DE1284009B - Stabilization and increase of the electrical conductivity of liquid hydrocarbons or their mixtures - Google Patents

Description

1 2

The low electrical conductivity of slight at least one alkyl substituent with 8 or more Hydrocarbons, like gasoline and kerosene, result in carbon atoms.

in practice often to difficulties, since z. B. in the case of the additives used according to the invention

Pumping through narrow pipes and hoses as a result of polymers or mixed polymers is not just one practice the associated friction on the container 5 stabilizing effect, so that the means of walls accumulate electrostatic charges, which the alkylsalicylic acid derived salts achieved increased give rise to explosions. Due to the presence of electrical conductivity, it lasts longer, but one water increases this risk considerably. even has an increase in them in some cases It is observed from the German Auslegeschrift 1050 338.

known that one has the electrical conductivity of io The polymers used as additives Hydrocarbons, halogenated hydrocarbons, preferably a molecular weight between 50,000 and fen and other organic liquids with as little as 1,500,000.

electrical conductivities, which is a dielectric If a mixed polymer is used, then one is

constant under 8 and an average of 12 carbon monomers preferably have an unsaturated aliatome, can be increased by adding 10 ~ ⁷ to 15 phatic carboxylic acid. Readily available commercially 10 ~ ² moles per liter of a salt of a polyvalent acids are acrylic acid and methacrylic acid. It is metal with a molecular weight of over 200 and one, however, also possible to use other compounds as a compound with a molecular weight of over 200 and starting materials, for example «-ethyl, a product value of molecular weight times specific acrylic acid, crotonic acid, isocrotonic acid, tiglic acid, conductivity, measured at 25 ° C in benzene with such an angelic acid, vinyl acetic acid, vinyl propionic acid, concentration of 1 g per liter, of at least 10 ~ ¹⁰ maleic acid and fumaric acid.

dissolves in the organic liquid, this second being the unsaturated organic carboxylic acids

Additional compound can also be a salt, whose directly or indirectly branched or straight-chain Anion and cation, however, of those of the first salt a-monoolefins or with esters of unsaturated must be different. 25 organic carboxylic acids and saturated alcohols

In particular, one or with esters of saturated organic carbon-chromium alkyl salicylate is suitable for this purpose in combination with the calcium acids and unsaturated alcohols copolymer salt a sulfosuccinic acid dialkyl ester. be sated, these esters a saturated ver

However, it has been shown that the conductivity of branched or straight carbon chains with at least hydrocarbon mixtures containing such additional 30 8 carbon atoms,
contain substances, decreases again in the course of time, suitable olefins are preferably obtained by

especially in the presence of water or alkali. Columns of waxy paraffins.
According to the invention, the following mixtures of a freshly refined mineral oil fraction of lower polymeric properties can be used: stearyl methacrylate - than one which has previously been treated with an adsorbent, methacrylic acid; / 5-oxyethyl methacrylate-stearyl like silica gel. A white methacrylate — methacrylic acid; jS-Oxyäthylmethacryschaftliche explanation for these phenomena could lat — Laurylmethacrylat — methacrylic acid; Lauryl cannot be found for the time being. methacrylate — methacrylic acid; Lauryl methacrylate-

Surprisingly, it has now been found that stearyl methacrylate - methacrylic acid; Stearyl meththese disadvantageous phenomena due to the use of acrylate crotonic acid; Stearyl methacrylate — vinyl acetic acid free acid groups or their salts de-acid; Lauryl methacrylate — stearyl methacrylate — containing crops Have polymers repaired. tonsic acid; Lauryl methacrylate - stearyl methacrylate -

Accordingly, the invention relates to the vinyl acetic acid; Stearyl methacrylate-Cetene-1-vinyl turn from a polymer or copolymers acetic acid; Lauryl methacrylate mixtures of tetramite a molecular weight of at least 5000 and not 45 decene, pentadecene, hexadecene, heptadecene and octa more than 2,000,000, which is either one or more decene-methacrylic acid.

