DE2112781A1 - Defoamer composition and process for its preparation - Google Patents

Description

DR. E. WIEGAND DIPL-ING. W. NIEMANN 2112781

DR. M. KÖHLER DIPL-ING. C GERNHARDT '

MQNCHEN HAMBURG TELEPHONE: 55547 «8000 MÖNCHEN 15," · TELEGRAMS: KARPATENT NUSSBAUMSTRASSE IQ

W.i | O325 / 71

Mobil Oil Corporation, New York, N.Y. (V.St, Aj

Defoaming Agent Composition and Process for their production «

The invention relates to defoaming agent compositions for systems containing water. In particular, the invention relates to defoamer compositions » which comprise a low molecular weight polyethylene very finely dispersed in a suitable carrier.

U.S. Patent 3,336,223 relates to improved means for extending the useful life of an additive lubricating oil, according to US Pat the U, S. patent this is achieved in that one incorporates the additive into a solid thermoplastic polymer and deposits this composition in the PI. Examples of useful polymers are the ethylene-propylene copolymer having a molecular weight in the range of 200,000 to 300,000 and polyisobutylene with a molecular weight in the range of 81,000 to 135 000 *

BATH ORIGINAL

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According to U, S. Patent 3 3 ¹ JO 19 ¹ "the production of a rolling oil is provided" whereby a distillation mineral oil (straight distillate mineral pil) with atactic polypropylene at a temperature in the range from ^ 9 to '93 ⁰ C ( 120 to 200 ° P).

According to the invention is a defoaming composition intended for systems containing water containing a polyethylene with a molecular weight of about 500 to 25,000 dispersed in a carrier therefor, wherein the composition is obtained by heating the support and the polyethylene to a temperature sufficient to cause the polyethylene to dissolve, and cooling the resulting material to such an extent or at such a rate that that a stable dispersion of the polyethylene is produced in the carrier.

To facilitate the application of the composition to aqueous systems, an emulsifying agent, preferably a nonionic, to be present in it if the Carrier is not soluble in water or emulsifiable by itself.

In preparing the composition, the oil or oil and emulsifier are heated to a temperature high enough to dissolve the polyethylene. This temperature can be about 100 to 120 ⁰ C in the range of about 9O ⁰ C to 150 ⁰ C, preferably _1. The polyethylene is then added and the mixture is stirred at the solution temperature until dissolution has occurred. ·

All of the carrier can be added initially. Preferably, however, 20 to 252? of the entire carrier

BATH 10984 1/1665

applied to dissolve the polyethylene during the Rest is added after dissolution. The temperature of the additional support can be the same as the initial one of the materials or it can be the additional Carriers have a lower temperature «In the latter case, the additional carrier serves as a means to achieve the cooling rate in order to prevent the formation of polyethylene particles of undesirable size as discussed below.

It can be seen that the polyethylene is present in the composition in the form of a very fine dispersion. Polyethylene in this state is necessary, as apparently the effectiveness of the composition decreases, the coarser the polyethylene particles are in it.

In addition to the requirement that the polyethylene be in the finely dispersed state, presumably the size of the polyethylene particles in the dispersion must be within a certain range, probably in the range of about 0.1 µm. However, since the particle size is so small, the extraction of the defoaming agent and the measurement of the The size of the polyethylene particles is practically impossible. Without being limited by this theory, however, it is likely that the desired particle size will be in the Thickness area of the liquid film is located in the There is foam, which is acted on properly »

Fülyathylendispersidnen with the desired physically. Properties are obtained by taking the cooling the hot polyethylene solution, which can be used Contains emulsifier at at least one temperature

BATH ORIGINAL

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-H-

regulates at which the polyethylene particles have solidified sufficiently. This will usually be a temperature of at least 60 ^° C. The time within which such cooling must be accomplished varies depending on the type of polyethylene and the carrier used. It has been found, however, that the cooling rate can be too rapid or too slow, producing polyethylene particles in the composition which are ineffective (see Example 1), probably because they are too small or too large in size, respectively.

For the production of compositions which are effective defoaming, the solution is to an extent or at a rate of about 2 to 2O ⁰ C per minute - are preferably per minute cooled from about 3 to 10 ⁰ C. External coolants can be used to bring about this cooling rate. / Or cooling can take place, as indicated earlier, i. E. the majority of the carrier can be added at storage temperature to a solution made from the polyethylene (or the polyethylene plus emulsifier) and a smaller portion of the total carrier required can be added at such a rate that the desired cooling rate results.

