g. Gafen® LB 400), fatty amines or ethoxylated Fatty amines (e.g. Noramox® 011) or ethoxylated fatty acid amides (e.g. Dionil® W100) and / or antioxidants, like glycols, in question. Common additives (without Glycols) can e.g. B. in an amount of 0 to 20 wt .-%, preferably in an amount of 4 to 10% by weight be.  

It is an essential feature that the invention functional liquids, based on the existing polyoxyalkylene polymers, 0.2 to 5% by weight contain modified polyethers of the formula (I). This amount is preferably 1 to 2% by weight.

In the modified polyethers of formula (I) the units (O-CHR²-CHR²) and (O-CHR³-CHR⁴) in Blocks, statistically distributed or partially in blocks and some are statistically distributed.

Preferred modified polyethers of the formula (I) are those in which
R¹, R² and R³ for hydrogen,
R⁴ for methyl,
R⁵ is a C₁ to C₆ alkyl radical,
Y for -O-CH₂-CHOH-CH₂- or

p for zero, 1 or 2,
q for zero or 1,
x for an integer from 10 to 50 and
y represents an integer from 8 to 40,
where R = formula (II)
R⁶, R⁷ and R⁸ are each independently methyl or phenyl,
R⁹ is hydrogen or methyl,
n is an integer from 3 to 20 and
m zero or an integer from 1 to 20
and in the case R = formula (III)
R¹⁰ each have a C₆ to C₁₃ alkylene radical or an optionally substituted by methyl C₆ to C₁₃ cycloalkylene or arylene radical,
R¹¹ each have a C₂ to C₇ alkylene or C₅ to C₇ cycloalkylene radical and
in R¹² the symbols R¹ to R⁵, p, q, x, y and Y have the meaning given above as preferred.

Particularly preferred modified polyethers of the formula (I) are those in which
R¹, R² and R³ for hydrogen,
R⁴ for methyl,
R⁵ is a C₁ to C₆ alkyl radical,
Y for -O-CH₂-CHOH-CH₂- or

p for zero or 3,
q for zero or 1,
x for an integer from 15 to 35 and
y represents an integer from 12 to 25,
where R = formula (II)
R⁶, R⁷, R⁸ and R⁹ methyl,
n is an integer from 4 to 10,
m zero or an integer from 1 to 10
and in the case R = formula (III)
R¹⁰ each have a C₆ to C₁₃ alkyl, cycloalkyl or aryl radical,
R¹¹ each have a C₂ to C₃ alkylene radical and
in R¹² the symbols R¹ to R⁵, p, q, x, y and Y have the meaning given above as being particularly preferred.

The preparation of those suitable for the present invention modified polyethers of formula (I) for example in DE-OS 27 56 770 (types with R = Formula (II)) and DE-OS 33 30 197 (types with R = Formula (III)) described.

Functional liquids according to the invention with the previously Characteristics described are characterized by that despite the presence of foamable systems, these are e.g. B. polyoxyalkylene polymers and Room temperature water soluble silicones (= products of Formula (I) with R = Formula (II)), very good foam damping have a very good air separation ability and compared to corresponding functional liquids without content of modified polyethers of the formula (I), no or only an insignificant change in the thickening effect demonstrate. This property picture is over the temperature range from 10 to 60 ° C is particularly pronounced.

In the production of functional according to the invention Liquids should be taken care that the polyoxyalkylene polymer and the modified polyether  Formula (I) does not match without a diluent. So you can z. B. proceed so that the polyoxyalkylene polymer and the modified polyether at the same time stir in water and if necessary beforehand, adding other ingredients simultaneously or afterwards. You can also first the polyoxyalkylene polymer and then the modified polyether or first the modified polyether and then the polyoxyalkylene polymer mix with water and if necessary to a Add additional components at any time. You can also start with a mixture of polyoxyalkylene polymers, modified polyether and little water and / or produce alcohol or glycol and this Then concentrate on the for by diluting with water a functional liquid according to the invention required Bring concentration profile.

In some cases it has been observed that the functional liquids described so far Temperatures in the range of 10 to 40 ° C are not always one optimal combination of good foam absorption, good Air separation ability and good thickening effect achieved becomes.

A special embodiment of the present invention, at which even at temperatures in the range 10 to 40 ° C always an optimal combination of good foam absorption, good air separation capacity and good thickening effect is achievable is characterized by that one described above as preferred polyoxyalkylene polymers  uses, which subsequently to the hydrophilic Polyalylene oxide block E yet another hydrophobic Molecular part H included.