free acid groups or their salts from an earth It is also possible to add the acid groups subsequently

to introduce alkali metal or an organic nitrogen base into the polymers or copolymers, as well as saturated, branched or straight side chains by z. B. initially contains compounds with an ester with at least 8 carbon atoms, which produces from 50 or nitrile groups and then wholly or partially saponifies one or more of the following monomers,
derived: The salts of the alkaline earth metals, in particular

a) an unsaturated mono- or dicarboxylic acid, ^so ? ^ f ^particular calcium salts or the above-mentioned

polymeric compounds are used. Also the

b) an ester of a saturated alcohol with a monovalent or polyvalent organic salts ₅₅ unsaturated carboxylic acid, nitrogen bases are suitable for use.

c) an ester of an unsaturated alcohol with a The hydrocarbon mixture contains these new saturated carboxylic acid, polymeric additives preferably in an amount

". _x . , ". . , ",. , from 0.0002 to 0.001 percent by weight.

d) a monoolefm with at least 10 and not _6o

used for quantities in amounts of from 0.00001 to 0.02 percent by weight, that the hydrocarbon stabilizing and increasing the electrical conductivity mixture contains 10 ^-7 to 10 ^-5 gram-atom of the respective speed of liquid hydrocarbons or carbon metal per liter. The beneficial effect of these hydrogen mixtures with a dielectric con- 65 metal salts in relation to the increase in conductivity constant of 8 or below, which can be achieved by the use of salts, ins-salts of a metal with an atomic number special from calcium salts, the Dioctylsulfobernbis 28 and an alkylated salicylic acid with a succinic acid ester can still be improved. The last mentioned

3 4

Salts are also expediently in such amounts of 334 parts by weight with a molecular weight of

used that the hydrocarbon mixture 10 ~ 'polymeric compound of 5000 and one molar

up to 10 ~ ^B gram atom of the metals concerned per ratio of the monomers jS-oxyethyl methacrylate,

Liter contains. Stearyl methacrylate and methacrylic acid of 10: 2: 1.

The invention is of particular relevance to 5 The polymeric compound C has been used in the following

the light petroleum fractions in the boiling range of the way produced:

Petrol and kerosene, for example fuels for 3718 parts by weight of stearyl methacrylate, 2794 Ge carburetor engines and for gas turbines for propulsion by weight lauryl methacrylate, 260 parts by weight Jo-Oxyvon Aircraft. ethyl methacrylate and 103.3 parts by weight of methacrylic

In the examples below, the folioic acid was dissolved in 27,500 parts by weight of benzene.

lowing polymeric compounds used: dissolved. The interpolymerization was thereby

. _o . ,, ... ... directed that the solution is brought to a temperature of

A. Stearyl methacrylate methacrylic acid; ₈₀ o _{C would require 52 parts by weight of} benzoyl peroxide

B. / S-Oxyethyl methacrylate — stearyl methacrylate — was added. A second solution was also made up of methacrylic acid; ₁₅ by adding 312 parts by weight /? - Oxy-

C. the polyethyleneimine salt of the copolymer ethyl methacrylate and 86 parts by weight of methacrylic / 3-oxyethyl methacrylate — lauryl methacrylate— acid to 1592 parts by weight of benzene. 45 minutes after stearyl methacrylate-methacrylic acid; the beginning of the interpolymerization in the first

D. the caldum salt of the copolymer lauryl solution was added to the second solution of the first solution in methacrylate-methacrylic acid ^ao partial amounts. The reaction mixture was

E. Cetene -1- di - η - butyl ester of maleic acid ^{poured into} methanol. The resulting mixed polymer mono-n-butyl ester of maleic acid. was then dissolved in benzene whereupon the solvent was evaporated in vacuo at a temperature

Each of these polymeric compounds is removed in the post-temperature range of ^{0 ° C.} One received on this

standing with the above capital letters contain 6620 parts by weight of a copolymer

draws, and the production of these polymeric compounds with a molecular weight of 100,000 to 500,000 and one

bonds is described, whereby for the preparation of the molar ratio of the monomers stearyl methacrylate

but within the scope of the invention no protection bean lat, lauryl methacrylate, β-oxyethyl methacrylate and

is said. Methacrylic acid of 5: 5: 2: 2.

