EP1067168A1 - Use of polymers as anti-misting additives in waterbased coolant lubricants - Google Patents

Abstract

Copolymers with units derived from acrylamide (I) and alkali metal acrylamido alkylsulfonate (II) are used in amounts of 0.01-2 wt.% to prevent mist formation in water-based cooling lubricants. Copolymers with units derived from acrylamide (I) and alkali metal alkali metal acrylamido alkylsulfonate (II) of the given formulae are used in amounts of 0.01-2 wt.% to prevent mist formation in water-based cooling lubricants; R<1> = hydrogen (H) or 1-4 carbon (C) alkyl; R<2> = branched or linear 1-6 C alkylene; Y = an alkali metal . An Independent claim is also included for water-based cooling lubricants containing 0.01-2 wt.% of this copolymer in addition to the usual base materials and optionally functional additives.

Description

The present invention relates to the use of polymers which Contain structural units of acrylamide and of acrylamido sulfonic acids for Suppression of fog formation from water-based cooling lubricants.

When machining metal, wear is reduced by Tools used in general coolants. These can be with the for example, when cutting or grinding metals Swirling speeds of tool or workpiece into the environment become, which causes an undesirable fog formation. The state of the art knows different approaches to reduce this fog formation (antimisting).

EP-A-0 811 677 discloses water-based metalworking fluids which contain antimisting copolymers. On the one hand, these copolymers exist from structural units either from acrylamido sulfonic acids or from sulfonated styrene are derived, on the other hand, from structural units Acrylamides or acrylic esters.

EP-B-0 642 571 discloses the use of polymers with a Molecular weight over 1,000,000 units as an antimisting additive, the Polymers from the group of polyalkylene oxides, polyacrylamides, Polymethacrylamides or acrylamide / methacrylamide / unsaturated carboxylic acid copolymers are selected.

GB-A-22 52 103 discloses polymers as an antimisting additive consisting of structural units are built up, which differ from water-soluble acrylamides, acrylic acid and derive water-insoluble acrylamides.

Additives to reduce the formation of fog in metalworking already provide for reasons of health protection entrusted with such work People, is an important tool. Such additives are therefore the subject intensive research and development work. The present invention lies based on the task of providing additives with improved properties.

Surprisingly, it was found that polymers based on acrylamide and Acrylamido sulfonic acids are very effective fog inhibitors.

worin

R¹

H oder C₁-C₄-Alkyl

R²

einen verzweigten oder unverzweigten C₁-C₆-Alkylenrest

Y

ein Alkalimetall oder Ammonium bedeuten,

zur Verhinderung der Nebelbildung in wasserbasierenden Kühlschmierstoffen.The invention relates to the use of copolymers which contain structural units which are derived from the compounds of the formulas 1 and 2

wherein

R ¹

H or C ₁ -C ₄ alkyl

R ²

a branched or unbranched C ₁ -C ₆ alkylene radical

Y

is an alkali metal or ammonium,

to prevent the formation of fog in water-based cooling lubricants.

The copolymer defined in this way is also used in the following as an antimisting additive designated.

abgeleitet aus" bedeutet hier, daß die angegebenen olefinisch ungesättigten Verbindungen unter Verlust wenigstens einer C-C-Doppelbindung abreagieren und das Copolymer somit entsprechende Struktureinheiten enthält.The term

derived from "here means that the specified olefinically unsaturated compounds react with loss of at least one CC double bond and the copolymer thus contains corresponding structural units.

The invention further relates to water-based cooling lubricants, these antimisting additives included.

R ¹ preferably represents hydrogen. In a preferred embodiment, R ² represents an alkylene radical of the formula 3.

The structural unit of formula 2 is preferably by the copolymerization of Acrylamidopropenylsulfonic acid (AMPS) shown.

Preferred number average molecular weights of the copolymers are between 100,000 and 2,000,000, especially 250,000 to 1,000,000 units.

The relative viscosity or the k value serve as an indicator of the molecular weight. To determine the k value, the copolymer is dissolved in a certain concentration (usually 0.5%) and the outflow time at 25 ° C. is determined using an Ubbelohde capillary viscometer. This value gives the absolute viscosity of the solution (η _c ). The absolute viscosity of the solvent is η _o . The ratio of the two absolute viscosities gives the relative viscosity z = η c η O the k-value can be determined from the relative viscosity of the function and concentration using the following equation: Lg z = 75k 2 1 + 1.5kc + k c

The molar amounts of the structural units of the formulas 1 and 2 complement one another in a preferred embodiment to 100 wt .-%.