From a chemical point of view, the carrier used can vary widely depending on its compatibility with the system on which the defoaming agent composition should be applied vary. In any case, the wearer must have at least a moderate

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Lichkelt compared to polyethylene at the manufacturing temperature and very little or no solubility show at the application temperature. Can be used, for example, hydrocarbons, mineral oils, fatty acids, Fatty acid esters and emulsifiers, among these substances are the naphthenic and paraffinic ■ Mineral oils, rapeseed oil or rapeseed oil, butyl stearate, tall oil, tetraisobutylene, sodium, petroleum sulfonate (sodium petrol sulphonate) and the like included.

The emulsifier used can be of any type. However, it must be compatible with the system to which the defoamer is to be applied. Non-ionic agents are preferred, since they are the least harmful and least sensitive, e.g. means of the following chemical structures

CH ₃ - (CH ₂ ) _11-13 - (OCH ₂ - CH ₂ ) ^ OH (Genapol XO5O) or

• ^C 9 ^H 19 " ^c 6 ^H 2j- (° ^CH 2 - CHg) ₅ OH (Marlophen 85)

As indicated above, the polyethylenes useful in the invention can have molecular weights between have about 500 and 25,000. Copolymer polyethylenes are also useful. The invention is not a particular one Form of polyethylene is limited. However, polyethylene in the form of pellets or spheres is preferred. Obviously, polyethylene can also be used in other forms. The specified preference only results from the fact that pelleted

10 9 8 41/16 8 5

Polyethylene from the standpoint of both ease of handling and ease of dissolution Appropriate is »

The invention is explained in more detail below with the aid of examples, the parts mentioned being based on weight unless otherwise stated.

example 1

Preparation of compositions with different cooling rates _t

188 g of acid-refined naphthenic mineral oil (25 es) at 37.8 ° C (100 ⁰ F) and 10 g of polyethylene A (the properties of which are given in Example 2) were ^{stirred in a * 100 ml glass beaker at HO 0} C until all of the polyethylene was dissolved. A cooling was carried out on three different V irons, each time freshly prepared mixtures were used,

(a) The hot mug was kept quiet at ambient temperature for 2k hours. A cloudy, slightly gel-like oil resulted,

(b) The hot mug was placed in a trough through which tap water quickly ran. Simultaneously the mixture was stirred intensively using a standard laboratory stirrer at 500 rpm » A cel-like oil resulted,

(c) The hot mug was placed in a trough filled with water at 20 ° C and the mixture was stirred smoothly by moving a glass rod along the walls of the mug at about 20 laps per minute until the contents reached a temperature of 25 ^{Had reached 0} C, Ea resulted in a weak gel,

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Only mixture (c) was found "effective as." this is described in Example 9.

Example 2

Manufacture of compositions with rapeseed oil as a carrier and various polyethylenes »

1 * 7 parts of rapeseed oil and 3 parts of polyethylene A, B or C were stirred and ^{heated to 115 0} C, which resulted in clear tongues. The heating was interrupted, the stirring was continued and 50 parts of rapeseed oil at 30 ⁰ C were continuously in poured the beaker within about 5 minutes, whereby a drop in temperature to about 70 ⁰ C was brought about. Stirring was continued until the temperature had dropped ^{to about 30 ° C.} Cloudy, roughly gel-like oils resulted.

A. B. C. - 3,000 2,000 3,500 10 000 0.92 0.92 O ₁ »92 104-108 93 104-106 180 570 ca,

Properties of polyethylenes;

Molecular weight (average)
Density at 20 ° C, g / ml
Melting temperature? C

Viscosity at 140 ^° C. cp

Polyethylene B is a copolymer

Example 3

Preparing a composition with a fatty acid ester as a carrier,

The composition was prepared as in Example 2 with polyethylene A, with rapeseed oil replaced by butyl stearate was replaced. A cloudy, soft gel resulted.

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example k

Preparation of a composition with a carrier __

The composition was made similar to Example 2 with polyethylene A, with rapeseed oil through distilled tall oil was replaced. A very soft gel resulted,

Example 5

Preparation of a composition with a hydrocarbon as a tracer »

The composition was prepared as in Example 2 with polyethylene A, with rapeseed oil replaced by tetraisobutylene was replaced. A soft gel resulted.