The polymeric compound A was in the following 30 It was' the polyethyleneimine salt of this mixed

Way made: polymer made. For this purpose were

338 parts by weight of stearyl methacrylate and 17.2 parts by weight of the copolymer in 380 parts by weight of methacrylic acid were dissolved in 1200 parts by weight of benzene, and this solution was dissolved in parts of carbon tetrachloride. A solution of 1.5 parts by weight was used to add 1.5 parts by weight of dodecyl mercaptan to the solution. Polyethyleneimine with a molecular weight of 1,000,000 was added. Then 1.73 parts by weight, determined by the light scattering method, in 67 parts of azoisobutyronitrile were added with stirring, the solution being mixed by parts by weight of water. The solvent was maintained at a temperature of 75 ° C, the reaction mixture was stirred until WO by heating up the mixture was 1 _^3/4 hours. removed to a temperature of 125 ° C. In the solvent still present after cooling to a temperature of 20 ^° C. 40 reaction mixture, the reaction mixture was then poured in 3000 parts by weight into methanol by evaporation in vacuo. The polymeric compound has been removed at a temperature of 75 ⁰ C. The amount deposited from the solvent and then spoiled on the polyethyleneimine salt amounted to the latter by evaporation in vacuo at a 115 parts by weight.

Temperature exempted from 0 ° C. The yield was 45%. The polymeric compound D was obtained in the following

to 318 parts by weight, the molecular weight of the resul- wise produced:

animal copolymers to 100,000 and the molar 254 parts by weight of lauryl methacrylate and 86 Ge ratio the monomers stearyl methacrylate and parts by weight methacrylic acid became a mixed poly-methacrylic acid in the copolymer to 3.6: 1. subjected to merization by heating the solution

The polymeric compound B was contained in the following 50 of both substances in 1300 parts by weight of xylene

Wise made: the duration of 22 hours at 130 ° C, after 1.5 times

338 parts by weight of stearyl methacrylate, 26 parts by weight of di-tert-butyl peroxide have been added

parts jS-oxyethyl methacrylate and 8.6 parts by weight were. The solvent was then removed by distillation

Methacrylic acid was removed in 400 parts by weight of nitro-Heren the reaction mixture in vacuo,

benzene dissolved. After the addition of 40 weight 55 wherein the temperature rose to 15O ⁰ C. The result-

share benzoyl peroxide found the interpolymerization animal copolymers, which have a molecular weight of

at a temperature of 90 ⁰ C instead. 20 parts by weight 90,000 and the monomers lauryl methacrylate and

Benzoyl peroxide was added to methacrylic acid at half hour intervals in a molar ratio of 4: 1

added. 2 hours after containing a total amount, the addition of 0.75% by weight

60 parts by weight of benzoyl peroxide added 60 parts of calcium hydroxide to 15 parts by weight of the

had been, the reaction mixture was cooled to make interpolymers neutral, then in 30 portions

and poured into 1200 parts by weight of methanol. According to parts by weight of xylene and 3 parts by weight of methanol

Removing the methanol layer was dissolved. After refluxing for 1 hour was

desired polymeric compound-containing layer, the greater part of the solvent is distilled off. Of the

into a mixture of 800 parts by weight of methanol and the remainder of the solvent was after filtration

400 parts by weight of benzene poured. As a result, the solution was distilled off in vacuo. One received

the polymer compound. After drying, 15.3 parts by weight of the calcium salt with a

of the product in air gave a yield of calcium content of 1.54 percent by weight.

The polymeric compound E was used in the following Way made:

Ceten-1 and maleic anhydride in xylene in a molar ratio of 1: 1 dissolved were subjected at a temperature of 130 ⁰ C the copolymerization. The latter was initiated by adding di-tert-butyl peroxide in an amount of 0.1 percent by weight, based on the weight of the monomer mixture. The interpolymerization lasted 24 hours. During this, a further amount of 1 percent by weight of di-tert-butyl peroxide was added in partial amounts to the reaction mixture. The resulting mixed polymer of cetene-1 and maleic anhydride, which had a molecular weight of 5000 and contained 1 mole of cetene-1 per mole of maleic anhydride, was partially esterified with n-butyl alcohol. For this purpose, 20 parts by weight of n-butyl alcohol and 1 part by weight of naphthalenesulfonic acid were added to 50 parts by weight of the resulting copolymer dissolved in 100 parts by weight of benzene. The resulting solution was distilled, the water present in the distillate was removed, and the remainder of the distillate was continuously returned to the boiling solution. The liquid was cooled and washed with water after 0.7 parts by weight of water separated out. The volatile constituents were removed from this liquid by evaporation in vacuo. In this way, 68 parts by weight of the polymeric compound E were obtained with a molar ratio of the monomers cetene-1, dibutyl ester of maleic acid and monobutyl ester of maleic acid of 10: 9: 1.