In a further preferred embodiment, the copolymer contains from 2 to 50% by weight of the structural units derived from Formula 1. It also contains Copolymer preferably 50 to 98 wt .-% structural units of formula 2, in particular from 20 to 35% by weight of structural units of the formula 1 and 65 to 80% by weight the structural units of formula 2.

In a further preferred embodiment, however, the copolymer can contain further comonomers. In such a further preferred embodiment, the copolymer contains structural units which are derived from compounds of the formulas 4 and / or 5,

In formula (4), R ³ and R ^{4 are} H or C ₁ -C ₄ alkyl. Furthermore, R ³ and R ⁴ , including the -N-CO group, can form a ring with 5, 6, 7 or 8 ring atoms. Rings with 5, 6 or 7 ring atoms are preferred. R ³ and R ⁴ can comprise heteroatoms, preferably they comprise only carbon atoms. In a particularly preferred embodiment, formula 4 stands for a structural unit of the formula 4a.

In a further particularly preferred embodiment, formula 4 stands for N-vinylcaprolactam. In a further particularly preferred embodiment, it is a structural unit of the formula 4b.

In formula 5, R ⁵ and R ⁶ independently of one another represent a terminally unsaturated alkenyl radical having 3 to 5 carbon atoms. R ⁷ and R ⁸ independently of one another are C ₁ -C ₄ alkyl. X is an anion. R ⁵ and R ⁶ preferably both represent an allyl radical. The proportion of structural units of the formulas (4) and (5) in the copolymer is independently up to 20% by weight, preferably independently from 10 to 20% by weight.

In a further preferred embodiment, the copolymer contains 5 to 20% by weight of structural units derived from acrylic acid.

The copolymers according to the invention are by copolymerization of Compounds of the formulas (1) and (2) and optionally (4) and / or (5) producible. The process for the preparation of the copolymers is state of the art Technology described and is set out below.

The copolymers can be prepared by the methods of solution polymerization, bulk polymerization, emulsion polymerization, inverse emulsion polymerization, precipitation polymerization or gel polymerization. The polymerization is preferably carried out as a solution polymerization in water or as a precipitation polymerization.
When the copolymerization is carried out in a water-miscible organic solvent, the reaction is generally carried out under the conditions of the precipitation polymerization. The polymer is obtained directly in solid form and can be isolated by distilling off the solvent or by suction and drying.

As a water-miscible organic solvent used to carry this out Manufacturing processes are suitable, especially water-soluble Alkanols, namely those with 1 to 4 carbon atoms, such as methanol, ethanol, propanol, Isopropanol, n-, sec- and iso-butanol, but preferably tert-butanol.

The water content of the lower alkanols used as solvents should not exceed 6% by weight, otherwise lump formation in the Polymerization can occur. Preference is given to a water content of 0 to 3 wt .-% worked.

The amount of the solvent to be used depends on a certain amount Degree according to the type of comonomers used. As a rule, per 100 g Total monomers 200 to 1,000 g of the solvent used.

When the polymerization is carried out in reverse emulsion, the aqueous Monomer solution in a known manner in a water-immiscible organic solvents such as cyclohexane, toluene, xylene, or heptane high-boiling gasoline fractions with the addition of 0.5 to 8% by weight, preferably 1 up to 4 wt .-%, known emulsifiers of the W / O type emulsified and with conventional Free radical initiators polymerized.

The principle of inverse emulsion polymerization is known from US 3,284,393. In this process, water-soluble monomers or mixtures thereof are mixed in polymerizes the heat to high molecular weight copolymers by first the monomers or aqueous solutions thereof, with the addition of water-in-oil emulsifiers in a water-immiscible, the coherent Emulsified phase-forming organic solvent and this emulsion in Heated in the presence of radical initiators. The comonomers to be used as such in the water-immiscible organic solvent be emulsified, or they can be in the form of an aqueous solution between Contains 100 and 5 wt .-% comonomers and 0 to 95 wt .-% water be, the composition of the aqueous solution a question of Solubility of the comonomers in water and the intended Polymerization temperature is. The relationship between water and the Monomer phase is variable within wide limits and is usually included 70:30 to 30:70.