Such further molecular parts H can be introduced by using a polyoxyalkylene polymer as described above Type consisting of the molecular parts S, P and E. and contains in part E terminal OH groups, with z. B. 4 to 30 moles of propylene oxide (per equivalent of OH groups) and in the presence of a catalyst, with fatty acids, Fatty acid esters or fatty acid chlorides, each with 6 up to 30 C atoms, with glycidyl ethers with 4 to 30 C atoms, with α-olefin oxides with 4 to 30 carbon atoms or with Monoisocyanates reacted with 12 to 22 carbon atoms. These Implementations can be carried out according to methods known per se (see e.g. Organikum, 16th edition, p. 407 and Houben-Weyl, volume 14/2, p. 425 ff. And volume E4, p. 142 ff).

Reactions with α-olefin oxides are preferred 4 to 18 carbon atoms with (partially) aromatic glycidyl ethers 6 to 20 carbon atoms and monoisocyanates with 12 to 22 carbon atoms Atoms.

Reactions with aliphatic, aromatic or araliphatic monoisocyanates with 15 to 18 carbon atoms.

The built up from the molecular parts S, P, E and H. Polyoxyalkylene polymers are new compounds.  

Such new connections are made by a separate one own patent application includes. With the new connections are polyoxyalkylene block copolymers, those from a bound to a starter molecule (S) hydrophobic polyoxyalkylene block (P) and then a hydrophilic polyalkylene oxide block (E) exist, where (S + P) the reaction product of (S) with 20 to 45 moles (per equivalent of active hydrogen in S) Propylene oxide or a predominantly containing propylene oxide Ethylene oxide / propylene oxide mixture, and on this, if necessary after a partial or complete amination of the OH- at S + P Groups, 5 to 30 moles (per alkylene oxide unit in P) Ethylene oxide or one containing predominantly ethylene oxide Polymerized ethylene oxide / propylene oxide mixture which are characterized in that they then another one at the polyalkylene oxide block E. contain another hydrophobic part of the molecule H. Like such containing further hydrophobic molecular parts H. Polyoxyalkylene polymers can be made and so that the nature of these other parts of the molecule is H. described above.

The built up from the molecular parts S, P, E and H. Polyoxyalkylene polymers can be used in the inventive functional liquids as the only polyoxyalkylene polymers be included. It can also be known Polyoxyalkylene polymers in a mixture with the new polyoxyalkylene polymers are present, with the proportion of new Polyoxyalkylene polymers, based on the total available Polyoxyalkylene polymers, e.g. B. 5 to 20% by weight  can be. One can also in known, from the Molecular parts S, P and E built polyoxyalkylene polymers (see DE-OS 38 36 902), the OH end groups in the molecular part E only partially on one of the above Implement procedures and so more hydrophobic Molecular parts H only on individual, but not on all Attach molecular part S to outgoing strands.

In the production of the functional according to the invention Liquids with the new, from the molecular parts S, P, E and H are built polyoxyalkylene polymers no restrictions to consider. So you can too first the new polyoxyalkylene polymers with modified Polyethers of the formula (I) without the addition of a Mix diluent and mix from this mixture Add water and possibly other components a functional liquid according to the invention produce.

Examples

The following materials were used in the examples:

A. Mixtures of water, alcohols and for functional ones Liquids usual additives

A1 45 parts by weight of water
15 parts by weight of monoethylene glycol
15 parts by weight of diethylene glycol
4 parts by weight of dipropylene glycol
1 part by weight of Gafen® LB400 (polyoxyethylene octadecylene ether phosphate)
0.1 part by weight of tolutriazole
0.4 parts by weight of diethanolamine
0.5 part by weight of Rewocoros® RA-BE (boric acid amine ester)
Add triethaolamine until the pH is 9.

A2 as A1, additional 2.5 parts by weight of Dionil® W 100 (ethoxylated fatty acid amide)

A3 as A2, additional 2.5 parts by weight of Noramox® 011 (ethoxylated oleylamine)

A4 as A1, additional 2.5 parts by weight of Noramox® 011 (ethoxylated oleylamine)  

B. polyoxyalkylene polymers General manufacturing process for polyoxyalkylene polymers

1st stage: The starter was placed in a reactor and mixed with aqueous potassium hydroxide solution. Then was heated to 120 ° C under reduced pressure and distilling off water.

2nd stage: Then at 105 to 120 ° C propylene oxide, optionally together with ethylene oxide with stirring at such a rate introduced into the reactor that a pressure of 4 bar was not exceeded. After finishing the alkylene oxide addition was continued for 4 hours left to react.