Example I.

A gasoline having an initial boiling point of 80 ⁰ C and a final boiling point of 110 ° C was an amount of a solution in xylene of a chromium-C ^ -Cig-alkyl salicylate, C ₁₄ -C _ls alkyl phenol containing, with a content of 2.10 weight percent of chromium added, that the chromium content in the gasoline to 4 x 10 ^-7 gram atom of chromium per liter is totaled. The electrical conductivity of part of the mixture was measured immediately afterwards. The change in electrical conductivity was then measured again after 7 days and after 35 days.

Another part of the mixture was added 10 percent by volume of water, followed by the whole Mixture was shaken. After settling, the electrical conductivity of the gasoline layer became

ίο definitely. 7 days later the fluids were Shaken again, whereupon the electrical conductivity of the subsequently formed gasoline layer was determined. This procedure was repeated 35 days after the water was first added to the mixture.

Still another part of the solution of the chromium alkyl salicylate in the gasoline was divided into portions, each of the latter being a polymeric compound in an amount of 0.001 percent by weight was added. The polymers used

ao compounds are listed in Table I below. The electrical conductivity of these subsets was measured while the changes in electrical conductivity after 7 and after 35 days were measured.

A fourth part of the solution of the chromium alkyl salicylate in the gasoline was also used in aliquots and each of the latter became a polymeric compound in an amount of 0.001% by weight added using the same polymeric compounds as used in the mentioned in the previous section. After adding 10 percent by volume of water to each portion and shaking the liquid mixture after settling became the electrical conductivity determined by the gasoline layer. Seven days later the liquids were shaken again; afterward the electrical conductivity of the resulting gasoline layer of each portion was determined. This procedure was repeated 35 days after the initial addition of water to each aliquot.

The results obtained are summarized in Table I below.

Table I.

composition

Electrical conductivity in units
(1 unit = 10- «Ohm- ¹ · cm- ¹ )
after 7 days 35 days 0 days 200
150 130
80 400
400 515
850 555
6250 442
430 1000
1440 1180
6350 595
567 4900
6800 4500
5700 3300
3300 5000
8000 5150
7000 1280
1320 940
1900 1200
2500 465
473

Without polymer compound

dry

after shaking with water

With the polymeric compound A

dry

after shaking with water

With the polymeric compound B

dry

after shaking with water

With the polymeric compound C

dry

after shaking with water

With the polymeric compound D

dry

after shaking with water

With the polymeric compound E

dry

after shaking with water

The above table shows that without the addition of a polymeric compound of the invention, the electrical conductivity of a gas, wherein 4 × 10 ^-7 gram atom of chromium in the form of Cm ^- were added Om-C ₁₄ -C ₁₈ -alkylsalicylat decreases after some time . This decrease is even more pronounced when the gasoline comes in contact with water rather than being kept dry. However, this decrease is counteracted by the addition of a polymeric compound according to the invention. In many cases an increase in electrical conductivity can even be observed in relation to time. This increase is even greater when the gasoline comes into contact with water with the addition of chromium alkyl salicylate and polymeric compounds according to the invention. It should be noted here that the polymeric compounds C and D cause an immediate increase in the electrical conductivity of the gasoline containing the chromium alkyl salicylate. When the aliquots of gasoline to which 4 x 10 ~ ⁷ gram atoms of chromium in the form of chromium C ₁₄ -C ₁₈ alkyl salicylate and the polymeric compounds A, B, C, D and E were each added in an amount of 0.001 percent by weight , with 10 percent by volume of a 0.5 _^0/0 by weight (wt.) sodium hydroxide solution instead of 10 percent by volume of water was shaken, to give the results summarized in Table II results.