To the monomers in the water-immiscible organic solvent to emulsify to a water-in-oil emulsion, the mixtures are 0.1 to 10% by weight, based on the oil phase, of a water-in-oil emulsifier was added. Those emulsifiers which are relatively low are preferably used Have an HLB value. The HLB value is a measure of hydrophobicity and hydrophilicity of surfactants and emulsifiers (Griffin, J. Soc. Cosmetic Chemists 1, (1950), 311). Substances with a low HLB value, e.g. below 10, are generally good Water-in-oil emulsifiers.

In principle, any inert water-insoluble liquid, i.e. each hydrophobic organic solvents can be used. In general Here hydrocarbons are used, whose boiling point is in the range from 120 to 350 ° C. These hydrocarbons can be saturated, linear or branched Be paraffinic hydrocarbons, as are predominantly found in petroleum fractions, these also contain the usual proportions of naphthenic hydrocarbons can. However, aromatic hydrocarbons such as, for example, can also be used Toluene or xylene and the mixtures of the above hydrocarbons as Oil phase can be used. A mixture of is preferably used saturated normal and iso-paraffin hydrocarbons, up to 20% by weight Contains naphthenes. A detailed description of the process can be found for example in DE-A-1 089 173 and in US-3,284,393 and 3,624,019.

Copolymers with molecular weights of over 1,000,000 are obtained if the polymerization in aqueous solution by the process of the so-called Gel polymerization is carried out. 15-60% by weight solutions of Comonomers with known suitable catalysts without mechanical Mixing using the Trommsdorff-Norrish effect (Bios Final Rep. 363.22; Macromol. Chem. 1, 169/1947) polymerized.

The produced in this way, in the form of aqueous jellies After mechanical comminution, copolymers can be processed using suitable apparatus be dissolved directly in water and used. But you can too after removal of the water by known drying processes in solid form preserved and only be dissolved in water again when they are used.

The polymerization reactions are in the temperature range between -60 and 200 ° C, preferably between 10 and 120 ° C, performed both under Normal pressure as well as under increased pressure can be worked. Usually the polymerization is carried out in a protective gas atmosphere, preferably under nitrogen executed.

To initiate the polymerization, high-energy electromagnetic or corpuscular rays or the usual chemical polymerization initiators can be used, e.g. B. organic peroxides such as benzoyl peroxide, tert. Butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, azo compounds such as azodiisobutyronitrile or 2'-azo-bis (2-amidinopropane) dihydrochloride and inorganic peroxy compounds such as (NH ₄ ) ₂ S ₂ O ₈ or K ₂ S ₂ O ₈ or H ₂ O ₂ if necessary in combination with reducing agents such as sodium bisulfite and iron (II) sulfate or redox systems which, as the reducing component, contain an aliphatic or aromatic sulfinic acid such as benzenesulfinic acid and toluenesulfinic acid or derivatives of these acids, such as, for. B. Mannich adducts of sulfinic acid, aldehydes and amino compounds, as described in DE-C-13 01 566, contain. 0.03 to 2 g of the polymerization initiator are generally used per 100 g of total monomers.

The polymerization batches are optionally small amounts of so-called moderators added to the course of the reaction harmonize that they flatten the response rate time diagram. she thus lead to an improvement in the reproducibility of the reaction and thus enable uniform products with narrow molecular weight distribution and high To produce chain length. Examples of suitable moderators of this type are Nitrilo-tris-propionylamide or monoalkylamines, dialkylamines or trialkylamines such as e.g. Dibutylamine. Also in the production of the copolymers according to the invention such moderators can be used with advantage. Furthermore, the Polymerization approaches so-called regulators are added, which the Molecular weight of the polymers produced by a targeted Set chain termination. Useful known regulators are e.g. Alcohols like Methanol, ethanol, propanol, isopropanol, n-butanol and amyl alcohols, Alkyl mercaptans such as e.g. Dodecyl mercaptan and tert. Dodecyl mercaptan, Isooctylthioglycolate and some halogen compounds such as e.g. Carbon tetrachloride, Chloroform and methylene chloride.

The copolymers become water-based cooling lubricants in amounts of 0.01 to 2, preferably 0.1 to 0.5 wt .-%, based on the formulated Cooling lubricant added.

The composition of the water-based cooling lubricants can be very be different. Such cooling lubricants often contain natural ones paraffinic, naphthenic or paraffinic-naphthenic mineral oils in addition other additives. Such cooling lubricants can also be made from ester oils, fatty oil derivatives, synthetic hydrocarbons, poly-α-olefins such. B. Polyisobutenes or polybutenes, polypropylene glycol, trimethylolpropane ester, Neopentyl glycol ester, pentaerythritol ester, di- (2-ethylhexyl) sebacate, di- (2-ethylhexyl) adipate, Dibutyl phthalate and / or esters of phosphorus-containing Acids exist.

