DE2318131A1 - WATER CLEAR ADJUSTABLE POLYMERLATICES AS AQUATIC COOLING LUBRICANTS - Google Patents

Description

Clear water adjustable polymer latexes as aqueous Kühlschmi e rmi11 e 1

Cooling lubricants should be used in metalworking alongside one good cooling effect aucii a reduction in friction between the tool and cause the workpiece. Both claims can, however difficult to reconcile.

Well-known cooling lubricants are e.g. aqueous emulsions of mineral oils, Soaps or fats or aqueous solutions of sodium nitrite and triethanolamine, and also aqueous solutions of (Tri) alkanolamine borate alone or in combination with fatty acid alkanolamine salts (German Patent 818 67I »German Auslegeschrift 1 205 903) · For the purpose of corrosion protection you can Such cooling lubricants, additions of e.g. alkali or amine salts aromatic sulfonate nidocarboxylic acids (German Interpretation document 1 297 798).

It has now been shown that cooling lubricants of the above-mentioned composition have a good cooling effect and a show good corrosion protection in metalworking, but not their lubricating effect in heavier machining operations sufficient.

Numerous proposals have already been made for improving the lubricating effect been made. For example, extreme pressure (EP) additives known per se have been incorporated into the aqueous cooling lubricants Incorporated chlorine, phosphorus and sulfur base. The result

409843/0554

Hoe 73 / F 801 (Ge h8 ?.)

The improvements that can be achieved are, however, minor, and some fillers show disadvantages in the course of use by hydrolytic cleavage of the additives.

In the German Offenlegungsschrift 1 59 ^ 6 "51 it is proposed to add the aqueous cooling steps in polyolefin dispersions. This measure brings an improvement in the lubricating values, but leads to an exercise in the case of lubricants which are clear per se Naturally existing turbidity leads to an increase in the turbidity, since the polyolefin dispersions have partial sizes that are in the order of magnitude of the wavelength of visible light or above and thus strongly scatter the incident light. However, cloudy cooling lubricants are highly undesirable because Experience has shown that the service life of emulsions with relatively coarsely dispersed particle slurries is relatively short, so that separation can occur.

The present invention is now based on the object that Lubricating properties of aqueous cooling lubricants without impairment to improve their clarity.

Surprisingly, this is possible because the aqueous Cooling lubricants mostly based on acrylate, so-called. supplies water-clear polymer dispersions.

The invention therefore relates to the use of acrylic or methacrylate-based polymer latices which can be adjusted to make water clear by adding amine as an additive to improve the lubricating effect of aqueous cooling agents for metalworking in an amount of 0.01 to 20 ^c ß>, calculated according to the solids content of the latex, based on the total weight of the cooling agent.

A09843 / 0554

Hoe 73 / F 801 (Ge 482)

The polymer latices to be added according to the invention improve the lubricating action of the aqueous metal working fluids to at least as much as polyolefin dispersions, without, however, adversely affecting the transparency like these. Cooling lubricants which contain the additives claimed are also distinguished by their very good emulsion stability at low and high temperatures. Under water clear dispersions of aqueous copolymer latexes are understood to be based on (meth) acrylate, which by a content of 10 wt raindestesn -fo (meth) acrylic acid and from 0.1 -. Aborting acting 5 wt .- ^ o a polymer chains substance such polyhalogen or mercaptans are labeled. Such dispersions, which have solids contents between 20 and 60, preferably 35 to 45% by weight, become water-clear through the addition of water-soluble amines such as ammonia, lower alkylamines or triethanolamines, etc.

The composition and production of the water-clear dispersions are known in principle and, for example, in the German Offenlegungsschriften 1 811 247, 1 811 012 and 2 059 6O6.

Differentiate between the water-clear dispersions proposed as additives their chemical structure and their physical behavior are very much different from polyolefin dispersions. While the latter is based on the well-known mineral oils in the lubricant sector or paraffins and slurries of water-insoluble Represent polymer particles in water, the former is determined by the ester or acid grouping of the polymerized (Meth) Acryloononation bestows the property under uptake to swell so strongly of water that it can see in the realm of the visible Light can no longer be distinguished from the surrounding aqueous medium in terms of its refractive index and thus the criterion "water-clear" own. In principle, the latices are quite usable drilling and cutting oils as well as aids on their own. for non-cutting metalworking, such as the drawing of Wires and deep drawing, since they combine the high cooling effect of aqueous systems with the good lubricating properties of polymer

4 09843/0 55 4 - n

Hoe 73 / F 801 (Ge 482)

unite dispersions. In practice, however, it is mostly from Advantage of using additives such as anti-corrosion agents, Bactericidal, mineral oil emulsions with or without the addition of known ones chlorine-, phosphorus- ixnd / odei ^ sulfur-containing additives, Foam inhibitors and the like. To move more to their application technology To design properties optimally.