3rd stage: The reaction mixture became aqueous again Potash lye added and at reduced pressure distilled off at 115 ° C. water.

4th stage: Ethylene oxide was then at 105 to 120 ° C, optionally together with propylene oxide with stirring at such a rate introduced into the reactor that a pressure of 4 bar was not exceeded. After finishing the alkylene oxide addition was continued for 4 hours left to react. Then the educated one Polyether neutralized with acetic acid.  Specifically, the polyoxyalkylene polymers B1 to B8 prepared as shown in Table 1.  

Table 1

C. Modified polyether

C1 mixed modified polyether of formula (I) with R = formula (II), R¹ = R² = R⁴ = hydrogen, R³ = R⁶ = R⁷ = methyl, R⁵ = n-butyl, Y = -O-CH₂-CHOH-CH₂-, p = 3, q = 1, x = 19 or 26, y = 20 or 15, n = 3 to 6 and m = zero.

C2 mixed modified polyether of formula (I) with R = formula (II), R¹ = R² = R⁴ = hydrogen, R³ = R⁶ = R⁷ = methyl, R⁵ = n-butyl, Y = -O-CH₂-CHOH-CH₂-, p = 3, q = 1, x = 16, y = 12, n = 6 to 12 and m = zero.

C3 modified polyether of formula (I) with R = Formula (III), R¹ = R² = R⁴ = hydrogen, R³ = Methyl, R⁵ = n-butyl, p = zero, q = zero, x = 21, y = 16, R¹⁰ each toluene and R¹¹ each Ethylene, in the radicals R¹² each R¹ = R² = R⁴ = hydrogen, R³ = methyl and R⁵ = n-butyl are.

D. Polyoxyalkylene polymers with additional hydrophobic Molecular part H

In polyoxyalkylene polymers obtained in Section B. became a lower by one of the following methods hydrophobic molecular part H introduced.  

Method 1:

100 g of polyoxyalkylene polymer were dissolved in 200 ml of toluene dissolved and dewatered azeotropically. Under nitrogen cooled to 70 ° C and then 0.5 ml of boron trifluoride diethyl etherate added. After stirring for 15 minutes at 70 ° C cooled to room temperature and an n-alkyloxirane or a glycidyl ether was added and the mixture was stirred for 1 hour. Then it was neutralized with sodium carbonate, solid components separated by filtration and still existing Distilled off solvent.

Method 2:

400 g of dried polyoxyalkylene polymer (12 hours at 16 mbar kept at 80 ° C), 0.05 g of diazabicyclooctane and 500 ml of dry dioxane were combined and 1 Stirred for one hour at room temperature. Then was Added n-alkyl monoisocyanate and boiled for 2 hours heated at reflux. Then at 16 mbar and 130 ° C. the solvent distilled off and finally solid components separated by filtration.

Method 3:

200 g of dried polyoxyalkylene polymer (12 hours at 16 mbar kept at 80 ° C), 1 g NaOH and 300 ml dry Dioxane were added and added for 30 minutes Room temperature stirred. Then a fatty acid chloride added and another hour at room temperature  touched. Then at 16 mbar and 130 ° C Solvent distilled off and finally solid components separated by filtration.

Specifically, those with another were hydrophobic Molecular part H provided polyoxyalkylene polymers B 1.1 up to B 8.2 as shown in Table 2.  

Table 2

Examples 1 to 41

In a mixture of water, alcohols and for functional Liquids usual additives (see materials A.) various thickeners (see materials B. and D.), and modified polyethers (see materials C.) added. Thus water and / or was required Diethylene glycol added until a viscosity grade ISO VG 46 (see DIN 51 519) was available. The each in % By weight of the materials B., C. and / or D. refer to the respective so produced finished functional liquid.

The tendency to foam on these functional liquids measured according to DIN 51 566. 200 ml the respective functional liquid in a 1-1- Blow through the test tube with an air flow of 3.6 l / min. The pressure was 50 mm water column compared to the 200 ml Filling at a pre-pressure of 20 mm water column. The Measurement was taken either after 5 minutes or after reaching it a foam volume of 800 ml ended, each after what used to be the case.

Furthermore, these functional liquids the air separation capacity measured according to DIN 51 381. The measurement was in each case after reaching 99% of the Initial density ended. Details are given in Table 3 evident.  

Table 3

Examples that do not contain Group C material are not according to the invention and are used for comparison.