Example 6

Preparation of a composition having an anionic emulsifier as a carrier

The composition was prepared as in Example 2 with polyethylene A, Piüböl being replaced by a sodium petroleum sulf onate (sodium petrol sulphonate) of the type used in emulsifiable metal cutting fluids is used. A cloudy, roughly gel-like mixture resulted,

Example 7

Preparation of a composition with a nonionic sr. Emulsifying medium as a carrier ; -

The composition was prepared as in Example 2 with polyethylene A, whereby rapeseed oil was replaced by an emulsifying agent which was produced by condensing 1 mole of lauryl alcohol with 5 moles of ethylene oxide (Genapol XO5O); after heating, the mixture from Olkin remained at 120 ⁰ C, apparently the polyethylene did not dissolve

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completely up. A cloudy oil resulted, which openly visibly contained relatively coarse solid particles.

Example 8

Preparation of a composition comprising mineral oil as a carrier and an emulsifying agent

20 parts of an acid-refined naphthenic mineral oil (25 es) at 37.8 ° C (100 ⁰ P) and 10 parts

CH ₃ - (CH ₂ ) _11-13 - (0CH ₂ - CH ₂ J ₅ OH (Genapol XO5O)

were stirred together in a suitable reactor and ^{heated to HO 0} C by means of an immersion heater, 3 parts of polyethylene A (the properties of which are given in Example 2) were added, and the mixture was ^{stirred at HO 0} C until dissolution had taken place. The heating was interrupted and there were 67 parts of the mineral oil at. added about 15 ⁰ C in a steady stream over a period of 10 to 15 minutes, after which the temperature was .gefallen to about 55 ⁰ C. This corresponds to a per min Äbkühlungsgeschwindigkeit 5.5 to 3.7 ⁰ C. Stirring was then continued until the temperature reached 25 ⁰ C. A very cloudy, cloudy, weakly gel-like oil resulted. This oil had the following properties:

Density at 15 ° C

Flash point

Neutralization number viscosity at 20 ^° C

at 37.8 ⁰ C at 50 ⁰ C

0.91 g / ml C. 190 ° mg / KOH / g t 0.1 CS, approximately 350 it. approximately 75 it" approximately 32

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- ίο -

The oil is easily emulsifiable with water, but the

-in
• Emulsion is / stable, about 6.0 $ of the oil separated after about 30 minutes. The defoaming effectiveness of the oil is described in Examples 9-14.

Example 9 - Evaluation of the products of Examples 1 to 8

The products of Examples 1 to 8 were tested to determine their defoaming effects in the following manner determine;

Mixtures of 95 # of emulsifiable oil and 5 $ of the test products were stirred for 30 min at 50 ⁰ C. 5 parts thereof were mixed with 95 parts of distilled water and tested for defoaming effectiveness.

The foam test was carried out by placing 100 ml of the aqueous liquid to be tested in an 11-glass bottle brought it, closed it with a stopper and shook it vigorously for 15 seconds. The foam heights were measured according to different times. The results are shown in Table I.

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Table I.

Foam tests with emulsions made from mixtures of emulsifiable oil A with de- foaming compositions,

Defoaming composition foam height

in mm after 5 seconds

Emulsifiable oil A without defoaming composition

from example 1 a from example 1 b from example 1 c from example 2 A of Example 2 B of Example 2 C of Example 3 of Example 4 of Example 5 from Example 6 from Example 7 from Example 8 85

85 85

10 12

Traces of foam traces of foam 12

Traces of Foam IiI 20

+ see footnote of Table II.

10 9 8 A1 / 16 6 5

Example 10

Determination of the product of Example 8, incorporated in various emulsifiable oils

Mixtures of 95 $ of the emulsifiable oils which are given in Table II and 5% of the product of Example 8 were 30 min at 5O ⁰ C stirred, 5 parts of it were mixed with 95 parts of hard water (90 ppm) and the foam was as described in Example 9, tested. The results are given in Table II.

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Table II

Foam tests with emulsions produced from mixtures of emulsifiable oils with the product according to Example 8

Foam heights in mm after 5 seconds emulsifiable oil without product
according to the example with product
8 according to example 8 A. 60 2 B. 60 0 C. 42 0 D. 35 8th E. 22nd 0 P. 50 4th G 44 5 H 12th 0

+ A- contains about $ 70 next to naphthenic material

anionic and nonionic emulsifiers. B - contains about 60% naphthenic material besides

anionic and nonionic emulsifiers «C - contains about 75% naphthenic material in addition to

anionic emulsifiers.
D - contains about 8155 naphthenic material in addition to not

ionic emulsifiers.
E - contains about 77i> naphthenic material in addition to anionic emulsifiers and small amounts of

nonionic emulsifiers. P - contains about 73? naphthenic material alongside anionic emulsifiers.