Another embodiment of cooling lubricants are aqueous solutions of inorganic salts such as phosphates, borates, carbonates and organic Anti-rust agents such as amines, alkanolamines and substituted alkanolamines, as well as their reaction products with inorganic and organic acids. Such acids include, for example, natural or synthetic carboxylic acids such as caprylic acid, ethylhexanoic acid, capric acid, 2,2,4-trimethylhexanoic acid, Benzoic acid, substituted benzoic acids, dicarboxylic acids with 6 - 22 carbon atoms, Phosphoric acid esters, bicarboxylic acid half-esters or dicarboxylic acid halamides, Citric acid, gluconic acid, carbonic acid, phosphoric acid, polyphosphoric acids, Boric acid. Furthermore, cooling lubricants often contain water-soluble ones Lubricants such as glycols and polyglycols as well as ethers or esters of polyglycols and other additives for setting the desired properties.

Water-based cooling lubricants are in the German standard DIN 51385 described. Reference is hereby made to this standard.

Among these basic materials, the vast majority of cooling lubricants other functional additives, such as Additives to improve lubricity, antiwear agents, Corrosion inhibitors, antioxidants, anionic or nonionic emulsifiers, Solubilizers, anti-foaming agents, biocides and / or surfactants.

For the production of a usable water-based cooling lubricant the named raw materials, the copolymers defined here and, if applicable, functional additives mixed with water.

1. 0,1 - 2 Gew.-% einer Verbindung der Formel (6)

mit R', R'' = H oder CH₃

neutralisiert mit einem kurzkettigen Alkanolamin wie beispielsweise Triethanolamin, 0,01 - 2 Gew.-% des erfindungsgemäßen Copolymeren sowie Wasser ad 100 Gew.-%;

oder

2. 0,1 bis 2 Gew.-% einer Verbindung der Formel (7)

neutralisiert mit einem kurzkettigen Alkanolamin, 0,01 bis 2 Gew.-% des erfindungsgemäßen Copolymeren und Wasser ad 100 Gew.-%;

oder

3. 0,1 bis 2 Gew.-% einer Verbindung der Formel (8)

neutralisiert mit einem kurzkettigen Alkanolamin, 0,01 bis 2 Gew.-% der erfindungsgemäßen Copolymere sowie Wasser ad 100 Gew.-%.

In preferred embodiments, the cooling lubricants according to the invention contain the following components:

1. 0.1-2% by weight of a compound of the formula (6)

with R ', R''= H or CH ₃

neutralized with a short-chain alkanolamine such as triethanolamine, 0.01-2% by weight of the copolymer according to the invention and water ad 100% by weight;

or

2. 0.1 to 2% by weight of a compound of the formula (7)

neutralized with a short-chain alkanolamine, 0.01 to 2% by weight of the copolymer according to the invention and water ad 100% by weight;

or

3. 0.1 to 2% by weight of a compound of the formula (8)

neutralized with a short-chain alkanolamine, 0.01 to 2% by weight of the copolymers according to the invention and water ad 100% by weight.

In addition to compositions 1, 2 and 3, a polyalkylene glycol in one Amount of 5 to 20 wt .-% are added. It is an EO / PO block or copolymer that has lubricating properties.

Examples

The effectiveness of the copolymers according to the invention is as follows Prevention of fog formation from aqueous cooling lubricants is exemplified.

A device specially designed for this purpose is used to determine this effectiveness used. The device comprises a container with a height of 15 cm and a diameter of 9 cm. The test item is placed in this container Coolant filled in. From the outside is a line that runs in a frit ends, a gas stream (generally air) is blown into the cooling lubricant. The The strength of the gas flow is checked by means of a flow meter. The frit, About which the gas flow is blown into the container is approx. 1 cm above the bottom of the container. There is a disperser (Ultra Turrax. 1 cm above the frit M 25). If gas flows through the frit into the cooling lubricant, a dispersed fog above the liquid surface Coolant. The presence of this fog is confirmed by 2 halogen spotlights made visible, the light rays of which run over the surface of the liquid, that observation of the scatter caused by the fog is possible.

When the tests were carried out, a non-additive cooling lubricant was used in filled the container and observed the formation of fog. Then it became copolymer according to the invention added as a 5% aqueous solution until the No more fog was observed. The consumption of copolymers up the specified measured value is for the disappearance of fog.