Table II

composition Electrical conductivity in units
(1 unit = 10 "" ohms- ¹ x cm " ¹ )
after
0 days | 7 days I 35 days 6250
6350
5700
7300
1020 9500
4730
4470
6700 With the polymeric compound A
With the polymeric compound B
With the polymeric compound C
With the polymeric compound D
With the polymeric compound E 380
617
3070
1300
410

Table II shows that the contact of the gasoline with the sodium hydroxide solution significantly improves the beneficial effect of a polymeric compound of the invention on the electrical conductivity of the _{gasoline containing a chromium C 14} -C ₁₈ alkyl salicylate.

Example II

To the solution of chromium alkyl salicylate in gasoline as described in Section 1 of Example I was added a solution of the calcium salt of dioctylsulfosuccinic acid containing 2.00 percent by weight calcium in the same gasoline to which the chromium alkyl salicylate had been added, and in that the calcium content of the gasoline amounted in such an amount to 5 x 10 ^-7 gram atom per liter. The electrical conductivity of this mixture was measured.

Part of this mixture was divided into three parts. An amount of 0.001 percent by weight each of the polymeric compounds A, C and D was added to each of the latter, whereupon the electrical conductivity of these partial amounts was determined. A portion of each portion was then intimately mixed in a mixer with 1 percent by volume of water. The electrical conductivity of the gasoline layer was determined after 1 and after 2 days. A second portion of each portion was also intimately mixed in a mixer with 1 percent by volume of an aqueous solution containing 30 percent by weight sodium hydroxide and 5 percent by weight sodium nitrite. The electrical conductivity of the gasoline layer was determined after 1 and after 2 days.
Similar experiments were carried out with another portion of the gasoline prepared as described in the first section of this example, in an amount of 0.0002 percent by weight each of the polymeric compounds A, C and D instead of 0.001 percent by weight. The table below summarizes the results obtained.

Table III

composition

Polymer
Weight percent

dry Electrical conductivity in units
(1 unit = 10- "ohm- ¹ x cm- ¹ )

I after thorough mixing
! with a solution
of NaOH and NaNO ₂

after thorough mixing
with water

after 1 day! after 2 days

after 1 day

after 2 days

Without polymer ..,
With polymer A
With polymer C
With polymer D

With polymer A
With polymer C
With polymer D

0.001
0.001
0.001

0.0002
0.0002
0.0002

720
3300
4900
7800

2900
2600
3850

470
3500
5500
7300

3200
2450
4100

140
1700
2300
3050

2200

990

1870

320
1930
2150
3200

2450
1010
1870

809 639/1528

From this table it can be seen - that the present a polymeric compound of the decrease in the electrical conductivity of gasoline, which a Chromium-Cju-Qg-alkyl salicylate and the calcium salt added to the dioctylsulfosuccinic acid, even if the gasoline contains a aqueous solution of sodium hydroxide + sodium nitrite comes into contact.

Example III

Similar tests as described in Example II were carried out with a gasoline with

an initial boiling point of 80 ° C and a final boiling point of 110 ⁰ C, to which a ChTOm-C ₁₄ -C ₁₈ -alkylsalicylat is added in the stated of Example I in the first section quantity. The polymeric compounds A and C were added to this gasoline in various concentrations, and the electrical conductivity of the resulting mixtures was measured in a dry state. After adding 1 percent by volume of water and shaking the liquid mixture, the electrical conductivity of the gasoline layer was determined again after 1, 2 and 5 days after it had settled. The results are summarized in the table below.

Table IV

composition

Polymer
Weight percent dry

Electrical conductivity in units (1 unit = 10- "Ohm- ¹ · cm- ¹ ) I after 1 day [

II 2 days after 5 days 143 104 350 285 470 450 650 740 1330 1260 610 640 1930 1870 6100 6100 9200 8400