Ii the presence of the water-clear copolymer latices in the usual cooling lubricants in an amount of 0.01 to 20, preferably 0.1 to 5 wt .- ^, based on the total weight of the Kühlschmieriaittels, both the coefficient of friction is used in the Miechreibungsgebiet as well as the wear and tear between metal surfaces that are under Load sliding on each other, greatly reduced. Presumably this effect is based on the fact that the claimed Metal surfaces form a lubricating polymer film under the influence of frictional heat and high shear forces.

For the evaluation of the lubrication properties, the friction

2 Reichert wear balance, where the abrasion area F is in mm

and the specific surface pressure can be measured in kp / cm, as well as the four-ball apparatus - VIcA - used. With the VkA the coefficient of friction at a load of 100 kg and the wear diameter in mm on the stationary balls were determined.

The following examples are intended to explain the invention in more detail. They show that dispersions which can be adjusted to be water-clear are the polyolefin dispersions and are superior to conventional drilling oils.

Examples 1-10

It was the lubricating effect of various polyacrylate dispersions (Solids content 0.5, 1.0 and 5.0 wt .- ^) compared to equally concentrated Polyethylene dispersions and a drilling oil concentrate based on mineral oil on the friction wear balance according to Reichert and

409843/0554

Hoe 73 / F 801 (Ge H 82)

in the four-ball apparatus according to Shell-Boerlage with a load of 100 kg examined. In the following tables 1 and 2 are in column 2 the composition of the respective polymer or the formulation dos lubricant, in columns 3-5 are the associated examination results are recorded.

The abbreviations mean:

MMA = methyl methacrylate BuA = butyl acrylate

ÄA = s ethyl acrylate 'MeAS = methacrylic acid DDM = dodecyl mercaptan BTM = bromotrichloromethane

The preparation of a suitable polymer latex (that used in Example 1) is carried out, for example, as follows:

To 708 g of deionized water 37 * 5 S of a ^ fO ^ .igen aqueous solution of the triethanolamine salt of an alkyl sulfate and 2.5 β ammonium persulfate and 35 S of a mixture of

275 grams of MMA

25 g BuA

25 g ÄA

175 g MeAS and

10 g of DDM

admitted. The mixture is then heated to 80 ° C. with stirring. At this The remainder of the monomer mixture becomes temperature in the course of two Metered in for hours. Thereafter, 0.5 g of ammonium sulfate, dissolved in 20 g of water, is added, followed by a further two hours Temperature is stirred. After cooling to room temperature adjusted to a ρ .. value of 7 - 7 »5 with dilute ammonia solution. The dispersion obtained has a solids content of 40.3 wt .-%.

409843/0554

Tabel example

No.

Monomer composition and emulsifier system

Reichert exam

Four ball apparatus test.

Special surface pressing,

in kp / c: rr; 3O kp loading

actual

1OO ra friction path

Latex in drinking water egg

^p il 7 iReibzahl
kp,
Min.

Wear and tear-

durclimesser
kp, 1 min

A lot of latex in drinking water p.

• H 7

1.0

transparency

<iiiger latex in drinking water

^P H 7

CD CO OO · * »CO

MMA: BuA: AA: MeAS = 55: 5: 5: 35; 2 <jo DDM; 3 ^ϋ , ο triethanolamine alkyl sulfate (as emulsifier)

¥ ie example 1; Ratio 65: 5: 5: 25; 2 <p DDM; 2 ^ triethanolamine alkyl sulfate

Same as example 1j ratio 58: 13: 13: 16; 3 # BTM; 3 ^ Na-alkyl polyglycol ether sulfate

Vie Example 1; Ratio 65: 10: 10: 15 ;, 3 # BTM; 3 ^

Triethanolamine alkyl sulfate

¥ ie example 1; Relationship! 5.6: 15:15:14; 3 <? &DDM; 2 # Arr.monium alkyl polyglycol ether sulfate

Like example 55 3 $ DDM; 1 ^ o ammonium alkyl polyglycol ether sulfate

340

340

580

330

330

o _f o4o

0.055

0.050

0.010

0.592

0.616

0.438

0.722

clear

clear

clear'

clear

clear

clear

S O CJ!