G - contains about 7 ^% naphthenic material and 5JS fatty material in addition to anionic and nonionic

Emulsifiers "
H - contains about 60% naphthenic material and · 20Ji fat material in addition to anionic and nonionic emulsifiers «

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- 11 »-

Example 11

Determination of the product from Example 8 by addition to emulsions. , ,,, ·,.

Foam tests were carried out as described in Example 9 on various samples Emulsions which were prepared in hard water (90 ppm), with and without the addition of the product according to the example The results are given in Table III.

Table III

Foam tests with emulsions after adding the product from Example 8

5% EmuSions of Foam higher after ι in mm , 15Si addition emulsifiable oil without addition 10 min with 0 after after 50 after 10 min 5 see iö 5 see 2 A. 60 8th 12th 7th B. 60: 28 12 · 0 C. * »2 9 0 5 D. 35 2 8th 0 E. 22nd 36 ' 0 2 P. 50 9 2 G 6th

+ See Table II for the definition of the oils.

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Example 12
Evaluation of the product of Example 8 by extended

Stir with air

5% emulsions (90 ppm) of emulsifiable oil B and a mixture of 95 $ emulsifiable Cl B and 5% of the product prepared in hard water as described in Example 8, which had been stirred at 50 ⁰ C währendI / 2Stunde. 5 liters of each emulsion were placed separately in a 20 liter bucket. Air was blown in an amount of 20 liters per minute by means of a glass tube. The following results were obtained:

(a) without product according to Example 8; -

After 1 hour, the foam crawled out of the bucket. When the air introduction was stopped after 2 days, the foam heights were 250 mm after 5 seconds and 5 mm, respectively after 10 min.

(b) With product according to Example 8:

After 1 hour, the foam height was about 100 mm. V ^T is stopped hen the air introduction after 2 days, the foam heights were 20 mm by 5 see or 0 mm after 20 see,

' Example 13

Evaluation of the product according to Example δ lh paraffin waehsemulsionen

Sight tests were carried out in accordance with ASTM D 892 at 2 ¹ I ⁰ C (190 nl emulsion in a 1000 ml glass cylinder, with air being introduced by means of a diffuser stone, 9 × 1 ml per minute). The product according to Example 8 was added to the emulsions in the ^ linder and distributed by gentle stirring. The tests were carried out with freshly prepared mixtures and those that had been ^{stored at 25 °} C. for 10 days. The results are given in Table IV.

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'Table IV 2112781
Paraffin wax etiulsions after
10 min , in ml 1 ml * after-
15 minutes. 200 0 ml - after
20 rain. 400 0 ml after
20 min. Λ:
ASTM foam tests with _Λ Viewing volume 480 . after
H5 min 0 ml after-
j.5 min. 0 ral ^to '
15 minutes. - +
Wax mul-
BjLonen % - addition vo]
Product like
Ex, δ ¹ straight after 130 450 0 rcl after
repeated
slow
Turn around d.
Cylinder A. 0.0 510 0 25th a fresh ο, ι 490 60 A, 10 ^Ta $ ^e 0.1 420 0 A, fresh 0.5 400 500 A, 10. ^Ta S ^e 0.5 300 80 B. 0 | 0 530 30th " fresh
Hy -. -ri 0.3 450 500 B, 10 days 0.3 4oo 80 C. 0.0 540 30th _c fresh 0.3 450 630 C, 10 days °, 3 4oo D. 0.5 690

0.0

with Ο, Ο ^ ΙΓ additional, Silicone emulsion

76Ο

660

^A "

400 r.l after repeated lan3Sa.r-.sn Turn over d, "cylinder

} ^ke% paraffin wax unbleached and about ivasser «

B - contains 55% satchel and about W water.

C - contains about 20 pounds each of unbleached paraffin wax, raw crust wax (crude scale wax) and from silt wax and about 35/5 V / water.