Without polymer.,
With polymer A
With polymer A
With polymer A
With polymer A

With polymer C
With polymer C
With polymer C
With polymer C

0.00002
0.00020
0.00200
0.02000

0.00002
0.00020
0.00200
0.02000 305
260
365
410
740

650
2100
4200
6100

150
320
325
610
1220

550
2300
6500
9500

Example IV

Further experiments were carried out with a gasoline with an initial boiling point of 85 ⁰ C and a final boiling point of 115 ° C. This gasoline was given such an amount of a solution in xylene of a C ₁₄ -C ₁₈ -alkylphenol-containing salt of trivalent iron with C ₁₄ -C ₁₈ -alkylsalicylic acid together with a calcium salt of the dioctyl ester of sulfosuccinic acid with a content of 2.30 percent by weight iron and a content added of 2.00 weight percent calcium, that the iron content and the calcium content in the gasoline to 4 x 10 ^-7 gram atom of iron per liter of gasoline and 5 · 10 ^-7 gram atom of calcium per liter of gasoline is totaled. The electrical conductivity of this gasoline mixture was measured immediately afterwards.

This mixture was then divided into three parts.

No polymeric compound was added to any part. After intimate mixing at 1 percent by volume Water in a mixer became the electrical conductivity of the gasoline layer after 11 days Part determined.

Polymeric compounds B and D were added to the other two parts, each of the polymeric compound in an amount of 10 · 10 ~ * Weight percent, after which each part is mixed with 1 volume percent water in a mixer and the ' electrical conductivity of the gasoline layers was determined after 11 days.

The results summarized in Table V were obtained.

Table V

Gasoline with 4-10 gram atoms of Fe per liter
and 5 x 10- 'gram atom Ca per liter of polymer
Weight percent

Electrical conductivity in units (1 unit = 10- "ohms- ¹ x cm- ¹ )

after thorough mixing

with water after 11 days

dry

Without polymer compound.
With polymeric compound B
With polymeric compound D

10 · 10- ⁴
10 ■ 10- ⁴

720

52 210 460

This table shows that the electrical time is also reduced and that this decrease is due to the tric conductivity of the gasoline mixtures, which are an addition of polymeric compounds according to the invention salt other than the chromium salt of an alkyl salicylic acid is inhibited. Similar results were obtained when using obtained in the presence of water after some formation of a cobalt salt of an alkyl salicylic acid.

Example V

To the same gasoline as used in Example IV, such an amount of a solution in xylene of a Cu-Cns-alkylphenol-containing salt of divalent cobalt with C ₁₄ -C ₁₈ -alkylsalicylic acid with a cobalt content of 3.03 percent by weight was added that the cobalt content in a gasoline on 4 · 10 ~ ⁷

Gram atom of cobalt per liter of gasoline. The electrical conductivity of this gasoline mixture was measured immediately afterwards.

This mixture was then divided into three parts, which were treated in a similar manner as is described in Example IV. The results are summarized in Table VI.

Table VI

Gasoline with 4 x 10 ~ ⁷ gram atoms of cobalt
per liter

Amount of polymer
Weight percent

Electrical conductivity in units (1 unit = 10- "Ohm- ¹ · cm- ¹ )

after
intimate mixing

with water
after 11 days

dry

Without polymer compound.
With polymeric compound B
With polymeric compound D

10 · 10- ⁴
10 · 10- ⁴

13th
15th
85

Claims (3)

Patent claims: 1. Use of a polymer or mixed polymer with a molecular weight of at least 5000 and not more than 2,000,000, which has either one or more free acid groups or their salts from an alkaline earth metal or an organic nitrogen base as well as saturated, contains branched or straight side chains with at least 8 carbon atoms, from one or is derived from several of the following monomers: a) an unsaturated mono- or dicarboxylic acid, b) an ester of a saturated alcohol with an unsaturated carboxylic acid, c) an ester of an unsaturated alcohol with a saturated carboxylic acid, d) an oc-monoolefin with at least 10 and no more than 40 carbon atoms, in amounts of 0.00001 to 0.02 percent by weight to stabilize and increase the electrical Conductivity of liquid hydrocarbons or hydrocarbon mixtures with a dielectric constant of 8 or below, which is a small amount of a salt made from a metal with an atomic number of 22 to 28 and a alkylated salicylic acid having at least one alkyl substituent with 8 or more carbon atoms contain. 2. Use of a mixed polymer according to claim 1, characterized in that the mixed polymer is derived from acrylic acid or methacrylic acid. 3. Use of a mixed polymer according to claim 1 or 2, characterized in that that the mixed polymer is from the lauryl or stearyl ester of acrylic acid or methacrylic acid derives.