Table 2,

example
No. Monomer composition
and emulsifier system or
(at 10) recipe dee
Lubricant Reichert exam 1.0 pounds Four ball apparatus test. Pre-wear
diameter
100 kp, 1 min. 0, ^ 54
0.442
0.454 transparency
5 $ latex
in drinking water
^p H 7 7th
8th
{Comp.)
9
(Cf.)
10
(Cf.) Like example 5 <
3 <$> DDM; without emulsifier
Ethylene; $ 0 tetrapropy
lenbenzenesulfonate; 3 / β
Paraffin sulfonate
Ethylene
$ 12 Ba-Laurate
Drilling oil concentrate
Mineral oil base with approx.
13 $ Cl (from chlorinated paraf-
fin? XCurtis S7) Special surface pressing
in kp / cm ² $ 30 kp Be
burden
100 friction path
Latex in drinking water
^P H 7 390
285
208
190 Friction coefficient
100 kp,
1 min. 5 $ latex in drink
water ρ _H - clear
cloudy
cloudy
cloudy $ 0.5 > ± g 0.0675
0.0500
0.0675 370

Hoe 73 / F 801 (Ge.482)

Example 11

It became a cooling lubricant concentrate by mixing the following Get substances:

70 parts by weight. 30 parts by weight

100 parts by weight.

Amine salt of an aromatic sulfonamidocarboxylic acid (corrosion protection agent)

Polymer dispersion according to Example 3 (40 wt Solid) (lubricant)

Water with 20

The concentrate contains 6% by weight of polymer and is in water

at 20

i.e. clearly soluble.

For the test "the Schmiexwert" was the concentrate in the ratio Diluted 1: 9 with water and diluted with a 3 »5 aqueous Corrosion detergent solution alone compared. That Corrosion behavior was determined according to the Ilerbert test on aqueous Solutions (1:50 or 1: 100) of lubricant concentrate or Corrosion inhibitor determined only. Experiment a) = lubricant combination, Experiment b) = corrosion protection agent alone. Test conditions as in Tables 1 and 2.

attempt Special area
Pressing
(ileichert scales) *)
Corrosion protection '
in water 1: 100 transparency 10 joige
dilution a)
b) 295 kg / cm ²
90 kg / cm ² 1:50 1/1
0/0 concentrate clear
clear 0/0
0/0 clear

Herbert test according to "IP standards for petroleum and its products No. 125 ". In this test, steel chips soaked with the test solution are placed in small heaps on a plate made of cast steel. After 24 hours you can judge the any rust formation that has occurred according to numerical values, where 0 means no corrosion and 6 means severely attacked, in each case divided into corrosion of the plate (number before the slash) and corrosion of the chips (number after the slash).

409843/0554

Q -

Hoe 73 / F 801 (Ge 482)

As can be seen, the addition of latex does not cause any clouding of the cooling lubricant and improves the lubricating effect quite considerably, although it only contains 0.6% by weight of polymer solids.

Example 12

This example shows that the addition of latex improves the lubricating properties without impairing the transparency. In 85 parts by weight. 15 parts by weight of a mineral oil-based drilling oil concentrate with about 135 »chlorine content from the chlorinated paraffin contained, a knock-out gallows polymer dispersion according to Example 3 are incorporated. The cooling lubricant concentrate obtained was tested in 10 ^ strength aqueous dilution compared to the diluted in the same manner without the addition Bohrölkonzentrat and another Boliröl with a chlorine content of 3 »8 $ and a sulfur content of 1, 3 i>.

substance Special area
Pressing
(Reichert-
Scale) *)
Corrosion protection
in water 1: 100 Transparency dilution mixture
Cf. 1
Cf. 2 260
125
185 1:50 0/0
0/0
0/0 concentrate transparent
clear
transparent
clear
milky-cloudy 0/0
0/0
0/0 clear
clear
clear

Herbert test IP 125

409843/0554

- 10 -

Claims (2)

godfather tansprüche . ■ ■■ Use of by. Amine additive water-clear adjustable Polyrnerlatic.es based on acrylate or methacrylate as the fault, he effect-improving additive to aqueous Kühlschiniormittel for metalworking in an amount calculated from the solids content of the latex from 0.01 to 20 wt. -Fo, based on the total weight of the coolant. 2. Water-clear, aqueous cooling lubricants for metalworking, consisting of a mixture of a) known, aqueous cooling lubricants based on emulsions or solutions of mineral oils, soaps, Fats, fatty acid alkanolamine salts, alkanolamine borates, Alkali nitrites, etc., which can also contain corrosion inhibitors, foam inhibitors, bactericides and the like, with b) water-clear adjustable polymer latices based on acrylate or methacrylate, the amount of polymer being from 0.01 to 20% by weight , based on polymer solids and total amount of cooling lubricant. 409843/0514