D - contains 5H of unbleached paraffin wax and about 36j £ water,

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example lh

The effectiveness of the product of Example 8 was tested in a glue or adhesive mixture containing 100 parts of urea-formaldehyde glue, 10 parts of wax emulsion D, 23 parts of water and 10 parts of hardening solution (17% ammonium chloride, 20% conc, ammonia solution, 6% % Water). 250 g of the glue mixture were placed in a 600 ml glass beaker (which was filled to a height ^{of 1 1/2 mm).} Air was introduced into the mixture as in the ASTM D 892 foam test, but only for 1 minute and the foam height was measured. The show heights were measured again after gentle stirring (only one round) and after several times gently turning or swiveling the cylinder with 5% of the product according to Example 8, the foam height after the introduction of air after one stirring round and after turning ^ 5 mm was 5 mm or 5 mm. 0 mm. Without addition, the foam heights were ^ 5 mm, 25 mm or 15 mm,

Example 15

Review processing the product of Example 8 in a clear water-soluble chemical coolant for Metal working

Foam tests as described in Example 9 were carried out with 5 igen dilutions of the coolant in distilled V / ater carried out and the foam height measured after 5 seconds,

(a) Without addition: 15 mm foam

(b) with the addition of IJi product gladly, example 8 des

Coolant before dilution} traces of foam

(c) with the addition of 30 mg of product according to Example 8 to 100 ml of the. dilution : Traces of foam

+ contains about 5 ^% water, about 3OJ? pure triethanolamine and about 5% of a water-soluble polyoxyalkylene polyol.

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Example 16

Evaluation of the product according to Example 2 C with a dishwashing liquid

i% product according to Example 2C was 995? mixed with a standard dishwashing liquid (dishwashing detergent). The foam tests were carried out as described in Example 9 with 1 # dilutions of the unchanged liquid and the mixture, and the foam heights were measured after 5 seconds.

Ca) © hne product according to Example 2 C: Bottle was filled with foam.

(b) with product according to Example 2C: 50 mm foam,

1 0 9 8 h 1/1 6 6 B.

Claims (1)

■ '. - 19 - Claims I, defoamer composition for water containing systems, characterized in that they are a polyethylene with a molecular weight of about 500 to 25,000 dispersed in a carrier therefor and by heating the carrier and the polyethylene to a temperature sufficient to cause the polyethylene to dissolve, and cooling the resulting material at a rate sufficient to provide a stable dispersion of the polyethylene to create in the carrier has been made. 2 «Composition according to claim 1, characterized in that it additionally contains an emulsifying agent . 3t composition of claim 1 or 2, characterized ge · denotes that the heating temperature is about 9O ⁰ C to 150 ⁰ C. ^I I. Composition according to one of Claims 1 to 3, characterized in that the heating temperature is ^{approximately 90 to 120 ° C.} 5. Composition according to one of claims 1 to ^ i, characterized in that the cooling rate is about 2 to 20 ° C per nin. 6, "A composition according to any one of claims 1 to 5, characterized in that the rate of cooling to 1O ⁰ C is about 3 minutes each. 7. Composition according to any one of claims 1 to 6, characterized in that the system is an aqueous emulsion system, 8, composition according to any one of claims 1 to 7, 109841/1665 the composition characterized in that / after the polyethylene has been dissolved, it is cooled to a temperature of at least 60 ⁰ C » 9 «Composition according to any one of claims 1 to 8, characterized in that the carrier consisted of a mineral oil, RUBOl ₉ butyl stearate, tall oil or tetraisobutylene 10. Composition according to one of claims 1 to 9 » characterized in that the polyethylene has a molecular structure w ight from 2000. 11, composition according to any one of claims 2 to 10, characterized in that the emulsifier consists of alkyl ethoxylate. 12 «Composition according to claim 11, characterized in that the alkyl ^{ethoxylate has 12 to I 1} J carbon atoms in the alkyl part and 5 ethoxyl groups. 13 »Method of making a defoaming agent composition for systems containing water, characterized in that a mixture of ehes polyethylene With a molecular weight of about 500 to 25 and a carrier heated for it, the polyethylene is heated dissolves in the carrier and then cools the resulting solution at a rate such that a stable Dispersion of polyethylene in the carrier is obtained. I ¹ I. The method according to claim 13, characterized in that the carrier contains an emulsifying agent, 15. The method of claim 13 or iH _t characterized in that the mixture is heated to a temprature from 90 to 120 ⁰ C. Method according to one of Claims 13 to 15, characterized in that the cooling rate is 2 to 2O ⁰ C per minute. 10 9 8 41/1 66 B. 17. The method according to any one of claims 13 to l6 _t, characterized in that the cooling rate is 3 to 10 ⁰ C per min .. 18, A method according to any one of claims 13 to 17, characterized in that the cooling is continued down to a temprature which is not higher than 60 ⁰ C. 109841/1665