Claims (7)

1. Functional liquids which contain water and polyoxyalkylene polymers, and optionally alcohols and optionally conventional additives, characterized in that, based on polyoxyalkylene polymers, they additionally contain 0.2 to 5% by weight of modified polyethers of the formula (I) R- (CH ₂ ) _p - (Y) _q - (OCHR¹-CHR²) _x - (OCHR³-CHR⁴) _y -OR⁵ (I), in which
R for or for R¹, R², R³ and R⁴ independently of one another are hydrogen or methyl,
R⁵ for a C₁ to C₁₈ alkyl, C₆ to C₁₈ aryl, C₇ to C₁₈ aralkyl or C₇ to C₁₈ alkaryl
Y for -O-CH₂-CHOH-CH₂-or p for zero or an integer from 1 to 8,
q for zero or 1 and
x and y each independently represent an integer from 5 to 100,
where in formula (II)
R⁶, R⁷ and R⁸ independently of one another each have a C₁ to C₁₀ alkyl or C₆ to C₁₀ aryl radical which may be substituted by halogen,
R⁹ is hydrogen or a C₁ to C₁₀ alkyl or C₆ to C₁₀ aryl radical which is optionally substituted by halogen,
n is an integer from 1 to 50 and
m zero or an integer from 1 to 50
and in formula (III)
R¹⁰ each represent a C₆ to C₂₀ alkylene radical or a C₆ to C₂₀ cycloalkylene or arylene radical optionally substituted by C₁ to C₄ alkyl or halogen,
R¹¹ each have a C₂ to C₁₄ alkylene or C₃ to C₁₄ cycloalkylene radical and
R¹² each means - (CH ₂ ) _p - (Y) _q - (OCHR¹-CHR²) _x - (OCHR³-CHR⁴) _y -OR⁵, where R¹ to R⁵ have the meaning given above. 2. Functional liquids according to claim 1, characterized characterized in that they contain 30 to 85% water and 0.02 to 20% modified polyethers Contain formula (I). 3. Functional liquids according to claims 1 and 2, characterized in that in formula (I)
R¹, R² and R³ for hydrogen,
R⁴ for methyl,
R⁵ is a C₁ to C₆ alkyl radical,
Y for -O-CH₂-CHOH-CH₂- or p for zero, 1 or 2,
q for zero or 1,
x for an integer from 10 to 50 and
y represents an integer from 8 to 40,
where R = formula (II)
R⁶, R⁷ and R⁸ are each independently methyl or phenyl,
R⁹ is hydrogen or methyl,
n is an integer from 3 to 20 and
m zero or an integer from 1 to 20
and in the case R = formula (III)
R¹⁰ each have a C₆ to C₁₃ alkylene radical or an optionally substituted by methyl C₆ to C₁₃ cycloalkylene or arylene radical,
R¹¹ each have a C₂ to C₇ alkylene or C₅ to C₇ cycloalkylene radical and
in R¹² the symbols R¹ to R⁵, p, q, x, y and Y have the meaning given above as preferred. 4. Process for the production of functional Liquids of claim 1, characterized in that the polyoalkylene polymer and modified polyether of formula (I) not without Brings together thinner. 5. Functional liquids according to claims 1 to 3, characterized in that it is in the Polyoxyalkylene polymers are those consisting of a hydrophobic bonded to a starter molecule (S) Polyoxyalkylene block (P) and then a hydrophilic polyalkylene oxide block (E) exist, where (S + P) the reaction product of (S) with 20 to 45 moles (per equivalent of active Hydrogen in S) propylene oxide or one predominantly Ethylene oxide containing propylene oxide / - Represents propylene oxide mixture and on this, if necessary after a partial or complete Amination of the OH- present on (S + P) Groups, 5 to 30 moles (per alkylene oxide unit in P) ethylene oxide or a predominantly ethylene oxide polymerized containing ethylene oxide / propylene oxide mixture have been and then another another hydrophobic molecular part H introduced has been. 6. Functional liquid according to claim 5, characterized characterized by such further molecular parts H have been introduced by using a polyoxyalkylene polymer, that from the molecular parts S, P and E exists and in part E terminal OH groups  contains, with 4 to 30 moles of propylene oxide (per equivalent OH groups) and in the presence of a catalyst with fatty acids, fatty acid esters or fatty acid chlorides each with 6 to 30 carbon atoms, with Glycidyl ethers with 4 to 30 C atoms, with α-olefin oxides with 4 to 30 carbon atoms or with monoisocyanates with 12 to 22 carbon atoms. 7. Functional liquid according to claims 1 to 3, 5 and 6, characterized in that, based on total polyoxyalkylene polymers 5 to 20 wt .-% polyoxyalkylene polymers containing one Molecular part H are present.