Cooling lubricant concentrates with the following composition are used (Figures in% by weight).

Cooling concentrate K1

6%

Genapol® 0-050 (C ₁₆ / C ₁₈ fatty alcohol polyglycol ether with 5 EO)

49.5%

Hostacor® 4154 (alkenyl succinic acid derivative)

3%

Tall oil fatty acid

37%

Shell Gravex® (mineral oil)

4%

VE water

0.5%

Foam Ban® MS 455-3A (polyglycol siloxane defoamer)

Cooling concentrate K2

30%

Hostacor® IT (compound of formula (8) neutralized with triethanolamine)

17%

Triethanolamine

1 %

Genapol® PF 10 (EO-PO block polymer)

4%

Butyl diglycol

48%

VE water

Cooling lubricant concentrate K3

45%

Hostacor® IT

17%

Triethanolamine

9%

Genapol® B (EO-PO block polymer)

1 %

Genapol® PN 30 (EO-PO block polymer)

5%

Butyl diglycol

23%

VE water

The concentrates given above were used 3% in water at 20 ° dH.

Composition of the copolymers (% by weight) Copolymer A1

30%

Acrylamide

70%

AMPS

k-value:

200

Copolymer A2

15%

Acrylamide

65%

AMPS

20%

VIMA

k-value:

190

The k value was determined according to Fikentscher, Cellulosechemie, 13 (1932), 58.

The results obtained are shown in the following table. Efficacy of copolymers, data in% by weight of copolymer based on the weight of the cooling lubricant
Effectiveness in Additive K1 K2 K3 A1 0.08 0.08 0.08 A2 0.12 0.18 0.18 V1 0.16 0.16 0.18 V1: Antimisting agent according to Example 6 from EP-A-0 811 677

The copolymers according to the invention increase the viscosity of them additive cooling lubricants not or only insignificantly. You don't have one Influence on their tendency to foam, anti-corrosion properties or Lubricating effect.

The shear stability of the additive cooling lubricants was checked by Ultraturrax were sheared at 10,000 rpm for about 10 min with cooling. After Shear, the antimisting effect is fully retained, which shows that the polymers do not decompose under shear.

Filtration of the cooling lubricants through a Seitz depth filter K300 60 DMR (Pore size 5 µm, pressure filter press) has anti-misting properties also no influence.

The additives of cooling lubricants with the copolymers according to the invention can either with the concentrate or with the formulated cooling lubricant be made. While the formulated cooling lubricant is always on Water-based, the concentrate can also be present as an oil-based substance which the copolymers are not soluble. In this case only copolymers according to the invention in the already water-diluted cooling lubricant be incorporated.

Claims (8)

Use of copolymers which contain structural units which are derived from the compounds of the formulas 1 and 2

wherein

R ¹

H or C ₁ -C ₄ alkyl

R ²

a branched or unbranched C ₁ -C ₆ alkylene radical

Y

mean an alkali metal,

to prevent the formation of fog in water-based cooling lubricants in quantities of 0.01 to 2% by weight. Use according to claim 1, wherein R ^{1 is} hydrogen. Use according to claim 1 and / or 2, wherein R ^{2 is} a radical of the formula (3)

stands. Use according to one or more of claims 1 to 3, wherein the Molecular weight of the copolymer between 100,000 and 2,000,000 units lies. Use according to one or more of claims 1 to 4, wherein the Copolymer 2 to 50% by weight of the structural units of the formula (1) and 50 to Contains 98% by weight of the structural units of the formula (2). Use according to claim 5, wherein the copolymer is 20 to 35% by weight Structural units of the formula (1) and 65 to 80 wt .-% structural units of the Contains formula (2). Use according to one or more of claims 1 to 6, wherein the copolymer contains up to 20% by weight of structural units derived from compounds of the formulas (4) and / or (5),

wherein R ³ and R ⁴ independently of one another are H or C ₁ -C ₄ alkyl, or R ³ and R ⁴ , including the -N-CO group, form a ring having 5, 6, 7 or 8 ring atoms, R ⁵ and R ⁶ independently represent a terminal alkenyl radical having 3 to 5 carbon atoms, and R ⁷ and R ⁸ independently represent C ₁ -C ₄ alkyl. Water-based cooling lubricant, comprising besides water, the usual Basic materials of these cooling lubricants and, if applicable, functional additives a proportion of 0.01 to 2 wt .-% of copolymers according to one or several of claims 1 to 7.